Ocean Acidification and Corals

Guest post by Steven Goddard
The BBC ran an article this week titled “Acid oceans ‘need urgent action” based on the premise:

The world’s marine ecosystems risk being severely damaged by ocean acidification unless there are dramatic cuts in CO2 emissions, warn scientists.

This sounds very alarming, so being diligent researchers we should of course check the facts. Ā The ocean currently has a pH of 8.1, which is alkaline not acid. Ā In order to become acid, it would have to drop below 7.0. Ā According toĀ WikipediaBetween 1751 and 1994 surface ocean pH is estimated to have decreased from approximately 8.179 to 8.104.” Ā At that rate, it will take another 3,500 years for the ocean to become evenĀ slightlyĀ acid. Ā One also has to wonder how they measured the pH of the ocean to 4 decimal places in 1751, since the idea of pH wasn’tĀ introduced until 1909.
The BBC article then asserts:

The researchers warn that ocean acidification, which they refer to as “the other CO2 problem”, could make most regions of the ocean inhospitable to coral reefs by 2050, if atmospheric CO2 levels continue to increase.

This does indeed soundĀ alarming, until you consider that coralsĀ becameĀ common in the oceans during theĀ OrdovicianĀ Era – nearly 500 million years ago – whenĀ atmosphericĀ CO2 levels were about 10X greater than they are today. (One might also note in the graph below that there was an ice age during the late Ordovician andĀ earlyĀ Silurian with CO2 levels 10X higher than current levels, and the correlation between CO2 and temperature is essentially nil throughout the Phanerozoic.)

https://i0.wp.com/ff.org/centers/csspp/library/co2weekly/2005-08-18/dioxide_files/image002.gif?w=1110

Perhaps corals are not so tough as they used to be? Ā In 1954, the US detonated the world’s largest nuclear weapon at Bikini Island in the South Pacific. Ā The bomb was equivalent to 30 billion pounds of TNT, vapourised three islands, and raised water temperatures to 55,000 degrees. Ā Yet half a century of rising CO2 later, theĀ corals at Bikini are thriving. Ā Another drop in pH of 0.075 will likely have less impact on the corals than a thermonuclear blast. Ā The corals might even survive a rise in ocean temperatures of half a degree, since they flourished at times when the earth’s temperature was 10C higher than the present.

There seems to be no shortage of theories about how rising CO2 levels will destroy the planet, yet the geological record shows that life flourished for hundreds of millions of years with much higher CO2 levels and temperatures. Ā This is a primary reason why there are so many skeptics in the geological community. Ā At some point the theorists will have to start paying attention to empirical data.
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Neil Crafter
January 31, 2009 9:24 pm

This has always seemed intuitively impossible to acidify the oceans, given how salty they are. How could CO2 possible overcome all that salt? But then nothing seems above the vast powers of this wonder molecule!

Robert S
January 31, 2009 9:27 pm

“The ocean currently has a pH of 8.1, which is alkaline not acid. ”
Acidification is the process of becoming acidic, and based on the fact that ocean pH has dropped, we can certainly say that is the case. Just to be clear, the end result of acidification is not necessarily an acidic ocean (which would be very unlikely).

CJA
January 31, 2009 9:38 pm

“One also has to wonder how they measured the pH of the ocean to 4 decimal places in 1751, since the idea of pH wasnā€™t introduced until 1909.”
It’s observations like this that will continue to make some of us without PhD’s skeptical of the thought process utilized by some of the leading climate scientists. Similarly, when you look at the surfacestations project and realize that the measurement of global surface temperatures has an inherent flaw, it does not make immediate sense to talk about minor temperature changes over the past 30 years–even if the math says its statistically significant.

mccall
January 31, 2009 9:39 pm

I suppose a better term would be “debased” — similar to the science that comes from many alarmists!

Richard Sharpe
January 31, 2009 9:45 pm

The bomb was equivalent to 30 billion pounds of TNT, vapourised three islands, and raised water temperatures to 55,000 degrees.

I suspect that it did not raise the water temperature to 55,000 degrees. That might have been the temperature at the center of the explosion, but I suspect that the water nearby flashed into steam …
Can you clarify?
I am also lead to believe that the current corrals and the ones before the KT event (I believe) were different, one being rugose corals and the other not. I might have the boundary wrong, though.
Perhaps some words should be said to indicate why corals back then are expected to have behaved the same as those of today in the presence of greater levels of carbonic acid or whatever in the seas, or that similar buffering was possible.

Jon
January 31, 2009 9:48 pm

I second “Robert S”. The tone of indignation is misplaced. Acidification is any decline in pH, no matter how alkaline the final result. That said, the terminology “acidification” draws upon the negative public connotations of something being “acidic” and is primarily used in ecological sciences.

David Archibald
January 31, 2009 10:01 pm

The temperature of large bodies of water is limited to 31degrees C due to the rate of evaporation increasing with temperature. When the Earth was warmer, the tropics remained the same, the rest of the planet heated up.

Mikey
January 31, 2009 10:04 pm

Use of the term acidification is just more BS terminology like using the term Climate Change when what you’re really talking about is human-caused global warming. It’s use is designed to insinuate the oceans are acidic. If they’re not it’s just lying agitprop. That’s not science. That’s english. Any school kid can figure that one out. In the long run using these BS terms will eventually be among the alarmists biggest mistakes. They’re allowing the average guy to get a peak at the BS their quote unquote science is based on.

Jon Jewett
January 31, 2009 10:07 pm

Neil,
Salt (NaCl) does not have an effect on maintaining the pH in this case. There may be other chemicals that would help to maintain the pH above 7.0 (i.e. basic, the opposite of acid). The effect of chemicals resisting a change in pH is called ā€œbufferingā€ and it would take someone more knowledgeable to know if sea water is a buffered solution.
CO2 dissolved in water makes a very weak acid called carbonic acid. It is so weak that we can drink it in soda pop. However, it does have an effect that we can see. Over zillions of years, CO2 dissolves in rainwater and that water with the weak acid percolates through limestone deposits. The weak acid slowly dissolves the limestone and creates caves. But it does take zillions of years.
Regards,
Steamboat Jack

Fraizer
January 31, 2009 10:11 pm

I am a reef aquarium enthusiast.
I add CO2 in a calcium reactor to provide free calcium carbonate for the corals.
I can tell you for a fact that my corals have never done so well since I began the regular addition of CO2. I actually have corals propagating to the point that I have to remove them and trade with the local fish store.
OK, this is slightly different than the natural environment, but the idea is to mimic the natural carbon cycle. CO2 is a fundamental building block of the marine ecosystem. Think of it a pumping CO2 into a hothouse for tomatoes.
So I would ask the folks that subscribe to the AGW proposition:
What is the ultimate solubility of an acid gas in an infinitely buffered alkaline solution?

hunter
January 31, 2009 10:20 pm

Robert S and Jon,
One of the most important tools of AGW fear promotion is to wring out of the statistical noise some numerical value indistinguishable from the noise, and then declare that numerical value is an established fact of grave implications.
There is not one shred of evidence that the AGW claim about acidification is true.
And since the oceans are strongly basic, and the alleged change, even if true, is so trivial, the use of the term ‘acidification’ is not one used to describe a process but rather to elicit acceptance of claims about AGW.
Additionally, please feel free to refer to any credible studies at all that show in the laboratory that a change in Ph of .04 in a marine tank of coral will have any effect at all on the coral. In fact a google of coral+Ph+lab yields no listing of any experimental results.
This pattern is true of basically every tenet of AGW dogma.

J.Hansford.
January 31, 2009 10:21 pm

More AGW hype and myth making.

Fraizer
January 31, 2009 10:29 pm

S (21:27:59) :
FYI, the natural ocean pH varies from about 8.1 to about 8.4 depending on a multitude of factors. I try to maintain my reef tank at 8.3 but that varies with temperature and lighting on a diurnal basis.
It is extremely difficult to measure pH IN THE LABORATORY with a precision of better than +/- 0.1.
Make no mistake. Corral reefs are in trouble. Largely from pesticide and fertilizer runoff as well as sewage sludge. CO2 is the least of their problems.

January 31, 2009 10:36 pm

Richard Sharpe (21:45:26) :
” The bomb was equivalent to 30 billion pounds of TNT, vapourised three islands, and raised water temperatures to 55,000 degrees. ”
I suspect that it did not raise the water temperature to 55,000 degrees. That might have been the temperature at the center of the explosion, but I suspect that the water nearby flashed into steam.

As I recall from nuke weapons school, ignition temp for hydrogen fusion is around 100 million degrees, so 55K is very likely the water temp some great distance away, unless the water has dissociated. Nearby, I don’t think you’ll find anything but plasma. šŸ™‚

Mike Bryant
January 31, 2009 10:44 pm

The coral are making a comeback after the tsunami. How is this possible with the acidification of the oceans?
http://www.physorg.com/news149768973.html

January 31, 2009 10:51 pm

To become acidic, the ocean would have to be below pH 7.0. Saying that “acidification” is just the process of moving closer to 7.0 is equivocation. A little word game, like saying you’re being Newyorkized just because you take a couple of steps eastward in Los Angeles. Heck, you haven’t even been Denverized, yet.
pH, by the way, is not an esoteric chemistry concept, it’s just a handy measurement scale, a shorthand, and can be calculated from other measures of acidity.

D. King
January 31, 2009 10:55 pm

Soft-shell lobstersā€¦Yummy!

Glenn
January 31, 2009 11:00 pm

“In order to become acid, it would have to drop below 7.0.”
I agree. The term “acidification” applied to ocean ph was apparently first
applied by global warming advocates. Whoda guessed.
http://en.wikipedia.org/wiki/Ocean_acidification
“Ocean acidification is the name given to the ongoing decrease in the pH of the Earth’s oceans, caused by their uptake of anthropogenic carbon dioxide from the atmosphere.[1]”
http://pangea.stanford.edu/research/Oceans/GES205/Caldeira_Science_Anthropogenic%20Carbon%20and%20ocean%20pH.pdf
“When carbon dioxide dissolves in the ocean it lowers the pH, making the ocean more acidic.”
Scientists, gotta love them. No, the oceans are not acidic, and lowering the ph a small amount will not make the oceans “more acidic”. Great PR, though.
http://www.google.com/search?hl=en&defl=en&q=define:acidic&sa=X&oi=glossary_definition&ct=title
Define acidic:
“being or containing an acid; of a solution having an excess of hydrogen atoms (having a pH of less than 7) ”
http://www.google.com/search?hl=en&q=define%3Amore
Define more:
“More” is the theme from the Italian movie Mondo Cane, from 1962

January 31, 2009 11:03 pm

At some point the theorists will have to start paying attention to empirical data.
You sure? It didn’t stop them from proclaiming unprecedented ice melt even though they find whole villages and 3000 year old tree stumps under the glaciers. I wondered if you would pick up on the bikini island bombs, didn’t bother those ever so delicate corals much at all.

sod
January 31, 2009 11:04 pm

a google scholar search of
coral+Ph+laboratory+experiment gives me 14000 RECENT hits.
http://scholar.google.de/scholar?q=corals+ph+laboratory+experiment&hl=en&lr=&scoring=r&as_ylo=2004

wes george
January 31, 2009 11:07 pm

First they claim an apocalypse is looming due to AGW.
But when self-evident cooling occurs they blur AGW to vague “climate change” Any climate evolution defying total climate stasis is the result of capitalist evil.
Of course, by definition, the climate is always changing and the concept of an optimum climate stasis is an idiotically impossible oxymoron.
Now that more and more people are becoming aware of the dual idiocy of a tautology ā€œclimate changeā€ and its implied oxymoronic corollary of a ā€œstationary climateā€ we are being prepared to move on to the next FUD, the acidification of the oceans.
Remarkably, the dire threats keep shifting, but the boogie man remains the same. And so does the collectivist socio-economic policy solutions.
What’s wrong with this picture?

Glenn
January 31, 2009 11:10 pm

After considering this “acidification” it occured to me to question whether
other factors could be involved rather than increased co2, if indeed that is the case at all. I know little about the subject, but “red tides”, created by the billions of tons of crap we have dumped into the oceans, manufacture domoic acid, which may cause similar reactions in seawater to calcium and such. Perhaps someone with more knowledge of the chemistry might take an interest.

Jon
January 31, 2009 11:12 pm

Hunter,
I’d like to take a moderate approach. Absolutism makes me uncomfortable. e.g., Klaus claiming that there is no global warming–none. That’s a sloppy step too far.
The second part of the post is good, but the bit about ridiculing the conjunction of “acidification” with a basic ocean pH is a step too far.
Skeptics need to have higher standards for themselves and their claims.

Neil Crafter
January 31, 2009 11:13 pm

Steamboat Jack
Thanks for that correction.
The use of the term “acidification” is scary to the average punter. The effect is to make the oceans very slightly less alkaline, but that term does not have the right scare factor for the AGW scarists.
Fraizer
Interesting that your corals are enjoying the extra CO2 boost you are giving them. I see that a number of corals form a symbiotic relationship with a particular family of algae and presumably it is the algae that benefit from the increased CO2.

Steven Goddard
January 31, 2009 11:24 pm

The BBC article was titled “Acid Oceans.” They are not acidic, rather they are alkaline.
The 55,000 degrees number is from the Science Daily article linked to in that paragraph. The radiative heat from even a small fission device (like at Hiroshima) was enough to instantly vaporize people miles away from ground zero. A thermonuclear weapon like at Bikini releases thousands of times more energy.
Why would anyone expect corals to be so much more sensitive to CO2 than in the past? The argument that is often made is that the lower pH from rising CO2 softens the aragonite in shellfish and coral. Yet we know that atmospheric CO2 levels were much higher when corals and many species of shellfish appeared in the oceans. The physical properties of aragonite have not changed.
The onus needs to be on the people making the claims that a few more ppm CO2 will kill the corals – not the other way around.

a jones
January 31, 2009 11:26 pm

May I suggest readers consult co2science.org which has excellent reporting and a good database on this subject.
Kindest Regards

Manfred
January 31, 2009 11:31 pm

The BBC title is ā€œACID oceans ā€˜need urgent actionā€˜ā€.
So the BBC get it wrong, like always, in recent history.

braddles
January 31, 2009 11:47 pm

To a chemist, a pH change of 8.1 to 8.0 would almost always be referred to as neutralization, not acidification. I guess that “Ocean Neutralization” wouldn’t gather as many headlines as “Acidification”.

Alan Wilkinson
January 31, 2009 11:50 pm

As an ex-chemist I confidently assert that acidification means becoming acid, not staying alkaline. It’s misuse in this context is simple propaganda, not science. Apologists for propagandists have a lost cause.
I’ve also seen chemical claptrap spouted in this context by biologists along the lines that acidification caused by higher CO2 levels reduces carbonate ion availability for calcification for shell, coral formation etc. Complete nonsense. There is no way adding CO2 to water ever reduces carbonate ion concentrations.

evanjones
Editor
January 31, 2009 11:52 pm

The 55,000 degrees number is from the Science Daily article linked to in that paragraph. The radiative heat from even a small fission device (like at Hiroshima) was enough to instantly vaporize people miles away from ground zero.
Nah, the Little Boy was a comparative firecracker. Half the people in the city survived. And most who died did not die in the blast, but in the ensuing firestorm. No way people miles away were vaporized. There were people who were burnt utterly at ground zero, leaving only shadows on the pavement–which was not destroyed by the bomb. (An H-bomb leaves no intact pavement.)
There were even conventional bombing raids that killed more people.
Bikini is a whole ‘nother bag of beans, though. There were like a couple dozen tests there (don’t recall whether they were A-bombs or H-bombs, though).

Glenn
January 31, 2009 11:56 pm

“The BBC title is ā€œACID oceans ā€˜need urgent actionā€˜ā€.
So the BBC get it wrong, like always, in recent history.”
Or maybe they are just playing along and turned the title into the joke that was the article. Acidification means to *make* acidic. You’ll notice they report “The researchers warn” and “they refer to”, not that the BBC is warning about ocean acidification.

Glenn
February 1, 2009 12:09 am

Another linked article to the OP:
http://news.bbc.co.uk/2/hi/science/nature/7745714.stm
“They sampled coastal waters off the north-west Pacific coast of the US every half-hour for eight years.
The results, published in the journal PNAS, suggest that earlier climate change models may have underestimated the rate of ocean acidification.”
There has been a problem off the NW Pacific coast for at least the last eight years with “red tides”, or “algal blooms”, which create acid and influence the chemistry of the ocean and sealife in various ways.

February 1, 2009 12:17 am

So they have (questionable) data over 243 years, what about to those years from 1994, i am missing the those 15 years, what did happen in that time?
Accoording to this it will take almost 5 centuries from 1751 to somewhere halfway the 23rd century for the PH to drop from 8.179 to 8.029. The sky is falling it seems? NOT.

Ted Annonson
February 1, 2009 12:34 am

Whenever I read something put out by the AGW crowd, it reminds me of the only thing I remember from my 1944 class in mathematical analysis which was the instructor saying—
Hucksters often take true numbers and facts and present them in such a manner that it creates a false picture of reality. (Not his exact words, but–)
He then gave the following illistration
Three salesmen were late for a convention and had a hard time trying to find a room for the night. Finally at one hotel the clerk said he had one single room for $30.00 and he could have two more beds installed, so each of them would only pay $10.00.(3x$10.00=$30.00 Right?)
Later the clerk started to think that maybe they payed too much for that crowded room, so he gave the bellboy $5.00 to divide among the three.
Since $5.00 is not divisable evenly by three, the bellboy just gave each $1.00 and kept $2.00 for himself. This meant that each salesman only paid $9.00.
($10.00-$1.00=$9.00 Right?) But 3x$9.00=$27.00 plus the $2.00 that the bellboy make $29.00(Right?), So where did the other dollar go?

Andrew McRae
February 1, 2009 12:50 am

Hey there Watters,
I saw this headline in the BBC headlines a few hours ago and was checking it for signs of lunacy. I should have known that WUWT (or allied sites) would have done the analysis for me already.
Well anyway, thought I’d post a link to some related data for discussion. Here’s a NOAA-funded study of ocean pH, comparing observations done in 1991 and 2006.
http://www.marine.usf.edu/PDFs-and-DOCs/publications/Sherwood-AGU2006.pdf
Now, on the one hand, they also report pH has in fact decreased by almost the same amount that was predicted by atmospheric CO2 models.
On the other hand, what I find unscientific about it (aside from it being a poster and not a journal paper) is that it says in Fig 11 at the bottom right corner that they have graphed the “delta-pH signal from anthropogenic CO2”. That is plainly false. They have measured a drop in pH. There is nothing about this study that disproves all alternative influences on pH aside from CO2. Plus there is nothing about this study that tells where the CO2 came from, let alone that it is from human activity.
Personally I think that since CO2 has a higher solubility in warmer water than cooler water, and since the satellite measurements (MMU) of the SST have definitely shown (via e.g. CRU) the surface warmed between 1991 and 2006, this would mean the ocean would have sucked in more CO2 even if atmospheric CO2 concentration had stayed the same between 1991 and 2006. All they’ve done is build a million dollar thermometer – not an AGW fingerprint detective.
If anyone else wants to check it out and give a different opinion on the significance of this result, I would like to hear it.
See ya,
– Andrew McRae.

CodeTech
February 1, 2009 12:57 am

Estimated mass of the oceans: 1.37×10^21 kg
Estimated mass of the atmosphere: 5.1 x 10^18 kg
Written out:
1,370,000,000,000,000,000,000 kg
5,100,000,000,000,000,000 kg
That means there is about 270 times more mass of ocean than atmosphere, and remember the interface between the two is a very very small portion of the two. Gigatons of CO2 exchange between the two on a regular basis:
Unfortunately, it is difficult to find real numbers because so much of the internet is polluted by AGW agenda articles, but from what I can see there is about a 90 gigaton yearly exchange between ocean and atmosphere. So lets put those three numbers together:
1,370,000,000,000,000,000,000 kg
5,100,000,000,000,000,000 kg
90,000,000,000,000 kg
And adding a fourth number: the amount estimated to be emitted by human activity. Once again, good luck finding any documented or non-hyped value, but I’m seeing it’s about 7 gigatons per year.
1,370,000,000,000,000,000,000 kg
5,100,000,000,000,000,000 kg
90,000,000,000,000 kg
7,000,000,000,000 kg
Simple arithmetic shows that “our” contribution of CO2 to the oceans is approximately 1/195,714,285 the mass of the ocean, or written out that is about one two-hundred-millionth.
I can’t even conceive of anyone seriously worried about this.

Steve Brown
February 1, 2009 1:17 am

Here in England the BBC is now recognised as being nothing more than a Socialist organisation which backs the Labour Government’s socialist agenda whilst being financed by a legally enforceable tax on the general populace (the TV ‘licence’ fee).
Have a look at the newspaper article linked.
http://www.telegraph.co.uk/comment/columnists/christopherbooker/4413474/BBC-abandons-impartiality-on-warming.html

deadwood
February 1, 2009 1:29 am

Someone please correct me if I have this backwards.
As I understand it warming oceans release CO2 because cold sea water holds more in solution.
Since CO2, when dissolved in seawater is an acid (H2CO3 – AKA carbonic acid), would not the ocean become less acidic as the seas warm?

John Edmondson
February 1, 2009 1:33 am

Did Steve Goddard ask the BBC to post his analysis of their article, in the interest of providing a balanced view?
If he did, I think we can guess what the reply was?

Bill D
February 1, 2009 1:46 am

The effect of changes in ocean pH on calcifying organs, such as corals, clams (and other molluscs) and certain plankton is a very active area of scientific experimental research. This research can be accessed in Goggle Scholar. Various key words, such as (ā€œocean acidification and calcifying organismsā€) give thousands of hits (try it!). Maybe 20% of these articles are available to the general public as PDFā€™s but the majority require subscriptions (because many scientific journals are ā€œfor profitā€ and even journals published by scientific societies are sustained by subscriptions).
I have enough expertise in aquatic invertebrate physiology and ecology to readily understand this literature. Although I have not published on the specific topic, I have, in the past few months been a reviewer of two papers on calcium balance in freshwater crustaceans submitted to peer reviewed journals, reflecting my specific expertise (search W.R. DeMott in Goggle scholar).
Freshwater organisms experience a much broader range in pH than marine organisms. Different species occur at lakes of different pHā€™s, for example. However, when we get to lakes of increasingly lower (more acidic) pH (and calcium concentrations), molluscs (snails and bivalves) are among the first to disappear followed by crustaceans and fish. Depending on lake pH we find different species that are adapted to a specific pH range. This has been very helpful for determining which lakes have been acidified by acid rain and which were naturally acidic (search under ā€œfossil diatoms and lake pHā€). Diatoms skeletons in sediment cores of mud allow reconstruction of past lake pH to the nearest 0.1 pH units.
Unfortunately, the rate of acidification of the worldā€™s oceans is about 100X faster than in the past and current rates of CO2 increase will quickly (within the next century) lead to more acidic oceans than have ben experienced in the last 10 million years (see review articles). This means that the coral species that now present will have difficulty surviving. This does not mean that all corals will go extinct. If acidification is not too fast, perhaps adaptations will occur that allow coral reefs to be rebuilt over the next thousands or 10’s of thousands or 100s of thousands of years. However, it is naive to think that the animals that currently occupy the worldā€™s oceans are the same ones that occurred millions of years ago when the worldā€™s atmospheric CO2 was higher and the oceans were more acidic. Animals (including corals) may have difficulty adapting to the rapid acidification (decades and centuries are short-term for evolutionary adaptations). The calcification of marine organisms is very sensitive to pH and does not require acidic (pH < 7.0) conditions to be markedly reduced.
This posting is the understanding of a scientist with a peripheral understanding of the relevant literature. Clearly, if I had the time and motivation to read more of the literature on this topic (say 100 of the top peer reviewed papers) I would be better informed. However, our understanding of the effects of pH change is solidly ground in 1000’s of scientific papers. This literature shows that ocean life is already being effected and will become much more serious in the coming decades, given current levels of human CO2 release. There is no need to readers here to speculate that the recent and ongoing changes in ocean pH are not important. As mentioned in the first line of this post, this is a topic of very intensive, experimental research.

redneck
February 1, 2009 1:53 am

Steven,
I would caution you about comparing modern day corals with corals extant in the Ordivician. The most common Ordivician corals belonged to the orders Rugosa and Tabulata while todays most common corals belong to the order Scleractinia. Sort of an apples and oranges kind of thing. Also the Rugosa and Tabulata became extinct at the end of the Permian whereas the first appearance of the Scleractinia in the fossil record is not until later in the mid-Triassic.
I also wonder where they collect the samples to measure the ocean’s pH. Do they take samples from near surface which are likely to have slightly lower pHs due to contamination from rainfall. Or do they take samples from deeper water.
It is my opinion that if they want to find out if the ocean is becoming less alkaline or more acidic they should be monitoring changes in depth of the lysocline and CCD (Carbonate Compensation Depth). The lysocline occurs where dissolution of CaCO3 increases significantly due to higher pressures and lower temperatures. The CCD is the depth at which the rate of dissolution of CaCO3 exceeds the rate of supply of calcium carbonate from calcareous pelagic organisms like foraminifera. Below the depth of the CCD no CaCO3 is present on the ocean floors. According to the Glossary of Geology the CCD in the Pacific Ocean occurs between 4000 and 5000m and in the Atlantic Ocean it is somewhat shallower. It also occurs at shallower depths in high latitudes than it does in tropical latitudes.

HasItBeen4YearsYet?
February 1, 2009 2:02 am

THEIR pH VALUE SEEMS TO BE VERY HIGH
Here’s a copy of a paper from 1988 where they are developing the technique, and they get very different number, with decreasing numbers as depth increases.
To say that the whole ocean has to have the same pH, regardless of location and depth is less than honest. But, hey, it’s the BBC, after all.

Demesure
February 1, 2009 2:09 am

To have 55 000 degree temperatures for water, you must have impossibly high pressures, which is of course impossible in an open container (the ocean), except for some cubic meters of water.
This kind of numbers is exagerated and sensationalistic.

King of Cool
February 1, 2009 2:14 am

More than 150 top marine researchers have voiced their concerns through the “Monaco Declaration”, which warns that changes in acidity are accelerating.
So what are the noticeable effects of this?
The oceans are not a static laboratory experiment. They are evolving parts of a constantly changing planet teeming with living species and bacteria.
Over 3500 delegates also attended the 11th International Coral Reef Symposium in Florida in July 2008. Sure, they identified acidification as a factor. But CO2 has been around in various quantities in the 500 million year evolvement of coral reefs which have survived remarkably well over this period.
The reef symposium also recognised that other major issues that would affect the survival of coral reefs were management, overfishing, run-off, development and local community attitudes. These I suspect are the real man made problems that we have to worry about.

February 1, 2009 2:30 am

Fraizer (22:11:28) : I am a reef aquarium enthusiast. I add CO2 in a calcium reactor to provide free calcium carbonate for the corals. I can tell you for a fact that my corals have never done so well since I began the regular addition of CO2.
Fraizer’s got it dead right, and so, unfortunately, has Hunter. I had an excellent discussion with Floor Anthoni about all this; he taught me that since the oceans always carry excess Ca++ ions, the fauna there will always utilize any spare CO2 to build shells and thusly regulate the balance. He also warns that “ocean acidification” stands poised to become the next bogeyman when the Climate Science hot air is punctured. There are local issues with the oceans: the danger is when they get falsely multiplied up.
I do recommend a visit to Dr Floor Anthoni everyone. He’s got what so few people have, a rounded grasp of his topic, hands-on, heart, and good science. Because he understands the subtle nature of ocean dynamics, he’s not in line with hard fundamentalist science headlines. But he can help people grasp the elusive powers of the ocean that we need to grasp but PC-landlubber modellers miss.

February 1, 2009 2:33 am

The fixation of carbon by oceanic animals is responsible for all the limestone in the world, is it not, from the white cliffs of Dover to Mt. Everest. I speculate that taken in total there is a lot more carbon in limestone than in fossil fuels. And a lot more annual fixation of carbon in the oceans than on land. Furthermore, terrestrial biomass is prone to combustion and de-sequesterization of the carbon, whereas in the oceans the calcium carbonate sinks and remains intact for eons.
Unless it is uplifted by plate tectonics, or is thermonuclearized, and even then marine critters replace it shortly thereafter.
Is any of that in the climate models??????

Neven
February 1, 2009 2:47 am

Steven,
Maybe you also could’ve said something about how parts of marine life will cope with a relatively rapid switch in pH? Will they be able to adapt? A lot of marine scientists say they won’t. The argument that corals in the Ordovician era – 500 million years ago – did well with high CO2 levels doesn’t say anything about adaptability of current corals.
And that’s the big question, isn’t it? Will corals etc be able to adapt to a rapid switch in pH? Why isn’t this question addressed at all in your piece?

HasItBeen4YearsYet?
February 1, 2009 2:57 am
RobJM
February 1, 2009 3:42 am

Coral exist in a symbiotic relationship with algae and many algae benefit from extra CO2 as it is potentially limiting in photosynthesis. Therefor it would be reasonable to expect that many coral would benefit from higher CO2 levels. Basic biology 101.

Reference
February 1, 2009 3:47 am

Ocean acidification? See
Are oceans becoming more acidic and is this a threat to marine life?
By Dr J Floor Anthoni

E.M.Smith
Editor
February 1, 2009 3:58 am

I thought this one was the biggest:
http://nuclearweaponarchive.org/Russia/TsarBomba.html
Maybe it wasn’t considered a weapon?
I’m also quite certain that any excess of CO2 in the ocean will rapidly be consumed by plants. It works in greenhouses. Add CO2, get more growth.
One of my major gripes about AGW as a thesis is the way that they almost universally confine biological processes to the production of methane. Life does so much more, including sequester CO2 as coal and oil. The oil via algae in shallow seas…

Glenn Rowe
February 1, 2009 4:09 am


This seems to be the key point in all global warming arguments. The warmists persistently ignore the growing mass of data showing that no matter how much they may wish that CO2 is demolishing the planet, there simply isn’t any evidence for it.
How on earth can we skeptics ever win the day when faced with religious zeal? No matter how much evidence is produced, the environmentalists still seem to have the world’s media and politicians in their pocket. That’s what I find most frustrating about the whole global warming argument. I try not to despair, but I’m at a loss as to how we can make the world sit up and take notice of the evidence. Any thoughts?

Glenn Rowe
February 1, 2009 4:10 am

Sorry, in my previous post I meant to quote the last sentence of the original posting but seem to have pressed the wrong button:
“At some point the theorists will have to start paying attention to empirical data.”

Alan the Brit
February 1, 2009 4:17 am

Fraizer:-)
When I was a young engineer (many moons ago) in 1991-2, I worked on the structural design of a bunch of underground sewage treatment pump houses/chambers in Negril, Jamaica. (Sadly I never got to go there on site due to being made redundant in the recession of that period). They desperately needed the treatment plants to boost tourism & to protect the surrounding coral reefs from degradation from pumping raw untreated sewage into the seas! There was no mention in the report of this coral reef degradation being caused by CO2 in the atmosphere despite that being a regular call from the alarmist camps!
Glenn;-)
I suggest then that the BBC reporting is maybe covering its rear for the possibility of greater cooling, & the world (sorry that should be rich western democracies) realising they’re being conned big time. One Adolf Hitler said in his book ‘the mass of the people are more likely to believe a big lie than a small one!’. If one thinks about it logically this is perfectly true, something that is so huge & incredible must be true! Most people I know over 40 have similar views to myself, perhaps there is a hidden tactic of waiting for all us old fogies over 40 to pop our clogs then the circle will be complete! Millionaire socialist (the very worst kind) Maurice Strong has made his position very clear, the people should be controlled, especially the western democracies. I find this kind of propaganda repulsive, the rich & famous are frequently seen using their popularity & clout to highlight social/environmental issues that require the necessary raising of taxes for everyone, when they are themselves wealthy beyond most peoples needs & wants or even desires, yet they will happily employ the skills of accountants to ensue they pay as little as possible!

Caleb
February 1, 2009 4:19 am

Here is a typical scare-your-socks-off article:
huliq.com/11/69071/modest-co2-cutbacks-may-be-too-little-too-late-coral-reefs
Please notice a small understanding of oceanic bio-chemistry is taken, and extrapolated into the future to create fear. It seems to me the larger picture would show all sorts of other bio-chemical reactions are involved, and that the ocean actually is a robust system which gobbles up CO2 with relish.
Often these articles point to “bleaching” as proof that bad things are occurring. However follow-up shows, in every case I’ve been able to check out, that the bleaching is followed by re-growth of coral.
It is possible, using the web, to visit tour guides who lead scuba tours of reefs in Australia and Indonesia, (and probably the Caribbean as well.) When you talk to such people, (who represent the-man-on-the-street in this case,) they either have seen bleached reefs recover, or have never seen a bleached reef and wonder what all the fuss is about.
As far as I have been able to learn, as a layman, the bleaching is usually caused by a short term addition of nutrients to the water the coral lives in. The nutrients favor plankton and algae which compete with coral. The nutrients come from dust drifting down, and the dust originates from distant places. In one case it was iron-rich dust from the sub-Sahara, caused by drought brought on by the warm phase of the AMO. In another case it was caused by a huge forest fire in Indonesia. As soon as the dust is gone the reef recovers. The reefs also have recovered when damage was due to the tsunami in Indonesia, or by careless fishermen. CO2 has not been a proven factor.
The bio-chemistry of the sea and the photo-chemistry of the upper atmosphere are fascinating subjects, and well worth further study, but people who pretend to be authorities on such subjects need to be a bit more humble. We are barely scratching the surface of the wonders involved.
Having been burned once, and seen my trust in the NASA and NOAH temperatures broken, I am shy of giving such people the benefit of the doubt again, when they produce scary articles. It seems they are bailing out of the temperature-scare, and hopping aboard the acid-oceans-scare.
The motto must be: “If you scare and don’t succeed; scare, scare again.”

February 1, 2009 4:21 am

After been studying the Global Warming movement and the bad science it is based on I have come to realize that the problem is not only limited to Global Warming but it goes much deeper and it now affects most disciplines of natural science.
Most scientists in these disciplines are disciples of what I call Apocalyptic Environmentalism of which the Global Warming Movement is just a part, although an important one.
This religion has its roots in the belief in a very fragile and delicate ecological balance. If this balance is changed, especially if this is caused by human activity, then the system will crash. In other words, if humans continue to industrialize, soon the birds will start falling from the sky, plants will start to dye and the only fish left in the oceans will soon by jellyfish.
Of course in reality the natural world is very adaptable and have adopted through evolution to at times very sudden and rapid change. The only stable thing in nature is change.
So we have today an army of researcher who look for trends, extrapolate these trends, then conclude that they will be catastrophic and then blame humans for the trends. This are then picked up by MSM as part of its tabloidisation. And because people and politicians respond to fears and are scientific ignorant they believe in it.
We are now in a period of cooling and eventually the global warming scare will die. How long that will take I donā€™t know, but when it dies, then I expect that they will push the ocean acidification scare to the max.

E.M.Smith
Editor
February 1, 2009 4:30 am

This link:
http://www.abomb1.org/atmosphr/ustests.html#Castle
lists “Bravo” at 15 Megatons and the largest of the U.S. atmospheric tests.
http://www.abomb1.org/testpix/index.html
has some nice pictures with this one being very nice:
http://www.abomb1.org/images/bakerb.jpg
When you consider that we were popping these puppies off about 6 a year in the 1954 series it does argue for coral being ‘tough stuff’…
Per the water flashing to steam: I think you need to also allow for the intense pressure it was under at the time it was heated. A nuke does kind of raise the pressure right under it when surface detonated. And the rapid arrival of the heating energy as radiation also has the molecules being ‘inertial confined’ during a lot of the heating…
There are manganese nodules and similar mineral deposits all over the ocean floor along with rather massive clay / silt on the bottom (perforated with worm holes). It would take one heck of a lot of ‘acid’ to get past the buffering of the sea bed and all those metal nodules…
http://en.wikipedia.org/wiki/Manganese_nodule
says 500 Billion Tons…
http://en.wikipedia.org/wiki/Manganese(II)_carbonate
says it is used as a fertilizer but has low solubility in water. Used in health foods. Yum! šŸ˜‰

David Porter
February 1, 2009 4:34 am

There have been many references to the bias of the BBC on this thread. Today, Christopher Bookerā€™s column in the Sunday Telegraph, highlights many more.
I realise this is slightly off topic but worth a visit to:
http://www.telegraph.co.uk/comment/columnists/christopherbooker/4413474/BBC-abandons-impartiality-on-warming.html

Alan the Brit
February 1, 2009 4:35 am

Glenn:-)
Forgot to add, when you look at the BBC’s website with its columns on the left hand side denoting topics for reference, when one actually logs on the “Science & Environment” section one notices that the two themes are separated, i.e. Science on the left & Environment on the right (don’t read too much into faction-ism). This suggests to me that the BBC does in fact consider the two as different topics, e.g. Science is science, & Environment is environment, & never should the two be confused, so perhaps they are being impartial after all but people just don’t notice it!

Sean
February 1, 2009 4:44 am

I have a stupid question regarding acidification and the sensitivity of modern coral vs. those 500 million years old. When Mt. Pinatubo blew in the ’90s it released massive amounts of sulfur dioxide in a short period of time. I could see how there could have been localized areas of the ocean where there was actual acidification for a period of time. What happened to the coral reefs in the areas that became more acidic, albeit for a brief period?

Ken Hall
February 1, 2009 4:48 am

King of Cool wrote: “The reef symposium also recognised that other major issues that would affect the survival of coral reefs were management, overfishing, run-off, development and local community attitudes. These I suspect are the real man made problems that we have to worry about.”
————————————-
I agree. However scientists work on grant money and many marine biologists who are specialising in coral research *may* see CO2 alarmism as a way to secure research grants. I suppose that “run off” alarmism is not as effective for securing a grant.
This is what really annoys me about the whole AGW alarmism. In mis-labelling CO2 as a pollutant, they are masking and taking the spotlight away from REAL pollution and environmental vandalism that is much more urgent than tackling a relatively harmless trace gas which is a very useful plant food.

John Philip
February 1, 2009 4:51 am

‘Acidification’ is simply the correct word for a negative shift in pH, as others have pointed out, the corals that became widespread in the Ordovician period, the Rugose and Tabulate, are now extinct- as a brief visit to wiki would have uncovered, so this point is actually evidence against the argument that the current species are robust against acidification.
If the corals are so tough, then why have we lost about a fifth of the reefs since 1950? While initially the main causes were overfishing and pollution, in recent decades it has been mass bleaching events, triggered by warmer waters that present the main threat – Coral bleaching occurs when coral is stressed, the coral expels the colourful symbiotic unicellular algae leaving it with a whitened bleached out appearance. I’ve seen a bleached reef first and hand and it is a sobering sight. Bleaching is not necesarily a death sentence, if the cause of stress is removed then the coral can regenerate quite quickly.
In one single year – 1998 16% of the coral was functionally destroyed, and the overall rate of loss is faster than that of the rainforests. In the future acidification by the CO2 enriched atmosphere may damage considerably the ability of corals to form hard structures.
The 2008 GCRMN annual status summary had
The condition of coral reefs in most regions of the world has progressively declined during the past 3 to 4 decades. Initial damage was largely caused by human activities, such as over- and destructive fishing, inappropriate coastal developments and land-use causing sedimentation and nutrient pollution, and outbreaks of coral and fish diseases and predators such as the crown-of-thorns starfish; all of which might have been exacerbated by human activities. However, since the first recognised mass bleaching event in 1982/83, there has been growing concern about the influence of climate on coral reefs. Unfortunately, these concerns have been vindicated by the increasing frequency and intensity of mass coral bleaching events, particularly in 1998 when approximately 16% of the worldā€™s reefs were functionally destroyed, in 2002 when reefs across the western Pacific were affected, and in 2005 when severe bleaching and coral disease caused up to 50% mortality in many areas of the Caribbean. Caribbean reefs were also subjected to 26 named storms, including 13 hurricanes in 2005. There is also growing recognition that increasing concentrations of atmospheric CO2 threaten the structural integrity of reefs by reducing the rate of calcification in corals.
Coincidentally the four-yearly International Coral Reef Symposium was held this year. The Outcomes communiquĆ© contains the stark sentence ā€˜The canary in the coral-coal mine is dead, but we still have time to save the minersā€™ and the assembled experts felt the need to issue a ‘Call to Action’ : .2008 is a critical time for coral reefs. At the 11th International Coral Reef Symposium held in July, midway in the International Year of the Reef, over 3000 experts from 75 countries assembled to face some hard truths: coral reefs are teetering on the edge of survival and it is our fault. High levels of carbon dioxide in the atmosphere have produced a lethal combination of hotter and less alkaline seawater. Pervasive overfishing, pollution, coastal development, and physical damage further undermine reef health, and consequently, that of the people and ecosystems depending upon them … Only by taking bold and urgent steps now can we hope to ensure that reefs will survive to enrich life on earth, as they have for millions of years before us. By failing to act we risk bequeathing an impoverished ocean to our children and future generations.
For those with a serious interest and a sub to Science here is a literature review, containing this plot of CO2, temp and pH from the Vostok ice cores. And the 2005 Royal Society report on the topic is here. (Large pdf).
JP.

February 1, 2009 4:55 am

Didn’t a British court find that coral bleaching as a result of AGW was an unsupportable claim?

John Egan
February 1, 2009 4:57 am

Here is just one gobbley-gook statement from the Royal Society paper –
“Ocean acidification due to increasing atmospheric carbon dioxide” –
http://royalsociety.org/displaypagedoc.asp?id=13314
used by many as evidence of ocean acidification.
“These additions of CO2 to the deep oceans cause its pH to decrease as the deep waters transit from the North Atlantic to the Pacific Ocean.”
How, exactly, do deep waters transit from the North Atlantic to the Pacific Ocean? I know that deep waters might transit from the SOUTH Atlantic to the Pacific. It is also possible for water to transit from the Arctic Ocean (considered by some to be an arm of the Atlantic); however, the Bering Strait is shallow – so there could be no deep water transit.

E.M.Smith
Editor
February 1, 2009 5:02 am

You know, maybe, given that ‘pee’ breaks down to ammonia, taking a few gazillion tons of fish per year out of the ocean (along with their pee production) might, just maybe, account for some of the measured pH change…
Near Alaska, Mt. Redoubt has punched a hole in it’s glacier and is getting ready to blow… Volcanos heating ice cover… who’d a thunk it…

Bill D
February 1, 2009 5:10 am

Frasier:
Unfortunately, adding CO2 to dissolve limestone is quite different from adding CO2 to oceans over decades, which lowers pH and makes it difficult for calcifying organisms like corals and molluscs to take calcium out of solution. This seems to be just the opposite of the results which you observed in your aquaria with corals. Presumably, if you lowered the pH of your aquarium this would have had a negative effect on your corals. This is what many scientific experiments are showing–that corals are sensitve to small decreases in pH and this results in lower Ca uptake.
To examine this in a scientific experiment, you going to need replicate aquaria and you are going to need to measure and control pH and calcium in solution. You can then measure coral growth and, perhaps, Ca uptake by the corals. If you had 9 aquaria, you could have 3 replicate controls and two levels of pH change with three resplicates of each. You could then compare your results with any number of published scientific studies.
If you study is published, then we could compare your results with those of other studies. To get your paper published you would need to read up on the literature so that your study could be placed in the context of studies already published.
Scientists rely on studies published in scientific journals rather than anecdotes published on blogs. Scientific debates occur in scientific journals. When scientists start a new line of research, this often involves reading a few hundred published articles. This helps provide an understanding of what is known and what is still controversial or unstudied.

Mike Young
February 1, 2009 5:13 am

By the way, what happened to the acid rain scare years ago? Was that “solved” or did we just move on to another more scary scare?

Garacka
February 1, 2009 5:24 am

So the headline should read; “Less Basic Oceans ā€˜Need Urgent Actionā€˜”, in lieu of ā€œAcid Oceans ā€˜Need Urgent Actionā€˜ā€.
Alternatively, “Less Basic Oceans are Fun to Study, but Urgent Government Funding Action is Needed”

David Holliday
February 1, 2009 5:28 am

Anytime I see someone say “it is naive”, “it would be naive” or any other variant of such in a purportedly scientific argument I immediately skip to the next response because I know that person has left the realm of arguing on the basis of facts and has entered into the realm of “common sense”. The history of science is repleat with examples of “common sense” that was not.

Ellie in Belfast
February 1, 2009 5:30 am

People don’t like change. They see it as a threat – always bad. Ecologists are guilty of this too, and we as a species find it all too easy to forget that our brief human lifespan is but a blink of a eye in terms of natural global change (as frequently discussed here!), species’ evolution and population shifts.
After a previous post on this subject I came across a very good presentation (I will try to find it again) on the subject of the decline in corals (Great Barrier Reef region) due to increased temperature, and one thing that struck me was that the future may bring a reverse of the decline, or a population shift as species from other (warmer) areas move in. A future “snapshot” study would conclude that these corals were part of the natural population. Also, once again (cf. CO2) how do we distinguish natural change from human cause and effect? Ecological alarmists always assume change is caused by man and is bad.
Regarding pH measurement:
“One also has to wonder how they measured the pH of the ocean to 4 decimal places in 1751, since the idea of pH wasnā€™t introduced until 1909.”
One thing 18th and 19thC scientists were good at was measurement – detailed, accurate measurement. In fact many were obsessed by accuracy. The term and concept (pH) was only putting a name and number to what was already being measured by wet chemistry. Colour changing indicators of acidity/alkalinity had been known for a long time; some of these have very defined colour change end-points.
Using large volumes and weak acids increases accuracy – under such conditions pH titrations to 2 decimal places requires care but is not difficult. One assumes that four decimal place accuracy comes from a calculated average of many measurements.

tarpon
February 1, 2009 5:44 am

Thanks Steve for the educational posting — The media used to do stuff like this, but has somehow forgotten how, as they stand in line for their PRAVDA credentials and bailouts.
I believe the correct term for loss of coral reefs, at least locally, is silting. Of course, a hurricane went through our area and what wasn’t silted over was ripped out by wave action. Really was spectacular what Andrew did to the place, not only was the reefs hit hard, but so were the shore line and mangroves, scars which still show to this day. I wonder what the cyclone data was like back then … hmmm.
One of the great features of WUWT is science education — And for that Anthony you are to be commended. After talking to recent graduates of the government public schools, science seems to get completely left out of the education curriculum and replaced with ‘paper or plastic’.
A pet peeve — I’ve often wondered how accurate the instrumentation that measured all these fantasy effects was in ancient times. I would bet that proxies are not accurate at all, and man’s instrumentation, well I doubt it worked for anything but basic measurement, much less was accurate. My guess would be instruments of old are only good in a general ‘ballpark data’ sense.

Ellie in Belfast
February 1, 2009 5:55 am

Lucy Skywalker (02:30:38) :
Thanks for the link to Dr Floor Antonini’s website. Facinating.

TJA
February 1, 2009 6:00 am

I don’t doubt that changes in PH will affect the balance of species, what I haven’t seen is any explanation of how they measured PH to 3 digits in the 18th century?

Bill D
February 1, 2009 6:02 am

My understanding of the scientific literature on coral reefs matches well with the comments of John Philip above. If coral reefs were only affected by pollution and overfishing, this would not be such a serious problem, since reefs far from human populations would be largely uneffected. For example, reefs near Florida might be at risk but the Great Barrier Reef of Australia would be relatively safe. Again, unfortunately, coral bleaching and death is occuring far from coastlines with significant local human impact.
Coral bleaching in recent years has mainly been associated with ocean heating events. The optimal temperature for corals is unfortunately, less that 2oC below the lethal temperature. Temperatures too hot cause loss of the symbiotic algae that contributes most of the energy that most corals use. When the bleaching becomes long term, the corals die. Many studies show direct plots between warming events and bleaching events over large expanses of coral reefs.
My readings suggest that the decreases in ocean pH are just becoming important corals and will become a more serious problem over the coming decades. This effect of CO2 on ocean pH is a relatively new finding that was not well known among scientists until recently.

Alan Chappell
February 1, 2009 6:03 am

BBC ? that’s what happens when drug addicts mix Heroin and Cocaine and fantasize, and the British Tax payer accepts this ?( doing a search on Google news it looks like the only British workers (tax payers) are Foreigners.)
Code Tech. (00.57.09)
Thanks for the math, even with a plus minus to the power of 20 it still looks good!

JimB
February 1, 2009 6:09 am

OT:
I had no idea that sea level rise was causing so many problems:
“As sea levels rise and world weather patterns worsen, flooding has become a major cause of rice crop loss. Scientists estimate 4 million tons of rice are lost every year because of flooding. That’s enough rice to feed 30 million people.”
From CNN:
http://www.cnn.com/2009/TECH/science/01/29/waterproof.rice/index.html
Amazing how they manage to insert little snipits like that…
So is it the flooding?…or the sea level rise?…how much of each?
JimB

Garacka
February 1, 2009 6:20 am

Andrew McRae (00:50:11) :
“Personally I think that since CO2 has a higher solubility in warmer water than cooler water, and since the satellite measurements (MMU) of the SST have definitely shown (via e.g. CRU) the surface warmed between 1991 and 2006, this would mean the ocean would have sucked in more CO2 even if atmospheric CO2 concentration had stayed the same between 1991 and 2006. All theyā€™ve done is build a million dollar thermometer – not an AGW fingerprint detective.”
Its the other way around on the CO2 solubility in water.

Steven Goddard
February 1, 2009 6:32 am

Here is a famous picture from Hiroshima of the shadow of a person and ladder burned onto a wall, which was undamaged from the shock wave.
http://history.independence.co.jp/ww2/raid/h02.jpg
It had to have been quite far away from ground zero, and had to have received huge amounts of radiative heat.
My belief is that nuclear proliferation in the Middle East is far more dangerous than a few tens of PPM of extra CO2, but apparently that is not in tune with the current thinking of the best minds in Washington, London and Brussels.

Steven Goddard
February 1, 2009 6:41 am

No doubt man’s activities have had a serious impact on the ocean. Instead of wasting endless amounts of money, time political will and “brainpower” focusing on CO2, why not concentrate on the pollutants and activities which are actually doing the damage? Corals and shellfish thrived in the oceans with CO2 levels much higher than at the present.
One of the first things that Geology students are taught in their freshman year is that the solubility of CO2 in seawater decreases as ocean temperatures rise. It is unfortunate that some climate scientists never learned this, as they might have avoided wasting their time trying to invert the interpretation of ice cores.

February 1, 2009 6:44 am

This is only “Climate Change” marketing, it is not about any scientific reasoning whatsoever. It is just a political issue. Fortunately nature does not follow our wishes. They will not succeed in changing the laws of nature.
Every chemical compound reaches an equilibrium state, say an end state, the one for CO2 is calcium carbonate (chalk, marble,etc.)
For sure, some day, in the future, our grandchildrens, will find AGWĀ“rs bones in a phosphates field….

Steven Goddard
February 1, 2009 6:49 am

Neven,
As I said earlier, the onus is on the people making the claims that a 0.1 drop in pH over a century or so will be catastrophic to corals and shellfish. I don’t know how to construct an argument against arm waving speculation, other than to point out again that CO2 levels were much, much higher in the past – and the oceans were teaming with life.

John Philip
February 1, 2009 6:56 am

Smokey – I guess you have in mind the Dimmock vs ‘Inconvenient Truth’ court case [point 9]. The judge actually found that attribution of bleaching solely to GW was unsupportable. Its particularly hard to understand the judicial thought processes on this one as the movie makes exactly the same point.
I am not sure that a law court is the optimal forum to determine the merit of a scientific argument: apparently the judge agreed: It was essential to appreciate that the hearing before me did not relate to an analysis of the scientific questions

Chris Schoneveld
February 1, 2009 6:57 am

Richard Sharpe (21:45:26) :
“I am also lead to believe that the current corrals and the ones before the KT event (I believe) were different, one being rugose corals and the other not.”
Many of the modern reef-building and non-reefal coral species were also present in the Cretaceous or had similar mineralogy as the Cretaceous corals.

Bill D
February 1, 2009 7:07 am

The losses of coral reefs worldwide over the last 30 years or so are attributed to ā€œcoral bleachingā€ which means that corals lose their algal symbionts and then die. Google Scholar lists over 15,000 hits on the key words ā€œcoral bleachingā€ and the first two articles are available free as PDFā€™s. These articles show that the bleaching events are linked to ā€œwarming events.ā€ That is, high peak ocean surface temperatures. Of course, the corals donā€™t care about the warming events are human-caused or ā€œnatural.ā€ If the ocean temperatures stay the same or continue to warm, most or all of the worldā€™s coral reefs will die off in the current century. If the oceans cool, the coral reefs should be able to recover unless acidification (decline in pH) causes them to die off.
http://scholar.google.com/scholar?q=coral+bleaching&hl=en&lr=&btnG=Search
Anyone interested in debating or discussing the decline in coral reefs should read at least a few of these articles.

Hell_is_like_newark
February 1, 2009 7:17 am

A while back I read an article originally from the NYT about experiments on ocean acidification. The original experiments where done by adding carbonic acid directly to what was basically a large salt water aquarium. Result: Corals started to die.
Some researchers decided to make the experiments a little more like the real world. Instead of adding acid, they bubbled CO2 into the water. Result: Algae growth accelerated which in turn created byproducts that coral needed to grow. The sea water became more acidic, but life blossomed in the aquarium (including the corals).
I can’t recall all the details and haven’t been able to find a copy of the article yet.. :+(

February 1, 2009 7:17 am

John Philip (04:51:14) :
“mass bleaching events, triggered by warmer waters that present the main threat” ……
“these concerns have been vindicated by the increasing frequency and intensity of mass coral bleaching events, particularly in 1998 when approximately 16% of the worldā€™s reefs were functionally destroyed,…”
1998 was the record El Nino year – ie massive warm waters. You aren’t suggesting that event was human caused as well??? I think we can all agree that was a natural event, thus so was that bleaching event.
“Caribbean reefs were also subjected to 26 named storms, including 13 hurricanes in 2005. ”
…. I suggest you read up on Dr. Bill Gray’s work on hurricanes – there is no statistical correlation between temperatures & # of or intensity of tropical disturbances. Also see the work of Nolan & Rappin (2008) which says there should be no correlation – because increasing shear in the warmer atmosphere offsets the increasing potential energy of the water- just as is observed. Here’s a layman’s link to that research:
http://www.sciencedaily.com/releases/2008/08/080812160615.htm
“Pervasive overfishing, pollution, coastal development, and physical damage further undermine reef health”
These are all defensible problems that are caused by mankind – but they have nothing to do with CO2 or acidification. Stick to the arguments that are defensible and you will be better off.
As a society, the use of non-defensible agruments, especially by those who know better, is a huge problem. You can see where this will lead. With time, this whole AGW hypothesis will unspool, but the general public, who doesnt have the time or interest to learn what is going on, will likely throw the baby out with the bath water. In other words, there are legitimate environmental issues that should be a concern (such as overfishing, pollution, etc), but if burned by the AGW scam, the general public will look at ALL environmental science as a scam and dismiss it all, which will be bad for society. If protection of the environment is truly the goal of the AGW camp (and not a socialistic political agenda, as many would suggest), then they need to realize that , in the end, they may achieve the exact opposite of what they are setting out to do. As a citizen that does care about the environment – as I spend most of my spare time recreating outdoors – the whole situation is a very sad state of affairs.

Bill D
February 1, 2009 7:18 am

Mike Young (05:13:05) :
By the way, what happened to the acid rain scare years ago? Was that ā€œsolvedā€ or did we just move on to another more scary scare?
Mike–regulation of the release of SO2 when burning coal has significantly improved the acid rain situation. Many lakes in northern New York, the Canadian shield and Scandanavia are still acidic from human-caused acid rain, but the overall situation is better. Rain fall down wind from coal burning and dense human populations is still more acid than “natural rain” but the situation is improved. Good studies on recovery from acidification come for the Sudbury, Ontaria region, where massive and local acid rain caused by smelting ore was stopped allowing a slow recovery of the lake food chains.

Tom in Florida
February 1, 2009 7:20 am

Neil Crafter (23:13:31) : “The use of the term ā€œacidificationā€ is scary to the average punter. The effect is to make the oceans very slightly less alkaline, but that term does not have the right scare factor for the AGW scarists. ”
You are absolutely correct. While “acidification” may be technically correct, I believe is was a conscious effort to scare the average joe. I believe if you ask most people on the street they will tell you that first thing the word “acid” brings to mind is flesh disolving liquids that kill everything.
I also believe the average joe thinks higher PH means more acidic. This is probably due to usually referring to things as more/less acidic and rarely referring to them as more/less basic; therefore they then make the incorrect conclusion that the words “more acidic” equate to “more PH”.

BraudRP
February 1, 2009 7:22 am

Supposedly before Industrialization the atmospheric CO2 content varied during Glacial periods and Inter-Glacial periods from as low as about 180ppm during Glacial periods and up to 280ppm during Inter-Glacial periods. The difference in atmospheric CO2 levels was supposedly to a large degree caused by the amount of CO2 the world’s oceans could contain under the existing conditions, the so called “out gassing”. So when earth temperature increases, oceans are less able to contain CO2 and CO2 causes more warming, but increased CO2 in the atmosphere increases the CO2 in the oceans… I am having a Vinnie Barbarino moment here! I am confused.

February 1, 2009 7:26 am

I haven’t read all the comments yet and may not have time, but I wanted to suggest that perhaps loss of coral reefs might be due to excess nitrogen and sedimentation, and even disease rather than CO2.
I mean Occam’s Razor and all that.
Mark

February 1, 2009 7:26 am

OK, so some sub-editor at BBC Online turned “relative acidification” into “acid” to save space and increase shock value, not much news there. The comparison with geological history is spurious (actually, somewhat confirmatory to the danger) because we are talking about different species. I can’t fathom any possible relevance to short-term effects of, and recovery from, a nuclear blast. Not much left, then.
This issue isn’t in the same class as the somewhat debatable (at least in scale) CO2->temperature link, which starts from a basic physical premise at the low end but requires theoretical models and large forward feedbacks to reach the wilder predicted catastrophic levels. The loss of corals seems to stem from simple, well-understood chemistry and biology, and most importantly, is actually being observed. Thanks to Bill D and John Philip for explaining this in measured terms.
Sorry, folks, and Anthony in particular, but I find this site – particularly in some of the guest posts – is drifting from what seemed to be a genuine concern for measurement accuracy and lets-check-it-ourselves popular science towards reactive, anti-all-environmentalism point-scoring. If that’s Anthony’s wish (which I seriously doubt, actually), that’s his privilege, of course, but I’m afraid the change may leave some of the former audience behind.

JamesG
February 1, 2009 7:28 am

John Philip
Firstly, acidification is only one way to describe it, neutralization is more correct and reduced alkalinity is yet another way – equally worrying to any ocean researchers. Acidification is simply the scary way – and my discussion with the author of that Wikipedia article (as JG17) proved beyond all doubt that the use of the word acidification was entirely a political decision, not a scientific one. When I requested the addition of the comment in the article about the sea still actually being alkaline – as per the pH scale we all learnt in high school chemistry, one of his return comments was:
“it’s unclear exactly who would feel misled other than someone who hasn’t a basic grasp of chemistry.”
Well clearly the BBC reporter didn’t have that necessary basic grasp of chemistry. And reporters inform the general public. He was quite simply misinformed and it wasn’t by accident but by design. Acid sea, factually incorrect as it is, is design to shock and the word “acidification” led him to incorrectly believe that the sea was acid. It’s pure propaganda.
I’d like to see the study that says bleaching is caused by acidity. Traditionally bleaching is caused by excess alkalinity. So acidity is not necessarily the first thing you might think about wrt bleaching. It could be fertilizer runoff to mention just one rather more likely candidate.
The reference to the Caribbean is good as far as it goes, but they completely fail to mention that the coral in Cuba is utterly pristine – as reported several times in National Geographic, latterly by the late Peter Benchley. Why pristine? Mostly because Castro doesn’t allow fishing boats there, plus some basic environmental protection measures. So the case against CO2 in the Caribbean falls apart completely when you consider Cuba. A mere error of omission? Unlikely because every marine biologist knows about Cuba’s coral, so it is almost certainly another deliberately political misrepresentation for propaganda purposes – likely in order to encourage funding.
So why is it important to be factually correct and precise with respect to the evidence against CO2 or acidification “stress” if the main aim is to get funding to improve things? Well, as others have said, there are very good reasons to worry about the real causes of ocean degradation, and they are usually human in cause too; fishing, runoff etc. Yet how do we begin to stop this pollution of the seas, which is most certainly far more dastardly and imminent than some imaginary “stress” caused by CO2, if those polluters are allowed and even encouraged to shift the blame to CO2 and then continue happily polluting?

Garacka
February 1, 2009 7:28 am

Ted Annonson (00:34:11) on the three salesmen:
1. So the logic error occurs when adding the $2 to the $27, because the $2 is part of the $27. The $2 should be added to the $25 that is in the clerk’s hands. Alternatively, if one asked how much money does each party have at given fixed times and applying the Conservation of Money principle:
a) Before any transactions:
3 salesman $30.00
Clerk …….. $0.00
bellboy…… $0.00
b) After 1st transaction:
3 salesman (now broke) …. $0.00
Clerk ………………………… $30.00
bellboy………………………… $0.00
c) After 2nd transaction:
3 salesman (still broke) …………………………… $0.00
Clerk … (Now 2nd guessing his compassion)… $25.00
bellboy… (Now Rich) …………………………………$5.00
d) After last transaction;
3 salesman (Thinking, what an idiot that Clerk was)…………..$3.00
Clerk … (Now banging his head against the wall) ………………$25.00
bellboy… (2nd guessing giving the salesman any of the $5)…..$2.00
2. In CO2 world, the equivalent is adding 2 bits of CO2 to 27 bits of Air and Ocean (= 7.407…percent), when it’s for all practical purposes already part of it.
3. Miraculously, CodeTech (00:57:09) numbers are in very close agreement with the salesman story. From Code Tech; Anthropogenic CO2 annual emissions are 7/90 = 7.8 percent of the Air + Ocean annual exchange.
4. Since 7.8 percent is very close to 7.407…percent, I have no other option but to conclude that Ted’s 1944 math instructor was leaving a message for us. He was the “1st skeptic” and more than deserving of a Nobel prize. In fact, he’s telling us that the Anthropogenic to Air/Ocean ratio is a universal constant = 2/27. Not more, not less, and that is the number that needs to go in the models.
5. Since I am the 1st to reveal this truth, I claim name ownership. Henceforth it will be known as “Garacka’s Rule”.

Steven Goddard
February 1, 2009 7:34 am

Consider the difference between a petroleum geologist and a climate researcher.
The geologist remotely studies the subsurface sometimes for years, then decides to ask his company to drill a multi-million dollar well. If he is wrong, he may well lose his job and reputation.
On the other hand, it is well understood that some research “scientists” need only come up with an alarming story, and they will get front page coverage on many of the world’s newspapers and in the halls of Congress and Parliament. Journalists and politicians want an alarming story. The truth behind it is secondary or often even unacceptable.
Has Lewis Pugh made it to the North Pole yet?
http://news.bbc.co.uk/2/hi/uk_news/7588329.stm

gary gulrud
February 1, 2009 7:41 am

“I actually have corals propagating to the point that I have to remove them and trade with the local fish store.”
You are a god. I’ve studied everything but can’t keep fish more than a couple months.
Aquarist sites are a great place to learn about the CO2 buffering system in the oceans. Perhaps, a reef aquarium log should be submitted with all papers for publication?

tarpon
February 1, 2009 7:48 am

Thanks for the link Lucy Skywalker, fascinating real science.

February 1, 2009 7:53 am

This is second post related to the initial graph ( as the topic matter is so different to the 1st post). This a geologic perspective on the subject, which I think provides definitive evidence that CO2 “acidification” isn’t a problem.
As a geologist, I find the top plot to be fascinating – especially the CO2 curve. A first order least squares fit to the CO2 curve basically shows that CO2 has generally been decreasing with time. There is a plot I wish I could show you, but I couldn’t find online for the post – the distribution of carbonate rocks with geologic time. As posted by Mike D. (02:33:26) :, carbonate rocks are by far the biggest CO2 sink in the carbon cycle over time, so this is very relevant. As a percentage of all sedimentary rocks, if plotted versus time, the carbonate % of total sediments would look very similar to the CO2 plot – much more carbonate rocks in the distant geological past, much less in recent geologic times. This is important because the vast majority of carbonate rocks are formed through biologic processes – plants & animals precipitating aragonite from sea water. Based on this observation, It would appear that the more CO2 available, the more that the organisms can extract from ocean – thus the bio-systems thrive better with more CO2 in the ocean – that’s what the geologic record says. This is consistent with what Fraizer (22:11:28) : posted relative to his aquarium experiment. It also says that even with the very high CO2 levels of the past -as much as 20x current levels, that the oceans were not sufficiently “acidified” that precipitation of aragonite was a problem.
Extrapolating further, 2 interesting thoughts :
1) Based on the geologic record, lack of CO2 may be the problem, not too much CO2.
2) The other implication is that the ocean carbonate factory is slowly depleting our atmosphere of CO2 over geologic time – putting all the CO2 into storage in carbonate rocks. Think about this long term if it continues- CO2 is plant food. Will we reach some point in the future where plant life is decreased / impossible due to lack of CO2? No plants = no animals = no food = no life. Of course, none of this would be in our lifetime, but it is something to ponder. How ironic ….

Steven Goddard
February 1, 2009 7:54 am

Unpolluted rainwater falling in the ocean has a pH of about 5.2, which is about one thousand times as acidic as seawater. Acid rain has been measured at about one million times as acidic as seawater. Every raindrop that hits the ocean makes it less alkaline.
http://en.wikipedia.org/wiki/Acid_rain
Perhaps Parliament should legislate an end to rainfall in the oceans, to reduce “ocean acidification?”

Matt Dernoga
February 1, 2009 8:00 am

I like how you think you know better than 150 marine researchers sounding an alarm. Lets “wait and see” until the ocean is a deadzone. Brilliant.
“The declaration, supported by Prince Albert II of Monaco, builds on findings from an earlier international summit.
It says pH levels are changing 100 times faster than natural variability.”
100 times faster? nothing out of line there!

February 1, 2009 8:05 am

Chemistry was always my weak link. I have tried reading reams of science review – including the Royal Society report, and just now, Floor Anthoni, and I am still confused!
Warming ocean waters release carbon dioxide and become more acid? Cooling oceans absorb carbon dioxide and…..?
Hence – solar induced 20th century global warming warms the oceans, with great spatial and depth variation, and there is outgassing and rising carbon dioxide levels BUT the current rise in atmospheric carbon dioxide is apparently clearly due to fossil fuels (c-14 already decayed) and not ocean outgassing (c-14 not decayed? but the deep water has been enriched from the sediments which may have long lost their c-14???)
I am more than somewhat confused. And I do recommend Floor Anthoni for his refreshing approach – even if it will take me a month to study and understand!

Brian Macker
February 1, 2009 8:16 am

Oceans have all sorts of buffering chemicals that prevent PH changes, have small relative surface areas to the atmosphere, are large bodies fed with comparatively small quantities of rain water, etc. One would expect that fresh water systems would be more quickly and severely effected by increases in PH caused by CO2. 1) They are fed by rain water in such quantities that it actually cycles the entire body of water. Thus having an enormous effective surface area to the atmosphere via the surface area of the droplets of rain. 2) Have no buffering chemicals like sodium bicarbonate.
Aquarium hobbyists often inject CO2 into their coral reefs and fresh water systems. Aquariums are already stressful environments due to the crowding of fish, high nitrogen levels, fluctuating PH due to buildup of organic acids, etc. One would think corals were so sensitive to changes in C02 causes PH fluctuation that hobbyists wouldn’t inject CO2. This goes double for fresh water setups.

D Johnson
February 1, 2009 8:16 am

Out of curiosity, I consulted my reliable Websters Unabridged Dictionary, which was published in 1989, before the ball got rolling on the “acidification” of the oceans issue. It defines “acidify”, the verb form, and “acidification” the noun form as: “to make or become acid; convert into an acid.”
It’s pretty clear to me that the term became applied to a slight reduction in alkalinity to elicit a fear reaction. Why don’t we say the ocean is becoming less caustic? šŸ˜‰
It’s sad how WIkipedia has been corrupted, and can only be trusted on non-controversial matters.

February 1, 2009 8:25 am

Though, as i said before, this is not about science but just marketing, it is useful to underline that for CO2 to increase its amount in sea water it needs a cooler sea water, then they have to choose between global warming, as they say, as a consequence of CO2 increase in the atmosphere, with warmer seas and less CO2 in the sea water, or colder seas with more dissolved CO2 in it.

Sekerob
February 1, 2009 8:27 am

RobJM, so you know Biology 101? Heard of Liebigā€™s Law of the Minimum?
Algae will take oxygen, the part that is missing in the oceanic dead zones, but they need other nutrients too, so doubt your envisioned scheme has a long lasting life, anywhere in the living world.

February 1, 2009 8:32 am

One last calculation based on the initial numbers presented. I’ll go with the assumption that there is a reasonable proxy for ph back in 1751 & there is a way to estimate it to 4 decimals….
If you assume the ocean PH is in equilibrium with atmospheric CO2 concentrations – which is the hypothesis put forward in the paper, then you can calculate at what concentration of CO2 the oceans ph reaches 7.0 – or neutral – before it goes acidic. It is a simple ratio calculation :
Ocean PH vs Atmospheric CO2
Year CO2 PH
1800 280 8.179
1994 357 8.104
differnces 77 -0.075
target PH 7.0
differnce from current ph -1.104
Ratio 14.72
Ratio * CO2 diff 1133.44
total value 1490.44
So, if in equilibrium, at 1490 ppm atmospheric CO2, the oceans reach a ph of 7.0. Of course, based on my last post & the initial plot, CO2 ratio have been higher in the geologic past. Possible implications:
1) The oceans ph & atmospheric CO2 are not in equilibrium, thus atmospheric CO2 isn’t as important to ocean ph as the hypothesis suggests.
2) There are other buffering mechanisms in the ocean that keep the ph above 7.0, regardless of atmospheric CO2.
3) Even the IPCC doesnt suggest that CO2 concentrations will get to this level – they are around 700 ppm in the year 2100. Reversing the calculation, if in equilibrium (which doesnt seem to be supported based on points 1 &2, + the geological record, but we’ll go with it anyway), the ocean PH would only drop to 7.7699 by the year 2100 (might as well go with the 4 decimal places) – which of course is still a base, not an acid.
4) Back one more time to John Philip (04:51:14) : – which says bleaching events are associated with warming events – such as the 1998 El Nino. We know that CO2 solubility decreases with increasing temperature – so a warming event would decrease the disolved CO2 in the area of warming – so we are having dying / bleaching events in water with LESS CO2 (and in theory higher PH). Again, the data always says more CO2 is better – at least when it comes to coral. The data appears to be not permissive of arguing the opposite.
In the whole “CO2 is bad” arena, the ocean acidification hypothesis is actually easier to conclusively debunk than AGW with only minimal digging into the data. Again back to post 1, this argument is so flimsy that all it really does is undermine the credibility of all environmental science. Enough said.

Steve Keohane
February 1, 2009 8:42 am

I made a comment a few weeks ago about the fallacious use of ‘acidification’. CO2 and its magical effects are just silly. Warm water holds less CO2, so unless there is some other source for acid, the oceans must be cooling to become less alkaline. The equilibrium of dissolved CO2 in the oceans, maxiumum levels, were reached long before we crawled out of the swamps. There is a lot more going on in our world than CO2, it needs a lot less attention than it is getting so we can tackle real problems.

Steven Goddard
February 1, 2009 8:53 am

Paul Clark,
I’m not following your logic at all. Bikini was hit by a series of thermonuclear blasts 50 years ago, and yet the corals are thriving despite an additional 55 years of rising CO2 in the atmosphere. Corals are apparently very resilient and adaptive.
Here are some nice drawings of Ordovician sea life. Not very different from today – with aragonite shells. Aragonite has not changed.
http://www.mcgill.ca/redpath/exhibits/special/ordovician_diorama/
After diving into the crater, Zoe Richards of the ARC Centre of Excellence for Coral Reef Studies and James Cook University says, I didnt know what to expect some kind of moonscape perhaps. But it was incredible, huge matrices of branching Porites coral (up to 8 meters high) had established, creating thriving coral reef habitat. Throughout other parts of the lagoon it was awesome to see coral cover as high as 80 per cent and large tree-like branching coral formations with trunks 30cm thick. It was fascinating Ive never seen corals growing like trees outside of the Marshall Islands. The healthy condition of the coral at Bikini atoll today is proof of their resilience and ability to bounce back from massive disturbances, that is, if the reef is left undisturbed and there are healthy nearby reefs to source the recovery.

Richard Sharpe
February 1, 2009 8:57 am

Jennifer Marohasy points to Craig Idso’s article on coral responses to CO2.
It is worthwhile reading what some real-world investigative research has shown as opposed to a bunch of armchair theorizing.

JamesG
February 1, 2009 9:01 am

Regarding “dead zones” mentioned above. Yes these are scary. They are known to be caused mainly by fertilizer runoff and over-fishing. Some scientists have tried to link it to global warming by some dubious theories. Nobody has yet blamed acidity as far as I know but that’ll be coming. Now you can believe in the CO2 catastrophism which now apparently says (ref Susan Solomon) yes we should cut our CO2 but it’s too late anyway (ok more guesswork and more propaganda) or you can presume that it’s more likely to be nothing to do with CO2 or global warming and that likely it’s just runoff and over-fishing – as we always suspected until the CO2 alarmists came along – and actually do something to prevent it.

Richard Sharpe
February 1, 2009 9:03 am

Jeff L says:

4) Back one more time to John Philip (04:51:14) : – which says bleaching events are associated with warming events – such as the 1998 El Nino. We know that CO2 solubility decreases with increasing temperature – so a warming event would decrease the disolved CO2 in the area of warming – so we are having dying / bleaching events in water with LESS CO2 (and in theory higher PH). Again, the data always says more CO2 is better – at least when it comes to coral. The data appears to be not permissive of arguing the opposite.

Yes. This is one very solid demonstration that alarmist are unwilling to think through the consequences of their claims and that they are solely interested in scaring people for political reasons.
Let me set this out in words of one syllable for you AGWers.
Higher CO2 is supposed to lead to higher temperatures, including ocean temperatures! However, higher water temperatures lead to lower levels of dissolved CO2 and thus higher Ph in the oceans, that is, lower acidification and corals should thrive, by your assumption.
This would seem to be a major fail on the part of the hysterical.

Neven
February 1, 2009 9:04 am

Steven,
“As I said earlier, the onus is on the people making the claims that a 0.1 drop in pH over a century or so will be catastrophic to corals and shellfish.”
But the onus is there. The style and content of your pieces induces me to believe you haven’t been looking for it. Like Bill D said:
“However, our understanding of the effects of pH change is solidly ground in 1000ā€™s of scientific papers. This literature shows that ocean life is already being effected and will become much more serious in the coming decades, given current levels of human CO2 release. There is no need to readers here to speculate that the recent and ongoing changes in ocean pH are not important. As mentioned in the first line of this post, this is a topic of very intensive, experimental research.”
Now the reason I feel induced that you haven’t done a broad research by using Google Scholar for example, is the fact that you talk about levels (ie CO2 levels being higher 500 million years ago and the oceans teeming with life) and not at all about the rate at which these levels are changing. That’s what the whole acidification-story is about, isn’t it?
Here’s a quote from the BBC article with the inaccurate ‘Acid Oceans’-title:
“It says pH levels are changing 100 times faster than natural variability. ”
Now pray tell me, if this is true, how can creatures adapt to changes that are 100 times faster than natural variability? That would be a problem, wouldn’t it? How would marine life have reacted 500 million years ago if pH levels would have changed 100 times faster than natural variability?

Terry
February 1, 2009 9:11 am

Jeff L –
pH is a logarithmic scale, so the math is a little more involved than finding a ratio. At the same time, I agree this is much ado about nothing, and the original article is terrible reporting.

robc
February 1, 2009 9:20 am

off topic,
BBC abandons ‘impartiality’ on warming,
Londoners might have been startled last Monday to see a giant mock-up of a polar bear on an iceberg, floating on the Thames outside the Palace of Westminster. They might not have been so surprised to learn, first, that this was a global warming propaganda stunt and, second, that the television company behind it is part-owned by the BBC.
http://www.telegraph.co.uk/comment/columnists/christopherbooker/4413474/BBC-abandons-impartiality-on-warming.html

Bob Coats
February 1, 2009 9:31 am

Most of these comments are just ignorant bloviating, reflecting a complete lack of understanding of basic geochemistry and oceanography. Go to the literature and do some reading, before you shoot your mouth off! Two good places to start are:
1. Hoegh-Guldberg, et al. 2007. Coral reefs under rapid climate change and ocean acidification. Science 318:1737-1472.
2. De’ath et al. 2009. Declining coral calcification in the Great Barrier Reef. Science 323:116-119.
These papers will lead you other good ones. If you can’t find them for free on line, then get thee to a library (remember what a library is?)

Bill D
February 1, 2009 9:32 am

This is frustrating for what is supposed to be a science blog. Many bloggers are drawing conclusions based on misunderstanding of basic principles of physics, chemistry and biology. Many of you seem to assume that the majority of scientists are either fraudulent or incompetent. However, this is not based on reading the science literature or even an understanding of what can be found in basic undergraduate text books. Perhaps scientist appear to be wrong because it seems implausible that humans can have widespread or global effects on the environment.
Scientific research is a very competitive field and the best way to get one’s manuscript rejected for publication is to drawn conclusions that are not well supported by the data and results of one’s study. It seems arrogant to me to assume that the majority of people doing basic research in environmental sciences are fraudulent or incompetent. Do you assume that medical science, for example is equally unreliable?
Scientists spend their lives looking for holes and weaknesses in the current literature. It makes no sense at all that people who devote their life study to understanding how nature works would overlook very simple (but often erroneous) factors that people with little training in science simply guess might be important or may have been overlooked. If you think that scientists have over looked or misintrepted the importance of some variable, you are going to need to spend a few months reading the scientific literature to find out if that is the case.
As an aside, “acidification” is the routine scientific term for a decrease in
pH. “Neutralization” is more ambigous, since it could mean either a decline from an alkaline pH or an increase from an acidic pH. We could invent a new term, such as “de-alkinization” but we don’t have such a term. Scientists use the term “acidification” because there is no other single word that accurately discribes this process and no one has come up with a better term. Use of the term “acidification” cannot be taken as an effort to exaggerate or dramatize.

jarhead
February 1, 2009 9:33 am

Steven Goddard asked “Has Lewis Pugh made it to the North Pole yet?”
According to Wikipedia … “The expedition coincided with some scientists predicting that the North Pole could be free of sea-ice for the first time this summer[1]; however, Pugh was forced to abandon his planned 745-mile trip about 500 miles from the North Pole due to ice.”
Back on topic, can anyone direct me to a data base of actual ph measurements over time? Thanks in advance for assistance.

Marcus
February 1, 2009 9:43 am

Gah! Acidification means “becoming more acidic” regardless of whether you are above or below pH 7! One could say “the process of the oceans becoming less alkaline” which would also be true, but kind of awkward which is why real scientists don’t use that terminology.
Two examples: One: if I say “today is 2 degrees warmer than yesterday” is this less true if yesterday was -30 degrees C or 80 degrees C? No! I could also say “today is 2 degrees less cold” but again, awkward.
Other example: for the fun of it, I did a search for “alkalinization”: I get hits like the following: “Alkalinization of the urine with potassium citrate to a pH of 6.5 to 7 is recommended”
Huh. But… that’s a pH below 7! This website is using the term “alkalinization” rather than “making urine less acidic” because of fear mongering! They want people to worry that their urine is going to turn into evil dissolving lye!
Look: if you want to argue that corals will survive a more acidic ocean, fine. Your best argument would probably rest on the study by Alina Szmant – look it up. I’d still think you’re wrong, and that acidification is adding stress on top of warming and pollution and overfishing, but I’d be willing to be convinced by further experiments along the lines of Szmant et al. that show that her conclusion is robust across a number of different coral organisms and conditions. (having worked with buffered solutions trying to keep various kinds of cells alive, I was often surprised by the impacts of what seemed like small changes in pH – that log scale can be deceiving sometimes)

Bill D
February 1, 2009 9:43 am

Jeff:
One problem with your analysis is the assumption that a pH of 7 has signficance for aquatic life. Currently living coral species will be long gone before a pH of 7.0 is reached.
Howevery, you need to read research by chemical oceanographers to be sure that your conclusions about debunking ocean acidification are valid. Compare your reasoning with a few dozen articles written by experts in ocean chemistry before you assume that they are wrong. I am not an expert in this field, but I have better trust in people who have published peer reviewed papers on the topic.

Marcus
February 1, 2009 9:56 am

Also, for those of you arguing about CO2 become less soluble in warmer waters:
Basically, Henry’s Law states that the equilibrium concentration of CO2 in the oceans will be proportion to the concentration of CO2 in the atmosphere divided by Henry’s coefficient. The coefficient increases with temperature.
So, if atmospheric CO2 is constant, increasing temperature would mean decreasing CO2 in the oceans.
But atmospheric CO2 has increased by 30%. Henry’s coefficient hasn’t increased nearly that much. So the increasing temperature of the ocean just means that the ocean is a smaller sink that it might have been otherwise, not that it is a source. (those of you who argue about the carbon cycle should also try to understand this reasoning)

Richard Sharpe
February 1, 2009 10:00 am

Bill D asks an interesting question:

Do you assume that medical science, for example is equally unreliable?

H pylori?
Anyhow, please connect the dots for us. So, increasing acidification has been proven to be bad for corals by sound scientific work … all well and good.
Increasing human-produced atmospheric CO2 is supposed to lead to increased atmospheric temperatures, which lead to increased sea-surface temperatures and temperatures of the seas where corals live, which is supposed to do what to the levels of CO2 in the ocean and thus the level of pH of the ocean?
Help me understand what is going on here. I like to understand all the causal chains. Perhaps I have one of the links wrong.

Richard Heg
February 1, 2009 10:01 am

http://www.newscientist.com/article/dn14085-acidic-champagne-sea-nothing-to-celebrate-for-corals-.html
“An exploration of natural “bubble streams” of carbon dioxide in shallow Mediterranean waters off the coast of Italy is the first to document the effects of ocean acidification in a real ocean setting.”

Richard M
February 1, 2009 10:01 am

Has any scientific study of coral impacts been done near underwater volcanoes. It would seem the environment around them would contain higher quantities of CO2 and hence give an idea as to the real world effects.

pablo an ex pat
February 1, 2009 10:03 am

Guys as an old fashioned chemist I must point out that the pH scale is logarithmic. To get the pH to move by 1 point you have to change the acidity or alkalinity by a factor of 10, by two points by a factor of 100 etc etc.
The oceans are naturally buffered by the Carbonate/Bicarbonate reaction. As more CO2 in introduced it forms Carbonic Acid. (H20 + Co2 = H2 CO3) the Carbonic Acid reacts with the Bicarbonate already present to form Calcium Carbonate. The ocean system is vast and the amount of Bicarbonate available to react is also vast, the Ocean pH has therefore a naturally self correcting mechanism making the premise of the BBC article essentially a non issue.
And yes Cold water has a higher ability to absorb CO2 than Warm water. So if the oceans are absorbing more they must be cooling eh ?

HasItBeen4YearsYet?
February 1, 2009 10:05 am

I don’t know why my post on this doesn’t appear above, but here’s the link again, with some additional info…
CO2 measurements in the ocean…
http://www.mgac.nsysu.edu.tw/ctchen/Publications/A/64.pdf
(note – (1) the pH values decrease with ocean depth (2) the pH values are much lower than those given by the BBC, even though they were made earlier than the BBC “report.” [surface pH of 7.916 to 7.945, and at 10 meters pH measured at from 8.183 to 8.184])
Here some of the same authors take measurements at different locations with the same result that pH decreases with ocean depth…
http://www.mgac.nsysu.edu.tw/ctchen/Publications/A/95.pdf
(Note that here the data show surface pH varying from about 8.25 to a little about 8.35, seemingly dependent on location, and that in this case the pH they observe is HIGHER than the BBC’s [8.104 to 8.179])
Conclusion – pH is a lot more variable than the warmers want you to believe, and that being afraid of a drop in some global average (a meaningless concept) by a tiny fraction of that value, and well within a much larger range, is not only not scientific, it’s just plain dumb; the BBC’s information is Bubkas.

Bob Coats
February 1, 2009 10:09 am

Bill D.: Thanks for that comment; well said! Seems that the American Disenlightenment is in full gallop here.

Robert Rust
February 1, 2009 10:10 am

Bill D
Unfortunately, the rate of acidification of the worldā€™s oceans is about 100X faster than in the past… This means that the coral species that now present will have difficulty surviving. … However, it is naive to think that the animals that currently occupy the worldā€™s oceans are the same ones that occurred millions of years ago when the worldā€™s atmospheric CO2 was higher… Animals (including corals) may have difficulty adapting to the rapid acidification …
—-
Fraizer (22:11:28) :
I can tell you for a fact that my corals have never done so well since I began the regular addition of CO2.
———-
When I see a post like this from Bill D AFTER the post from Fraizer – I have to conclude that one’s intuition carries more weight than facts. Maybe I’m naive, but facts carry more weight with me. Do I have that wrong, Bill?

February 1, 2009 10:11 am

Per Strandberg (04:21:10) : “Most scientists in these disciplines are disciples of what I call Apocalyptic Environmentalism of which the Global Warming Movement is just a part, although an important one.
This religion has its roots in the belief in a very fragile and delicate ecological balance. If this balance is changed, especially if this is caused by human activity, then the system will crash.”
Re the fragile and delicate ecological balance, this is what Adrian Wills had to say last week. He is the head of Eden, a new digital TV channel in the UK, which is part owned by BBC Worldwide. “The Earth is a fragile place and we were keen to launch with a message that would draw attention to the uncertain state of our finely balanced environment. Our aim is to reflect one amazing world, with one amazing channel that can address issues like climate change whilst providing an entertaining, informative experience by airing a range of high-end premieres, landmark natural history programmes and first class wildlife documentaries.”
The “message” he is referring to was, of course, the floating of a giant plastic sculpture of a mother polar bear and her cub (stranded on a plastic ice floe) down the Thames last Monday. This will be repeated in cities around the UK, such as Birmingham and Glasgow.
Could the media’s bias, in these matters, be any more evident?

HasItBeen4YearsYet?
February 1, 2009 10:12 am

I said, “the pH values are much lower than those given by the BBC, even though they were made earlier than the BBC ā€œreport.ā€ [surface pH of 7.916 to 7.945, and at 10 meters pH measured at from 8.183 to 8.184])”
Sorry, I just realized that’s confusing.
**the higher values for 10 meters were at a different location from the surface measurements.
**those values at 10 meters were higher in that case than the BBC’s, not lower as MOST of the other data on that site were.

TerryS
February 1, 2009 10:22 am

A couple of questions if anybody can answer them
How much carbonic acid would it take to change the oceans pH by 0.1?
What does that volume translate to in gigatonnes of C02?
Is the relationship between carbonic acid and ocean pH a direct one or are there factors involved that either increase or decrease its impact?

Peter Jones
February 1, 2009 10:25 am

Yes, and this is the real problem with being able to blame all environmental problems on CO2s contribution to global warming. It is that governments have a convenient reason to look away from finding the real source of the problem and the people buying the politicians, i.e., big business, are happy to have AGW as the main focus of our environmental efforts.

pablo an ex pat
February 1, 2009 10:27 am

You’d expect the pH to drop as the depth of the measurement increases. But then only to a point. That’s because as the depth increases the water is colder, cold water can absorb more Co2 which in turn reacts with more of the bicarbonate, which is alkaline, dropping the pH marginally.
Cold water is more dense than warm and so it sinks. I know with fresh water that the maximum density is found at 4 C which is why ice forms top down and not bottom up. Not sure about salt water.
If water didn’t have that endearing quality this would be a very different planet.

February 1, 2009 10:38 am

woodfortrees:

Sorry, folks, and Anthony in particular, but I find this site – particularly in some of the guest posts – is drifting from what seemed to be a genuine concern for measurement accuracy and lets-check-it-ourselves popular science towards reactive, anti-all-environmentalism point-scoring.

OK, let’s look at an empirical, real world experiment, rather than listening to opinions:

Fraizer (22:11:28) :
I am a reef aquarium enthusiast…
I can tell you for a fact that my corals have never done so well since I began the regular addition of CO2. I actually have corals propagating to the point that I have to remove them and trade with the local fish store.

I worked for over 30 years in a large metrology/calibration lab. Prominently displayed on a wall was a sign that said:

ONE TEST IS WORTH A THOUSAND
EXPERT OPINIONS

There are a lot of “expert” opinions here implying that coral bleaching is due to AGW. I prefer to listen to a real expert who tested that hypothesis in his reef aquariums.

Robc
February 1, 2009 10:51 am

1998 Coral Reef Bleaching in Indian Ocean Unprecedented, NOAA Announces
An episode of extremely high ocean temperatures migrated from south to north throughout the Indian Ocean during the first six months of 1998 causing considerable coral reef bleaching in its wake, the National Oceanic and Atmospheric Administration reports.
A somewhat similar episode occurred following the 1987 El Nino in the Indian Ocean; however, in 1988 the extreme sea surface temperature anomalies, toxic to corals, moderated sufficiently as the sun moved into the Northern Hemisphere. In that year, reefs in the Indian Ocean north of the equator were spared heavy bleaching.
In 1998, this has not been the case. Bleaching, earlier projected by NOAA, has been reported from the field on the following reefs: Seychelles; Kenya; Reunion; Mauritius; Somalia; Madagascar; Maldives; Indonesia; Sri Lanka; Gulf of Thailand [Siam]; Andaman Islands; Malaysia; Oman; India; and Cambodia.
This unprecedented round of bleaching in coral reefs throughout the Indian Ocean follows El Nino-related bleaching events during late-1997 and early-1998 both projected by NOAA’s satellite HotSpot charts and documented by reef scientists in Mexico (Pacific), Panama (Pacific); Galapagos; Australia’s Great Barrier Reef; Papua New Guinea; and American Samoa.
http://www.fishingnj.org/artcoral3.htm
Massive coral bleaching in Madagascar
Blue Ventures
October 6, 2006
“Global warming is a major threat to the world’s coral reefs, but there are other more direct threats as well that can be more immediately addressed,” said Harris. “Destructive fishing practices and nutrient runoff from villages and resorts are also killing these incredible underwater systems that provide vital resources for the people of Madagascar.”
http://news.mongabay.com/2006/1006-madagascar.html
No mention of acidification of ocean by either Harris or NOAA, is this another lot of BS.

Steven Goddard
February 1, 2009 10:58 am

“Natural variability” includes things like asteroid impacts, volcanoes, tsunamis, floods, droughts, ice ages, etc. Those who cling to the idea that nature is naturally “stable” are deluding themselves.
A key point of this piece is to point out the gap between the theorists and the observational record. One of my favourite Michael Crichton lines was from Jurassic Park – “life will find a way.” Clearly the corals have recovered exceptionally well at Bikini despite all the “thousands of papers” which predict they should have done otherwise. I have been near a few nuclear blasts, and I can assure you that they produce more rapid changes to the environment than CO2 increasing by 0.00009 concentration.
Good thing no scientists have yet been allowed to dump chemicals in the ocean to stop global warming. Who knows how much damage that will do?
Maybe people can write a few thousand more papers to convince the Bikini corals that they are supposed to be dead?

hunter
February 1, 2009 11:00 am

From Sod to so many other true believers, why can you not get it through your heads?
There is literally no rapid acidification happening.
Like so much else involved with the bizarre-o world of AGW, acidification is as real as alien abductions.
One sure sign of how bad AGW is, is this:
AGW ‘climatologists; keep rewriting non-climate science to ‘prove’ that CO2 and a ‘rapid’ change in _X_ is caused by CO2.
Corals have been under pressure by many human caused and natural factors for many many years. But *now* it is, like the forest scam or the phony Antarctic heating scam, all about AGW.

HasItBeen4YearsYet?
February 1, 2009 11:04 am

Chen-Tung A. chen, is a very prolific investigator. I don’t know enough to critique his work yet, but he’s got lots of data, and his methods do seem ok on superficial reading. Also, he seems to also have milking the AGW funding cow down to an art.
In this paper he has info on pH which also shows it’s variability. (see esp., figs 3 and 10)
http://www.mgac.nsysu.edu.tw/ctchen/Publications/A/86.pdf

Neven
February 1, 2009 11:13 am

I’ve never heard of the expression ‘American Disenlightenment’ before, but it’s the best possible description for remarks such as this one:
“There are a lot of ā€œexpertā€ opinions here implying that coral bleaching is due to AGW. I prefer to listen to a real expert who tested that hypothesis in his reef aquariums.”
The idea that someone rather believes some guy with an aquarium (God knows what he did and if he tells the truth) than thousands of peer-reviewed papers by scientists who spend a life time studying the oceans, makes my stomach churn. Smokey, you kill all the hope I have for humanity.

Richard Sharpe
February 1, 2009 11:14 am

Robert Rust says:

When I see a post like this from Bill D AFTER the post from Fraizer – I have to conclude that oneā€™s intuition carries more weight than facts. Maybe Iā€™m naive, but facts carry more weight with me. Do I have that wrong, Bill?

Unfortunately, we don’t know the state of Fraizer’s aquariums before he started adding CO2. It is an interesting data point, but to make it science would involve …
Of course, those guys who got the Nobel in Medicine for the discovery of H Pylori and their association with peptic ulcers got their start by listening to interesting real-world observations, or so I am lead to believe.

DaveE
February 1, 2009 11:17 am

When I see statements like this, “pH levels are changing 100 times faster than natural variability”, my BS alarms start ringing deafeningly.
What is their metric to decide what is “natural variability”?
It just brings back memories of “unprecedented” temperature rise.
DaveE.

Bill D
February 1, 2009 11:23 am

Richard Sharpe (10:00:02) :
Marcus’ comment about Henry’s law is the simplest way to look at CO2 equilibrium between the atmosphere and water. You can be sure that oceanographers are also considering effects of wind mixing and other factors. As Marcus points out, the effect of the increase in atmospheric CO2 in increasing CO2 in the ocean is much greater than the effect of water warming in reducing CO2 solubility
Scientist doing experiments and obsevations on the effects of pH and temperature on corals donot need to consider why the oceans are warmer, only that in the last 20+ years the increases in peak temperatures are too high for corals. However, if you want make predictions about the future, you need to know whether water temperature will continue to rise and if humans will continue to use large amounts of fossil fuels.
The oceans have been a major sink for carbon over the ages. For example, many studies have looked at how fecal pellets of copepods carry undigested carbon to deep sediments. There are hundreds of studies by oceanographers on how carbon and many other elements are transported from the upper mixed layers of the ocean to deep waters. In general, however, a lot of the carbon dioxide adsorped into the ocean is recycled in the upper layers even after it is taken up in photosynthesis. Deposing of carbon usually requires the transport of particulate matter to deep waters. Most algae sink too slowly to fall into deeper waters before decomposing. Diatoms have higher sinking rates and are therefore an exception. Some planktonic protists also have limestone skeletons and enter the sediments when they die.
Although this is not my field, I am aware of sessions of oceangraphy meetings that considered silica depletion (Si is required by diatoms) to be an important factor in determining the oceans effect as a carbon sink over past millenia and in the present as well. Over the last 20 + years thousands of studies have been published that are increasing our understanding of carbon cycling in the oceans and its potential effect on climate, past, present and future. Modeling studies are only a part of this effort.
The story of H. pilori is a classic in science. Scientists did not believe that this bacterium was an important cause of stomach ulcers until its discoverer published convincing results. When scientist think that they may have a new discovery, they work very hard to collect data and conduct experiments that will be convincing to other scientists. When you make a significant discovery and/or find a new test of an hypothesis, this is a good chance to write a convincing and successful grant proposal.

HasItBeen4YearsYet?
February 1, 2009 11:27 am

HERE’S AN INTERESTING CLAIM…
“The shelf water is now supersaturated with respect to calcite and aragonite, but could become undersaturated with a doubling of the current atmospheric CO2 level. The carbonate deposits on the shelf could then begin to neutralize excess CO2 and become an important excess CO2 sink.”
http://www.mgac.nsysu.edu.tw/ctchen/Publications/A/87.pdf
In other words, increased CO2 will result in better CO2 removal from atmosphere, i.e., it sounds like he’s saying it’s probably self regulating.

littlepeaks
February 1, 2009 11:27 am

I read an article in Chemical and Engineering News, a long time ago, describing the possibility of deep-sea disposal of CO2 — the CO2 under extreme pressure, forms a hydrate, which does not dissolve in the ocean water. I cannot find the article, but this article seems to capture the gist of it:
http://news-service.stanford.edu/news/1999/may12/co2disposal-512.html
(Hope that URL doesn’t wrap).
Didn’t see any mention of worries about changing th ph of sea water.

February 1, 2009 11:30 am

From Per Strandberg:
“After been studying the Global Warming movement and the bad science it is based on I have come to realize that the problem is not only limited to Global Warming but it goes much deeper and it now affects most disciplines of natural science.
Most scientists in these disciplines are disciples of what I call Apocalyptic Environmentalism of which the Global Warming Movement is just a part, although an important one.
This religion has its roots in the belief in a very fragile and delicate ecological balance.”
I submit that this religion is also rooted in the high cost of conducting most modern research in the natural sciences and the fact that getting tenure is tied to publishing research papers. In order to get research money, you have to “tow the party line”. This process filters out many reseachers with different belief systems. This is one of the reasons I got out of science as a career.

Steve Huntwork
February 1, 2009 11:39 am

Smokey:
Having two reef aquariums in my home, I must agree with Fraizer.
A buffer is the combination of an acid with a base, and that is called a salt. When a salt is in solution, the introduction of a very weak acid it neutalized by the buffer.
Last year, someone was debating with me on this same subject, so I had us both perform the exact same experiment.
We each setup two 1 liter test bottles and place 1 cm of Argonite in the bottom of these test containers.
Aquarium salt was then mixed to a specific gravity of 1.023 and placed into our test and control bottles.
To generate CO2, another bottle was created with aquarium tubing attached to its top. Each day, 1 tbs of baking soda and 1 cup of white vinegar was placed into the CO2 generation bottles and the gases were bubbled into the saltwater test bottle.
Each day, prior to the introduction of the CO2, Aquarium pH test strips were used to test the water in each of the test bottles.
For three months, my buddy and I conducted this experiment. He was absolutly convinced the the CO2 would acidify the saltwater.
I knew better!
Was this a perfectly controlled experiment?
No, but it got the point across to my buddy about the effect of a buffer (salt) in the solution.

February 1, 2009 11:40 am

Someone probably already asked, but what are the oceans historical rate of pH change, and how is that determined?

Bruce
February 1, 2009 11:53 am

I think this article implies that Coral is too stupid to evolve. Its kind of like people worrying about people from Bangledesh drowning when the mythical rise in Oceans occur. That too implies that the people from bangledesh who now cope with tides that rise and fall 15 feet are too stupid to deal with a few inches of ocean rise in 100 years.
In reality, the article proves that the BBC are too stupid to evolve and are incapable of dealing with facts and new information.

hunter
February 1, 2009 11:55 am

woodfortrees,
When the weedy invasive underbrush of AGW pseudoscience is cleared out, we can get to the real science of climate. Until then, it is fight and resist and expose the fraud of AGW.

John Philip
February 1, 2009 12:01 pm

There are a lot of ā€œexpertā€ opinions here implying that coral bleaching is due to AGW. I prefer to listen to a real expert who tested that hypothesis in his reef aquariums.
Category Error. The acidification (or de-alkalinisation) is a concern because it will make it harder for calcifying organisms to make hard structures. This requires seawater to be supersaturated with calcium and carbonate ions to ensure that once formed the CaCO3 does not dissolve. Lower pH reduces the carbonate saturation of the seawater, making calcification harder and also weakening any structures that have been formed. Feely et al found that a doubling of CO2 will reduce calcification by between 5-25% depending on species.
Coral Bleaching, on the other hand, in this context, is either a consequence of heat stress, or is made worse by heat stress.
Hypothesis testing is at the core of good science, of course, but you have to test the right hypothesis! It would be interesting to know of the pH if the aquarium was measured; however to test the global warming / bleaching hypothesis an experiment would have to be devised that increased the water temperature gradually to simulate the rise in SSTs over recent decades with occaional spikes of 2-3C to simulate El Nino events. Not an experiment I would recommend to someone who cares about the welfare of their aquarium …

Tim Clark
February 1, 2009 12:19 pm

Bob Coats (09:31:35) :
Most of these comments are just ignorant bloviating, reflecting a complete lack of understanding of basic geochemistry and oceanography. Go to the literature and do some reading, before you shoot your mouth off! Two good places to start are:
1. Hoegh-Guldberg, et al. 2007. Coral reefs under rapid climate change and ocean acidification. Science 318:1737-1472.
Warming and Acidifying Seas
The concentration of carbon dioxide in Earth’s atmosphere now exceeds 380 ppm, which is more than 80 ppm above the maximum values of the past 740,000 years (5, 6), if not 20 million years (7). During the 20th century, increasing [CO2]atm has driven an increase in the global oceans’ average temperature by 0.74Ā°C and sea level by 17 cm, and has depleted seawater carbonate concentrations by 30 Āµmol kgā€“1 seawater and acidity by 0.1 pH unit (8). Approximately 25% (2.2 Pg C yearā€“1) of the CO2 emitted from all anthropogenic sources (9.1 Pg C yearā€“1) currently enters the ocean (9), where it reacts with water to produce carbonic acid. Carbonic acid dissociates to form bicarbonate ions and protons, which in turn react with carbonate ions to produce more bicarbonate ions, reducing the availability of carbonate to biological systems (Fig. 1A). Decreasing carbonate-ion concentrations reduce the rate of calcification of marine organisms such as reef-building corals, ultimately favoring erosion at 200 Āµmol kgā€“1 seawater (7, 10)

Now that selection, from your article, is bloviating. Does anyone here believe the bolded assertion. Do you see the circuitous logic? More carbon leads to more bicarbonate leads to more…. What????? Do you see a chemist in the list of authors (below).
1 Centre for Marine Studies, The University of Queensland, St. Lucia, 4072 Queensland, Australia.
2 Marine Spatial Ecology Laboratory, School of BioSciences, University of Exeter, Prince of Wales Road, Exeter EX4 4PS, UK.
3 AJH Environmental Services, 4900 Auburn Avenue, Suite 201, Bethesda, MD 20814, USA.
4 University of Maine, School of Marine Sciences, Darling Marine Center, Walpole, ME 04573, USA.
5 The Chancellery, University of Queensland, St. Lucia, 4072 Queensland, Australia.
6 Marine Science Institute, University of the Philippines, Diliman, Quezon City, Philippines.
7 Ecology and Evolutionary Biology, E321 Corson Hall, Cornell University, Ithaca, NY 14853, USA.
8 International Network on Water, Environment and Health, United Nations University, 50 Main Street East, Hamilton, Ontario L8N 1E9, Canada.
9 School of Biology, Ridley Building, University of Newcastle, Newcastle upon Tyne, NE17RU, UK.
10 Department of Global Ecology, Carnegie Institution of Washington, 260 Panama Street, Stanford, CA 94305, USA.
11 National Museum of Natural History, Smithsonian Institution, Washington, DC 20013, USA.
12 National Oceanic and Atmospheric Administration, Coral Reef Watch, E/RA31, 1335 East West Highway, Silver Spring, MD 20910ā€“3226, USA.
13 Unidad AcadĆ©mica Puerto Morelos, Instituto de Ciencias del Mar y LimnologĆ­a, Universidad Nacional AutĆ³noma de MĆ©xico, Apdo. Postal 1152, CancĆŗn 77500 QR, MĆ©xico.
14 Wildlife Conservation Society, 2300 Southern Boulevard, Bronx, New York, NY 10460, USA.
15 Resource Management in Asia-Pacific Program, Australian National University, Canberra, 0200 Australia.
16 Institute of Marine Sciences, University of Dar es Salaam, Tanzania.
17 Environment Department, MC5-523, The World Bank, 1818 H Street, NW, Washington, DC20433, USA
Jon Jewett (22:07:22) :
Neil,
Salt (NaCl) does not have an effect on maintaining the pH in this case.
TerryS (10:22:40) :
A couple of questions if anybody can answer them
How much carbonic acid would it take to change the oceans pH by 0.1?
What does that volume translate to in gigatonnes of C02?
Is the relationship between carbonic acid and ocean pH a direct one or are there factors involved that either increase or decrease its impact?

Solutions of carbon dioxide in water can be of H 2 CO 3, or the salts of carbonic acid called bicarbonates (or hydrogen carbonates) and carbonates.
The ocean is filled with buffering cations, Mg, Na, Ca, K to name some common ones. The concentration or prevalence of any molecule containing CO3(and derivatives) in the ocean is subject to specific disassociation constants, temperature, and concentration of other molecules, etc., even if they don’t contain carbon (for example magnesium or calcium sulfate). Which means every molecule that can form a salt with carbon is present in the ocean, some in large concentrations, some miniscule. (I just knew that old Quantitative Analysis would come in handy—NOT).
Summation:
Technically speaking, NaCl is involved.
Terry, the ocean chemical makeup is very, very ,very complex. The questions you ask are still being debated, with wildly divergent numbers. Research in this area is even less “consensusified” than dCO2/dt.
Now I’m going to have a brewsky and watch the game. Burn me at the stake at your leisure.

Bill D
February 1, 2009 12:33 pm

Here’s my last point for this post.
I think that Frazier’s observation on how corals in his aquarium responded to CO2 AND calcium carbonate addition is a nice anecdotal observation. This is not be compared to the opinions of experts or to theory. Rather, as I scientist, I look to published articles where scientists used buffers, included controls, included replication and statistical analysis, measured coral growth and survival quantitatively, wrote up their methods, results and conclusions in detail, displayed data in graphs and tables, placed their study in the context of 20-50 other cited studies and subjected their work to review and criticism by experts. These studies show strong negative effects of decreased pH on corals while Frazier did not even measure effect of his additions on pH. I hope that everyone can agree that the published scientific papers are more convincing than Frazier’s observation. Google Scholar is relatively new, free search engine and makes it easier for scientists and especially, for people without paid subscriptions to other search engines to access the scientific literature. I hope that some of you, including Frazier, check read some scientific articles on effects of pH and temperature on corals.

John Philip
February 1, 2009 12:35 pm

BTW, Mr Goddard points to the recovery of the coral at Bikini atholl after the atomic tests there, and links to a report on a paper by Richards et al in Marine Pollution Bulletin discussed here by coral specialist and blogger Simon Donner.
Here’s an extract from that paper, courtesy of Donner If the disturbance event were to be repeated in the modern day, recovery would not be expected to be as high, due to the combination of additional stressors associated with climate change (Anthony et al., 2007; Lesser, 2007) and a possibly much altered atoll environment due to an additional 50 years of human occupation. Thus, in a twist of fate, the radioactive contamination of northern Marshall Island Atolls has enabled the recovery of the reefs of Bikini Atoll to take place in the absence of further anthropogenic pressure. Today Bikini Atoll provides a diverse coral reef community and a convincing example of partial resilience of coral biodiversity to non-chronic disturbance events.
Always go to the source ….

Steven Goddard
February 1, 2009 12:38 pm

Here is a good coral reef GIS resource, which shows overfishing and coastal development as being the primary sources of risk to coral reefs. I don’t see any mention of CO2 on the site.
http://reefgis.reefbase.org/default.aspx?wms=RGRRRCAR&bbox=-103.808693265072,25.8935666327375,-93.7331787563456,35.2426724764468&layers=Bathymetry,Countries,ReefOverfishing,Bathymetry

Herman Dobrowolski
February 1, 2009 12:50 pm

Most of the arguments made on this blog are incorrect because they present only part of the story. Listen to the voices of reason – woodfortrees and fraizer.
The facts are that carbon dioxide does reduce the alkalinity of sea water. However photosynthesis (corals contain photosynthetic organisms) accelerates, countering this affect. The effect of photosynthesis is far greater that the increase in carbon dioxide and necessarily slows down due to carbon dioxide deficiency. The overall effect is more coral.
This is borne out by sea observations around Australia during recent El Ninos. Increased temperature and carbon dioxide accelerate coral growth.

J. Peden
February 1, 2009 1:11 pm

Adolfo Giurfa (08:25:05) :
Though, as i said before, this is not about science but just marketing, it is useful to underline that for CO2 to increase its amount in sea water it needs a cooler sea water, then they have to choose between global warming, as they say, as a consequence of CO2 increase in the atmosphere, with warmer seas and less CO2 in the sea water, or colder seas with more dissolved CO2 in it.

Exactly.
Or else perhaps to escape this choice, the AGW scientists should tell us what atmospheric CO2 concentration it is which then effectively overcomes – by virtue of simple “mass action” – the decreased solubility of CO2 in warming water so that dissolved CO2 actually increases in this warming water, producing increased concentrations of Hydrogen ions [“acidity”].
So that then the World can have both acidifying Oceans, and warming Oceans and Atmosphere at the same time, as a result of atmospheric CO2.
CO2 + H2O H2CO3[Carbonic Acid] H[“acidity”] + HCO3[Bicarbonate]

Garacka
February 1, 2009 1:11 pm

Is “Bleaching” being used in a technical sense to mean exposure to more alkaline conditions or is it being used in a non-technical sense to refer to whitening?
If the 1st definition, than it means the oceans are becoming more basic as the surface waters warm and the corals are bleached.
If the 2nd definition, then something is happening to the Oceans and the corals are ejecting their algae and therefore whitening.

Bob Coats
February 1, 2009 1:15 pm

In Fraizer’s aquaria, were there control tanks, to which no CO2 was added? Did he measure water temperature, nutrient (N&P) concentrations, salinity, etc. Were the grazer and fish populations the same in the treatment and control tanks? Did he measure pH and CO2 concentration in the water? Were there any replications? If the answer to any of these questions is NO, then it was not an experiment, and cannot be used to falsify a hypothesis, though his observations might be used to formulate a hypothesis. It’s the difference between science and messing around.

David Porter
February 1, 2009 1:23 pm

Bill D (09:32:42) :
“As an aside, ā€œacidificationā€ is the routine scientific term for a decrease in
pH. ā€œNeutralizationā€ is more ambigous, since it could mean either a decline from an alkaline pH or an increase from an acidic pH. We could invent a new term, such as ā€œde-alkinizationā€ but we donā€™t have such a term. Scientists use the term ā€œacidificationā€ because there is no other single word that accurately discribes this process and no one has come up with a better term. Use of the term ā€œacidificationā€ cannot be taken as an effort to exaggerate or dramatize.”
You just could not be more wrong. The scientific term is neutralisation, which by definition means we are tending towards a neutral state. There is no need to invent any new term. The scientific heading for this thread would be correct if it said “OCEAN NEUTRALISATION AND CORALS”. As many others have said before me, the acidity term is used in an alarmist sense and is another reason why so many chemist are sceptics.
And as to your many references about how we should conceive of what scientist do, does grandma and sucking eggs mean anything to you?

J. Peden
February 1, 2009 1:23 pm

CO2 + H2O H2CO3[Carbonic Acid] H[“acidity”] + HCO3[Bicarbonate]
Sorry, my symbols between sides of the equations didn’t translate above:
CO2 + H2O = H2CO3[Carbonic Acid] = H[“acidity”] + HCO3[Bicarbonate]
the “=” is not correct, either, but so far it’s the best I can do.

Glenn
February 1, 2009 1:31 pm

Although not mentioned in the Monaco Declaration itself, ocean temperature
is clearly a concern, and an assumed element in coral bleaching to AGWers.
Here SST is used to provide alerts to bleaching “events”.
http://coralreefwatch.noaa.gov/satellite/virtual_stations/hawaii_virtualstations_timeseries_20062007.html
This Declaration clearly has elements of propaganda, as in ” Ocean acidification can be controlled *only* by limiting future atmospheric CO2 levels.” *Emphasis mine* “Can’t do it” gets it’s rear kicked by “did it” most every time.
I consider most if not all of that Declaration to be beyond what science can or should claim. Another example: “hundreds of thousands to millions of years will be required for coral reefs to return, based on the past record of natural coral-reef extinction events.” I have a hard time accepting that anything can or ever has recovered from an extinction event. This is junk science:
http://ioc3.unesco.org/oanet/Symposium2008/MonacoDeclaration.pdf

pablo an ex pat
February 1, 2009 1:52 pm

Mea culpa – erratum !
Sorry folks after thinking it through and then reading up a little more I should point out that I have erred.
The Carbonate/Bicarbonate buffering reaction I alluded to does in fact occur and is vital to retaining the health of the sea. The reaction is slightly different to the one described. The CO2 dissolves and forms Carbonic Acid, that Carbonic Acid reacts with Calcium Carbonate to form Calcium Bicarbonate.
As these two push and pull against each other the pH naturally varies between 7.5 and 8.5, right now it’s at about 8.2.
The alarmists are ringing the alarm bells because of an assumption that the mixing between upper layers of the ocean and the lower layers is thought to be a slow process taking up to 300 years. This would allow the CO2 to concentrate in the upper layers to the point where it overcomes the buffering and depresses the pH.
Here’s a link to a paper by Mr. G.E. Marsh, Argonne National Laboratory (retd) that discusses the above
http://www.gemarsh.com/wp-content/uploads/SEAWATER%20pH%20&%20ANTHRO%20CO2%20V2.pdf
There is no evidence that this long cycle time is true, it’s an assumption, there is evidence that the contrary is true i.e. the mixing is a lot faster than the alarmist assume that it is. e.g. Tritium from Nuclear testing in the Pacific in the 1950’s and 60’s has already shown up in the deep waters of the North Atlantic.

Glenn
February 1, 2009 2:08 pm

Another alarmist article indicting ocean temperature increase being responsible for coral bleaching and death:
http://www.sciencedaily.com/releases/2008/12/081228201342.htm
ā€œThis forecast bleaching episode will be caused by increased water temperatures and is the kind of event we can expect on a regular basis if average global temperatures rise above 2 degrees,ā€ said Richard Leck, Climate Change Strategy Leader for WWFā€™s Coral Triangle Program.
The bleaching, predicted to occur between now and February, could have a devastating impact on coral reef ecosystems, killing coral and destroying food chains.”
Does anyone seriously believe that ocean temperatures do not and have not in the past varied by a couple degrees? Why was the pollution problem in the Great Barrier Reef not mentioned, since pollution is known to cause coral bleaching and death? WHy did the article not mention that warmer water temperatures recapture CO2 and release it into the atmosphere?
I call it “biologists gone wild” at the local AGW bar.

H.R.
February 1, 2009 2:14 pm

Thanks for the post, Steven Goddard. I particularly liked your closing line.
“At some point the theorists will have to start paying attention to empirical data.”
Yup. And according to the early aero models, bumblebees couldn’t fly, yet bumblebees do fly. The aero-modeling gang had sense enough to observe bumblebees and go back to the drawing board.
The graph you included above would make most people stop and think for at least a moment, but apparently not. Unfortunately, I think I’ll be seeing pigs flying around before the CO2-driven AGW models are discarded.

February 1, 2009 2:20 pm

So they’ve made rebounds in some areas…however, most of the rest of the world’s coral is threatened.
I think scientists are too concerned with preserving the status quo to consider the rise of new species: don’t want anything interfering with our lifestyles.

Steve Huntwork
February 1, 2009 2:29 pm

Thanks, that is something that everyone who has attempted to grow a coral reef in a private aquarium soon learns.
I am not sure how you get the 7.5 to 8.5 variability, but at least you understood the basic concepts.
Later;
“The Carbonate/Bicarbonate buffering reaction I alluded to does in fact occur and is vital to retaining the health of the sea. The reaction is slightly different to the one described. The CO2 dissolves and forms Carbonic Acid, that Carbonic Acid reacts with Calcium Carbonate to form Calcium Bicarbonate.
As these two push and pull against each other the pH naturally varies between 7.5 and 8.5, right now itā€™s at about 8.2.”

Bill D
February 1, 2009 2:33 pm

David Porter (13:23:19) :
Neutralization can either mean adding base to an acidic solution or adding acid to a basic solution. Solutions can approach a neutral (pH = 7.0) from above 7 or above 7. “Neutralization is clearly ambiguous–it does not say whether a solution is becoming more acidic or more basic. It’s like saying the “weather is gettin more moderate.” That doesn’t even tell us if it is cooling from being hot or warming from being cold.

Steven Goddard
February 1, 2009 2:40 pm

John Philip,
The article did not say that Bikini corals were thriving in the past, but are now succumbing to CO2. What it did say is that the corals are thriving now.
“it was incredible, huge matrices of branching Porites coral (up to 8 meters high) had established, creating thriving coral reef habitat. Throughout other parts of the lagoon it was awesome to see coral cover as high as 80 per cent and large tree-like branching coral formations with trunks 30cm thick. It was fascinating I’ve never seen corals growing like trees outside of the Marshall Islands. ” “The healthy condition of the coral at Bikini atoll today is proof of their resilience and ability to bounce back from massive disturbances”
http://www.sciencedaily.com/releases/2008/04/080415101021.htm

Steve Huntwork
February 1, 2009 2:41 pm

neurotype:
“however, most of the rest of the worldā€™s coral is threatened.”
Oh?
My wife and I are very active scuba divers.
Where has this happended, and where we can we visually see it?
Why is it, that pollution is horrible somewhere else, but never in your location?

Bill D
February 1, 2009 2:52 pm

Garacka (13:11:58) :
Is ā€œBleachingā€ being used in a technical sense to mean exposure to more alkaline conditions or is it being used in a non-technical sense to refer to whitening?
If the 1st definition, than it means the oceans are becoming more basic as the surface waters warm and the corals are bleached.
If the 2nd definition, then something is happening to the Oceans and the corals are ejecting their algae and therefore whitening.
Bleaching is clearly used in the sense of whitening due to loss of the dinoflagellate algae. Death of the corals is due to a loss of the symbiotic algae as a source of nutrition. If the high temperature is short in duration, corals can sometimes recover from bleaching. However, bleaching kills the algae on a time scale of weeks.
The coral reefs have experienced fluctuations of 2oC in the past, but not from such a high starting point.
Someone in a past posting talked about pollution problems being an alternative explanation for bleaching events in the Great Barrier Reef. Was this just a “made up” idea? This vast area is not near sources of pollution. Can you provide a source of information on pollution problems?

John W.
February 1, 2009 2:55 pm

Could I suggest a “change” in terminology?
The phrase “climate change” has always struck me as subtly inaccurate at best, and misleading at worst. Could we begin using the phrase “climate variation” instead? It seems a much more appropriate way to describe what the climate is actually doing.

February 1, 2009 3:05 pm

Steve Huntwork (11:39:54) :

Having two reef aquariums in my home, I must agree with Fraizer…

For many years I had numerous tropical fish tanks up to 125 gallons. I never had reef [saltwater] tanks, but when I hooked up a CO2 injection system, the plant life exploded! I’m sure this will be critiqued as non-scientific, but the result of using those little 12-gram CO2 cylinders was really amazing. Plants grew at more than double their former rate.
Bob Coats (13:15:20) :

In Fraizerā€™s aquaria, were there control tanks, to which no CO2 was added?

It appears that it was a simple test to find out if injecting CO2 caused the water to become more acid. It did not.
And that physical, hands-on experiment is more impressive than people nitpicking someone else, instead of replicating the experiment themselves, wouldn’t you agree?
Neven:

“Smokey, you kill all the hope I have for humanity.”

Neven me boy, I’m sorry you’re hopeless. But try to cheer up. The world is not going to end, and the climate will keep chugging along within its normal and natural historical parameters. Nothing to get alarmed about.

Steve Huntwork
February 1, 2009 3:24 pm

Smokey:
I have 400 gallons of saltwater circulating between my sump in the basement and my two display aquariums on my living floor. On eis “only” 55 gallons and the other is “only” 95 gallons.
Argonite, as a buffer, is very important and why it is a vital part of my aquariums. I know all about the chemistry of buffers and why they are important in a saltwater environment.
Why is it, that pollution is horrible somewhere else, but never where you are located?
I live across the street from a High School, and my favorite trick it to provide every student with a camera.
TASK: Document any environmental pollution in this area!
After five years, nobody has been able to photograph a source of environmental pollution in our area.
Think about that…

pablo an ex pat
February 1, 2009 3:37 pm

Sreve Huntwork
The 7.5 to 8.5 natural variability of ocean pH is demonstrated on page 10, Figure A 2 of the link.
http://www.gemarsh.com/wp-content/uploads/SEAWATER%20pH%20&%20ANTHRO%20CO2%20V2.pdf

Steve Huntwork
February 1, 2009 4:12 pm

pablo an ex pat:
Outstanding!
I will wager $100 that you can not demonstrate that result, in an experiment that we both conduct under the exact same conditions.
Get your saltwater aquarium ready…
If your fish die, then you cheated!

John Game
February 1, 2009 4:43 pm

Steve Goddard’s post is helpful in putting ocean acidification in perspective, but remember that pH reflects the logarithm of the ion concentration – it is not a linear scale. So, when Goddard writes
“Between 1751 and 1994 surface ocean pH is estimated to have decreased from approximately 8.179 to 8.104.ā€ At that rate, it will take another 3,500 years for the ocean to become even slightly acid
Then if “rate” means that acidic substances (presumably cabonic acid from atmospheric CO2) are added at a constant rate per unit time, a much faster response in numerical pH per unit time will occur as one approaches nearer and nearer to neutrality. So, technically, it would not take 3,500 years to reach pH 7.0. Also, most of the change may have happened more recently than 1751, and taking a 250+ year time scale for the pH trend will underestimate the current rate of change if the change occurred mostly in recent decades.
I am not sure if this affects the overall argument. To assess the risk, one would have to know what are the pH tolerances of modern corals in our current oceans. I dare say there has been work on this, does anyone know of relevant publications? What happened at Bikini is not relevant, because once the bomb tests stopped, in a few yearsconditions presumably became similar enough to conditions prior to the tests that coral could grow back. The same is true when reefs are damaged by hurricanes, etc. – they eventually recover. But if the water becomes too cold/too hot/ too acid/too alkaline or in any other way toxic for them, and stays that way – that’s a different matter.
John G.

TerryS
February 1, 2009 4:43 pm

I’ve just been reading another BBC article titled “Mammoth-killing comet questioned”
You would think that this wouldn’t have a “climate change” angle but you would be wrong. The end section nicely weaves it in.

Of more importance to current climate watchers is the finding that during the 5,000-year period studies, the greatest incidence of fires occurred just after periods of abrupt climate change.

Periods of climate change result in the death of plants and trees that more readily provide fuel.

Its seems that any article on the BBC has to make a claim that we heading for a catastrophe.

February 1, 2009 4:49 pm

Robert S (21:27:59) :
ā€œThe ocean currently has a pH of 8.1, which is alkaline not acid. ā€
Acidification is the process of becoming acidic

Correct, but irrelevant, since the oceans are not becoming acidic, they are becoming very slightly less alkaline, or if you like, more PH neutral.
Get it right.
I really really dislike scaremongering foolishness such as that displayed by these AGW ‘scientists’.

DaveE
February 1, 2009 5:01 pm

TerryS (16:43:52) :
“Its seems that any article on the BBC has to make a claim that we heading for a catastrophe.”
This is welcome. It means that desperation is setting in.
DaveE.

February 1, 2009 5:02 pm

Ye gods man, do you guys get anything right before you criticize, comment and disparage? I’ll keep submitting comments here until you decide to actually publish them.
1) “Acidification” refers to the lowering of pH, not whether the liquid is an acid or alkili. Acidity refers to the concentration of hydrogen ions in the liquid, of which pH is a logarithmic measure. So a decline in pH indicates an increase in the acidic properties of the liquid, regardless of what the actual pH number is. The ocean is a tremendous buffer, and pH should generally change only on geological timescales, as indeed we know it has. The fact that we have been able to measure a decrease in modern instrumental time is very disturbing.
2) The decrease is driven by the increased concentration of carbon dioxide in the atmosphere. When CO2, which is very soluble, dissolves in seawater, it undergoes a series of chemical dissociations, first to form carbonic acid, then free bicarbonate ions, and finally carbonate ions. As the ocean becomes more saturated with CO2, this equilibrium is being shifted so that solid carbonate salts become more soluble. The most common biologically produced carbonate is calcium carbonate, one form of which is used by corals for the construction of their skeletons. Therein lies the reasons to worry about the corals as atmospheric CO2 concentration rises.
3) There is a lot that we don’t know about the potential impact of this issue. It will definitely be detrimental for a lot of organisms, and not only because of the attack on their skeletons, but also because the increase in CO2 in the water often causes hypercapnia; think of this as strangulation underwater.
4) Some organisms might benefit, and there is some experimental evidence to support this now. However, before we celebrate this, I’ve noted that the reports of these organisms generally involve species that are currently minor ecological components. If they rise to more dominant ecological roles, we’ll see a shift in community/ecosystem compositions and functioning. Whether these changes will be bad, neutral, or beneficial to other species, as well as human economic dependencies, is a wide open question. Be concerned gentlemen.
5) To the coral aquarium enthusiast who claimed that his corals have never done better since adding CO2 to his water, I’ll point out simply that he is making it easier for the corals to mineralize their carbonate skeletons. His aquarium water is definitely not at a saturation point. If he’s interested, keep ramping up the CO2 concentration, and see what happens. Science at home.

Alan Wilkinson
February 1, 2009 5:08 pm

John Philip (12:01:09) : The acidification (or de-alkalinisation) is a concern because it will make it harder for calcifying organisms to make hard structures. This requires seawater to be supersaturated with calcium and carbonate ions to ensure that once formed the CaCO3 does not dissolve. Lower pH reduces the carbonate saturation of the seawater, making calcification harder and also weakening any structures that have been formed. Feely et al found that a doubling of CO2 will reduce calcification by between 5-25% depending on species.

This is a misrepresentation of the basic chemistry.
There are two aqueous dissociation constants involved:
(1) H2CO3 H+ & HCO3- 2H+ & CO3–
as well as the solubility reaction involving Henry’s Law at the surface:
(2) H20 + CO2 H2CO3
Adding more CO2 to the sea whether by increasing atmospheric CO2 or by cooling the water which modifies Ks can only drive equation 1 to the right, increasing the amount of CO3– in the water.
Likewise, increasing the amount of CO3– in the water (by dissolving Calcium Carbonate can only drive equation (1) to the left (incidentally making the water more alkaline.)
In this scenario the only way the ocean can be made more acidic without also increasing carbonate concentrations is to remove the carbonate by forming more shells and coral, not less.
So the alarmists are actually complaining that the increased coral and shell productivity over the last two centuries is going to slow down because of the decreased alkalinity it has caused. That is the real message of Feeny et al., in basic chemistry stripped of its spin.

February 1, 2009 5:12 pm

And one more point. Corals from the Ordovician were in no way comparable to modern corals. They were evolutionary distinct. Those reef builders were rugose corals. Today’s scleractinian corals evolved from a separate evolutionary lineage probably no earlier than the Triassic.

MikeT
February 1, 2009 5:14 pm

It appears coral bleaching can be an ‘survival’/’evolutionary’ strategy:
http://www.worldclimatereport.com/index.php/2004/06/07/bleached-bond/
http://www.nature.com/nature/journal/v411/n6839/full/411765a0.html
and an alternative explanation for bleaching other than ocean temperature can be found at:
http://www.co2science.org/education/reports/corals/p1ch3.php

Alan Wilkinson
February 1, 2009 5:16 pm

Sorry, HTML tags wrecked my equations. Trying again:

John Philip (12:01:09) : The acidification (or de-alkalinisation) is a concern because it will make it harder for calcifying organisms to make hard structures. This requires seawater to be supersaturated with calcium and carbonate ions to ensure that once formed the CaCO3 does not dissolve. Lower pH reduces the carbonate saturation of the seawater, making calcification harder and also weakening any structures that have been formed. Feely et al found that a doubling of CO2 will reduce calcification by between 5-25% depending on species.

This is a misrepresentation of the basic chemistry.
There are two aqueous dissociation constants involved:
(1) H2CO3 ← K1 → H+ & HCO3- ← K2 → 2H+ & CO3–
as well as the solubility reaction involving Henry’s Law at the surface:
(2) H20 + CO2 ← Ks → H2CO3
Adding more CO2 to the sea whether by increasing atmospheric CO2 or by cooling the water which modifies Ks can only drive equation 1 to the right, increasing the amount of CO3– in the water.
Likewise, increasing the amount of CO3– in the water (by dissolving Calcium Carbonate can only drive equation (1) to the left (incidentally making the water more alkaline.)
In this scenario the only way the ocean can be made more acidic without also increasing carbonate concentrations is to remove the carbonate by forming more shells and coral, not less.
So the alarmists are actually complaining that the increased coral and shell productivity over the last two centuries is going to slow down because of the decreased alkalinity it has caused. That is the real message of Feeny et al., in basic chemistry stripped of its spin.

Alan Wilkinson
February 1, 2009 5:19 pm

Still having trouble with my HTML – obviously the carbonate ions should have two negative charges rather than the one HTML left me with.

February 1, 2009 5:19 pm

Bill D (11:23:10) :
if you want make predictions about the future, you need to know whether water temperature will continue to rise and if humans will continue to use large amounts of fossil fuels.

And of course, you’ll need to know if there is any measurable connection between the two. Until then, it remains a non secuiteur.
Happily though, water temperature is falling. While co2 continues to rise.
http://www.woodfortrees.org/plot/hadsst2gl/from:2004/scale:100/offset:-40/plot/esrl-co2/from:2004/offset:-380

G Alston
February 1, 2009 5:21 pm

OT sort of.
Don’t let ’em fool you. This too will be blamed on AGW…
http://apnews.myway.com/article/20090201/D962KB401.html

Bob Coats
February 1, 2009 5:30 pm

Tim Clark (12:19:04) :
If you really think that Hoegh-Guldberg and his co-authors have got carbonate chemistry wrong, but you have it right, then you should write a letter to the editors of Science Magazine, correcting their mistake(s). I will be watching for it, but not holding my breath.

Roger Knights
February 1, 2009 5:47 pm

“When I see a post like this from Bill D AFTER the post from Fraizer – I have to conclude that oneā€™s intuition carries more weight than facts.
The moderators are not constantly monitoring posts nowadays, as their number has been reduced from five to two, as Anthony has mentioned a few times here and there. Therefore posts are “batch processed” in bunches, and it will often appear as though a subsequent poster has ignored a previous one.
Reply: Well I just got back from Brazil so the number (of moderators) is creeping back up again ~ charles the moderator

Steven Goddard
February 1, 2009 5:51 pm

John Game,
Good point about the 3500 years to neutral. The number isn’t terribly meaningful though because of the buffering effects of limestone in the oceans. As pH decreases, more CaCO3 dissolves, tending to drive the pH back up. It would be simple enough to dump powdered CaCO3 into the oceans to keep the pH up, if people are worried about it. Remember that shellfish appeared in the oceans when atmospheric CO2 levels were much higher than the present.
As far as the bomb effect goes, of course it is important. The fact that the ecosystem has recovered from completely annihilated and highly radioactive in just 55 years, indicates a tremendous resiliency.

deadwood
February 1, 2009 6:08 pm

A problem with the hypothesis of CO2 causing dead zones in the ocean is the evidence from the deep oceans, where acidic fluids from black smokers associated with submarine volcanic activity are where life flourishes. I know from grad school days that the fluids measured at the vents are pH of between 2.0 to 5.5 (i.e weakly to strongly acidic).

E.M.Smith
Editor
February 1, 2009 6:09 pm

Steven Goddard (06:49:14) : I donā€™t know how to construct an argument against arm waving speculation, other than to point out again that CO2 levels were much, much higher in the past – and the oceans were teaming with life.
Are there any corals were a volcanic vent makes locally acidified water? I’d use Iceland as and example if only it were a few thousand miles more south… 8-|
Any tropical underwater volcano growing corals?
Nothing like an existance proof if you can find it.

Steven Goddard
February 1, 2009 7:28 pm

E.M.Smith,
I’m not trying to construct an argument that corals or shellfish can survive in acidic water. Because they can’t.
What I am saying is that corals and other shellfish have thrived at much higher atmospheric CO2 concentrations. The point being that the relationship between atmospheric CO2 and ocean pH is apparently not so simple as some might have us believe.

H.R.
February 1, 2009 7:41 pm

(17:02:48) :
[…]4) Some organisms might benefit, and there is some experimental evidence to support this now. However, before we celebrate this, Iā€™ve noted that the reports of these organisms generally involve species that are currently minor ecological components. If they rise to more dominant ecological roles, weā€™ll see a shift in community/ecosystem compositions and functioning. Whether these changes will be bad, neutral, or beneficial to other species, as well as human economic dependencies, is a wide open question. Be concerned gentlemen.[…]
I was reading the chart and admittedly ignorant of the different species of coral involved multi-MYA vs the present. I thought your point #4 was good. Something is going to fill a niche left by a failed species. How far can various current coral species (‘X’) “migrate” to become established in favorable voids left by species (‘Y’) where the environment became unfavorable to species (‘Y’)? Just wondering. Someone somewhere is probably studying that.
I think the answer to “Whether these changes will be bad, neutral, or beneficial to other species,…” is, all three.

Tim Clark
February 1, 2009 7:54 pm

Bob Coats (17:30:34) :
If you really think that Hoegh-Guldberg and his co-authors have got carbonate chemistry wrong, but you have it right, then you should write a letter to the editors of Science Magazine, correcting their mistake(s). I will be watching for it, but not holding my breath.

There have been at least four other posters, including Alan above, that concur with my point, showing elementary equations. Either show where the chemistry we present is in error, or propose another hypothesis. If you can’t understand it now, how will you be able to read the magazine?

George E. Smith
February 1, 2009 7:55 pm

Well teenagers drink carbonic acid by the gallon and it doesn’t seem to bother them
So just where has it been tried out; growing Corals in acid that is.
I would think that as ocean surface waters became warmer, that the surface waters would hold less CO2, and the process of driving the CO2 to deeper cooler waters would accelerate.
You don’t find a lot of people diving on the coral reefs in the southern ocean. Corals can migrate and find the conditions they prefer, and mostly they seem to prefer warmer waters. I don’t know whether they pick the water based on its pH or whether they find the food chain to their liking in warmer waters.

HasItBeen4YearsYet?
February 1, 2009 8:07 pm

CORALS WERE MEANT TO BLEACH? (another link for you, MikeT)
@E.M.Smith (18:09:27)
I looked for that yesterday, and found a few things which weren’t as clear as I wanted, but I think that line is definitely worth pursuing. My guess is that there isn’t much on it, and that if the environment proved the warmers’ points there would be, so the absence, while not proof they are wrong, is highly suggestive.
an ex pat
Indian Ocean winter pH range is about 7.87 to 8.23 (0.35 pH units!) over the Temperature Range of about 0.2 to 0.3 DegC.
http://www.mgac.nsysu.edu.tw/ctchen/Publications/A/58.pdf
If you haven’t seen these videos you might want to…

http://www.youtube.com/watch?v=m4SN1-vwBVs
…enjoy

HasItBeen4YearsYet?
February 1, 2009 8:10 pm

arrrrggg
I’ll try this in two sections because it’s not appearing at all…
ONE OF TWO
CORALS WERE MEANT TO BLEACH? (another link for you, MikeT)
@E.M.Smith (18:09:27)
I looked for that yesterday, and found a few things which weren’t as clear as I wanted, but I think that line is definitely worth pursuing. My guess is that there isn’t much on it, and that if the environment proved the warmers’ points there would be, so the absence, while not proof they are wrong, is highly suggestive.

HasItBeen4YearsYet?
February 1, 2009 8:11 pm

TWO OF TWO
an ex pat
Indian Ocean winter pH range is about 7.87 to 8.23 (0.35 pH units!) over the Temperature Range of about 0.2 to 0.3 DegC.
http://www.mgac.nsysu.edu.tw/ctchen/Publications/A/58.pdf
If you haven’t seen these videos you might want to…

http://www.youtube.com/watch?v=m4SN1-vwBVs
…enjoy

HasItBeen4YearsYet?
February 1, 2009 8:12 pm

APPARENTLY THIS ONE’S THE PROBLEM…
TWO OF THREE, NOW
an ex pat
Indian Ocean winter pH range is about 7.87 to 8.23 (0.35 pH units!) over the Temperature Range of about 0.2 to 0.3 DegC.
http://www.mgac.nsysu.edu.tw/ctchen/Publications/A/58.pdf

HasItBeen4YearsYet?
February 1, 2009 8:12 pm

THREE OF THREE
If you haven’t seen these videos you might want to…

http://www.youtube.com/watch?v=m4SN1-vwBVs

Neven
February 1, 2009 8:19 pm

Steven,
“Remember that shellfish appeared in the oceans when atmospheric CO2 levels were much higher than the present.”
Are they the same shellfish as today’s shellfish?
“As far as the bomb effect goes, of course it is important. The fact that the ecosystem has recovered from completely annihilated and highly radioactive in just 55 years, indicates a tremendous resiliency.”
A human being can survive a heavy car crash and recover completely after a certain amount of time. If however after the car crash the car drops into a river, the human being will not recover. Of course an ecosystem can survive a thermonuclear explosion when after that conditions return to normal. But the whole point is that there’s possibly a shift that is affecting those conditions. If the ocean pH reaches a certain threshold and you set off a thermonuclear bomb in an area where there is a lot of coral, the coral will NOT recover.
I don’t know much about the science, but this is just plain common sense.
“What I am saying is that corals and other shellfish have thrived at much higher atmospheric CO2 concentrations. ”
I’ll ask you again: Did these corals and other shellfish in the distant past have to cope with a rate of change that is a hundred times bigger than natural variability? If so, how did they do? You probably know this as you must have done some extensive research for your article.
“The point being that the relationship between atmospheric CO2 and ocean pH is apparently not so simple as some might have us believe.”
If this is the case then why is your article so incredibly simplistic? You’re not addressing the real issue at all, ie rate of change. You’re just beating about the bush because you don’t want CO2 to be linked to any possible adverse effects. This is misleading and I’m not really sure if you’re doing it on purpose or not. I would say you’re too smart not too notice the fallacies of your argument.

HasItBeen4YearsYet?
February 1, 2009 8:19 pm

an ex pat
My …“Indian Ocean winter pH range is about 7.87 to 8.23 (0.35 pH units!) over the Temperature Range of about 0.2 to 0.3 DegC”
SHOULD HAVE READ…
Indian Ocean winter pH range is about 7.87 to 8.23 (0.35 pH units!) over the Temperature Range of about 0.2 to 30 DegC
Sorry

Admin
February 1, 2009 8:22 pm

THIRD OF THREE, TAKE TWO
It wonā€™t let me give the You Tube links, so Iā€™ll try something differentā€¦
Link one
Link two
Reply: I accidentally deleted your post, and lost the links when I tried to recreate it from my cache. My sincere apologies.
Comment update. I recovered the links from the previous post.
FYI, posts here are moderated, so they don’t show up until approved. ~charles the moderator

HasItBeen4YearsYet?
February 1, 2009 8:31 pm

the moderator
“Reply: I accidentally deleted your post, and lost the links when I tried to recreate it. My sincere apologies.”
Stuff happens. I think I’ve gotten everything in these several posts, so nothing was lost. And, since I’ve posted it, it’s a good thing you can’t redo it so there won’t be any redundancy.
Regards

Richard Sharpe
February 1, 2009 8:31 pm

Neven asks:

Iā€™ll ask you again: Did these corals and other shellfish in the distant past have to cope with a rate of change that is a hundred times bigger than natural variability?

Please define natural variability?
Please also tell us what you are concerned with? Acidification? Temperature Increases?

HasItBeen4YearsYet?
February 1, 2009 8:36 pm

the moderator
Oh, but I see you did recostruct a lot of it. Sorry about the duplication, but sometimes moderators don’t get to restoring things until too late for comments to be read by the readers the poster intended them for, so since I didn’t know when you would get to it I tried to get the info out there. Sorry, and thanks for being so timely. Sorry I wasn’t expecting it.

February 1, 2009 8:37 pm

Bill D (09:43:50) :
“Compare your reasoning with a few dozen articles written by experts in ocean chemistry before you assume that they are wrong.”
You make a good point – and if I had time, I would, but I am offering my perspective as a geologist , not as an ocean chemist. The geologic record (my speciality) – and the basic chemistry of CO2 which is less soluble in warmer water (does anyone dispute that?) and the fact the quote from John Phillip that bleaching / dying events are worse in warm waters simply do not add up – all say more CO2 is better – at least for coral – so there is a huge disconnect here – which given the alarmist rhetorical makes me very very skeptical of these claims. You should be skeptical too. You don’t need to be an expert in ocean chemistry to recognize that there is a huge disconnect here.
As a side note, I am guessing almost all ocean chemistry research is funded by grants – and if you are funded by grants, your motives are suspect. Sad , but true. Anyone who has been in a graduate level science program & has seen the grant process knows this. You think “big oil” is motivated by money? That’s nothing compared to a college prof who will be unemployed & pennyless if he doesn’t get his grant. If the funders of the grant want the research to show that CO2 is evil, then the research will show it’s evil – to the best of it’s ability.
This again comes back to my original post on this thread. Science, not just climatology, is being irreparably harmed by politics seeping into it. We cant blindly trust anything that anyone publishes anymore because the process has become so corrupt – we must all be skeptical of all points put forward & make our own judgments of what is correct. Science has sold it’s soul to the devil & we are all paying the price. Fortunately, there are a few questioning minds out there, but the general public is being lead around by the nose by those who control the purse strings (govt , which in turn funds the grants) – being lead to believe that scientists are somehow above the fray. It would be funny if it wasnt so sad.

anna v
February 1, 2009 8:52 pm

Neven (20:19:08) :
I donā€™t know much about the science, but this is just plain common sense.
and
ā€™ll ask you again: Did these corals and other shellfish in the distant past have to cope with a rate of change that is a hundred times bigger than natural variability? If so, how did they do? You probably know this as you must have done some extensive research for your article.
The answer is yes, sometimes they did, when the temperatures started rising or falling rapidly, some research says within a few years. If you look at the thread below this one, co2-temperatures-and-ice-age, you can see it in the first figure.
You can also see that there is not “natural”. Rather that everything is natural and the most natural thing is transience.
As for the simplicity of this presentation, do you know the KISS principle? Keep It Simple Stupid. It is a prime driver of science, particularly of looking for a theory that fits the data. The simplest theory that fits the data wins every time. AGW theory is neither simple not fits the data.

Glenn
February 1, 2009 8:55 pm

Bill D (14:33:58) :
“Neutralization can either mean adding base to an acidic solution or adding acid to a basic solution. Solutions can approach a neutral (pH = 7.0) from above 7 or above 7. ā€œNeutralization is clearly ambiguousā€“it does not say whether a solution is becoming more acidic or more basic. Itā€™s like saying the ā€œweather is gettin more moderate.ā€ That doesnā€™t even tell us if it is cooling from being hot or warming from being cold.”
And if acidification only means to move more acidic, then a ph from 3 to 2 would also be acidification, yet the word itself would be ambiguous in that it not tell us if the ph were moving from base to acid. “The acidification of the oceans” could then mean that the oceans are already highly acidic. Oops, I used the word acidic.
One poster thinks the word clearly means simply to move the ph down, and claims that is some acknowledged or understood usage in science or a particular branch of science, leaving us to accept or reject his word for it.
Another poster argues that the word is used because no single word can express a reduction in alkalinity, as if using one word for a scientific process is ever an issue.
I may have omitted other arguments for why “acidification” should not be thought of as propaganda but rather as correct terminology or grammar, but none are convincing. And even less convincing when considering what often accompanies the word, “becoming more acidic”, which is clearly wrong. The oceans are not acidic. I have researched the definition at some length, and not found the word to be used to describe changes in alkalinity. You are welcome to do the same and return your results.
I’d think it safe to say that the general public regards the word acidification as “to make acidic”, or “acid”.
http://www.thefreedictionary.com/acidification
“the process of becoming acid or being converted into an acid”
http://www.answers.com/topic/acidification-chemistry
“(chemistry) Addition of an acid to a solution until the pH falls below 7”
http://www.chemistry-dictionary.com/definition/acidification.html
“This process happens when compounds like ammonia, nitrogen oxides and sulphur dioxides are converted in a chemical reaction into acidic substances. ”
http://en.wiktionary.org/wiki/acidification
“The act or process of making something sour (acidifying), or changing into an acid.The act or process of making something sour (acidifying), or changing into an acid.”

Robert S
February 1, 2009 9:11 pm

Tall Bloke
Correct, but irrelevant, since the oceans are not becoming acidic, they are becoming very slightly less alkaline, or if you like, more PH neutral.
Get it right.

I am sorry you are confused Tall Bloke, but as many have pointed out here (Bill D, Peter, Marcus), acidification is any drop in pH regardless of whether it starts out as alkaline, neutral, or acidic. You can call it what you like, but acidification will remain the correct–and thus, perfectly acceptable– term.

paminator
February 1, 2009 10:21 pm

Prof Tim Wootton (Dept. Ecology & Evolution,
The University of Chicago ) has a website at-
http://pondside.uchicago.edu/ecol-evol/faculty/Wootton/pH.htm
He recently hit the MSM with data on ph reductions at one site off Washington’s coast. From his website, here is what he says about the global pH database upon which pH trends critically depend;
“Hence, predictions have been made that ocean pH will decline with increasing atmospheric CO2 emissions, and that this decline will be sufficient to disrupt major physiological processes such as calcification. While the physics of this reaction are well known, there are surprisingly few published data of measurements of pH change in the ocean through time. Furthermore, although laboratory studies demonstrate that many calcifying organisms perform poorly in acidified water, extrapolating these results to predict the response in complex ecosystems is difficult.”
The database is, shall we say, sparse.
As to changes in ocean pH of 0.1 being alarming;
“Since 2000, we have been monitoring physical ocean conditions, including ocean pH, at our main study site in the northeastern Pacific Ocean: Tatoosh Island, Washington, USA. We use a submersible data logger to record water conditions at 1/2 hour intervals, yielding a dataset of very high temporal resolution (>40,000 datapoints total and growing) to explore changes in pH through time.
In contrast to the widely-held notion that the ocean is well buffered, our pH data exhibit a surprising degree of systematic variability through time. Even over the course of a day, pH typically varies by 0.24 units, a consequence of the uptake and production of CO2 through photosynthesis and respiration. Hence biological processes, which are often left out of models of ocean pH, can have strong effects.”
A graph at his site indicates daily thru seasonal variations at this one location at Tatoosh Island, WA shows variations from 7.4 to 8.9 pH. It would seem particularly specious to claim a teleconnection from this site to the other 99.99999999% of the world’s oceans as to what global ocean pH is today. How about a hundred years ago? A thousand?
As to our understanding of what impacts multiyear trends in ocean pH measured in shallow waters at Tatoosh Island;
“Over the entire span of the data, ocean pH is clearly declining as atmospheric CO2 increases, but at a rate an order of magnitude faster than predicted by current physical models.”
Sounds like we yet more worthless models.
We need much more measured data, and much less catastrophism.

anna v
February 1, 2009 10:23 pm

Ī‘

Bill D
February 1, 2009 11:01 pm

If we exclude all of modern science that is funded by grants then almost no science remains. We might as well say that science can only be done by people who are not paid to be scientists and we can also exclude anyone with an advanced degree who is actually working in his or her field of expertise.
Oceanographers, for example, often need ship time, which costs a lot of grant money. Almost all scientists need modern equipment, a large part of which is purchased from grants. The days when science was done by aristocrats from wealthy families using their own money is long gone. Doing pure theory does not require much equipment, but theoreticians, like Einstein, who started doing science on the side while working in a patent office, are also very rare. A big chunk of grant money goes to training students, including undergraduates and graduate students as well as postdocs. Without grants, the training of young scientists comes to halt.
Opinions have no basis in science. The opinions of experts, politicians and the public do not matter for scientific debates, only peer reviewed publications really count. (Of course opinions matter a lot in politics and policy decisions).
Some people on this blog seem to think that scientific articles are “opinions.” This is completely false. Articles in scientific journals are the presentation and analysis of data, observations, experiments and models. Sometimes journal articles also present new theory. Exaggerated claims or misrepresentation of cited articles is a cause for the rejection of a submitted manuscript. This is why the writing in scientific articles is very cautious and precise and why sections should not be quoted out of context.
I completely agree that the media, environmentalists and politicians often simplify, dramatize and exaggerate scientific results and conclusions. This is why you should read the original scientific studies described in scientific journals. Review articles that weigh the evidence of the publications of a field of research without presenting new data are also useful, especially when you don’t have the time to read all of the original studies or when you want to decide which of the original studies to read.

February 1, 2009 11:03 pm

ScienceDaily (Nov. 26, 2008) ā€” University of Chicago scientists have documented that the ocean is growing more acidic faster than previously thought. In addition, they have found that the increasing acidity correlates with increasing levels of atmospheric carbon dioxide, according to a paper published online by the Proceedings of the National Academy of Sciences on Nov. 24.
… The new study is based on 24,519 measurements of ocean pH spanning eight years, which represents the first detailed dataset on variations of coastal pH at a temperate latitudeā€”where the world’s most productive fisheries live.
“The acidity increased more than 10 times faster than had been predicted by climate change models and other studies,” Wootton said. “This increase will have a severe impact on marine food webs and suggests that ocean acidification may be a more urgent issue than previously thought, at least in some areas of the ocean.”

http://www.sciencedaily.com/releases/2008/11/081124141053.htm
This is the latest, “best available” science. Note that the rate of change is 10 times, not 100 times. Note that the base rate for comparison is a MODEL!!!!! Note that “the first detailed dataset” is 8 years long, not 100 years, not 1,000 years, not a million years.
This has all the hallmarks of junk science: inflammatory conclusions, inferences expanded far beyond the limits of the data, based on a model no less, and used by professional alarmists as justification for inducing panic.
Every point can be easily refuted: historical rates of pH change are unknown, correlation is not causation, ocean acidification cannot be due to atmospheric CO2 based on simple chemistry, the dataset is limited in time and location, and the postulated “urgency” is pure speculation designed to induce political hysteria.
So too, coral reef bleaching is blown completely out of proportion. It is limited to certain specific locations, causal factors are unknown, correlations with postulated factors are weak, and there is no historical data for comparison.
Oceanic carbon fixation occurs everywhere in the oceans, from under the polar sea ice to the warmest equatorial waters. Plankton, diatoms, mollusks, echinoderms, and other sea life as well as tropical corals are anabolic calcium carbonate producers. That fundamental life process is not limited to any narrow range of temperature or pH.
It is tragic that “scientists” today must abandon their integrity for research dollars, but it is nothing new and has been happening since the early days of alchemy. Buyer beware.

Glenn
February 1, 2009 11:07 pm

Robert S (21:11:53) :
“I am sorry you are confused Tall Bloke, but as many have pointed out here (Bill D, Peter, Marcus), acidification is any drop in pH regardless of whether it starts out as alkaline, neutral, or acidic. You can call it what you like, but acidification will remain the correctā€“and thus, perfectly acceptableā€“ term.”
Many here have pointed out that acidification in not any drop in ph, as well. I’d say because of that your response above shows that you are confused.
How about the terms in this article, correct or not with regard to “acidity” and “acidic”?
http://news.nationalgeographic.com/news/2008/11/081124-acidic-oceans.html
“oceans more acidic”
“the acidity increased”
“the increase in acidity”
“30 percent rise in ocean acidity”
Do you think “acidification” means “to make more acidic”? If so, is a ph of 8 acidic or not? Is 8 more acidic than 9? Does a drop from 9 to 8 signify an increase in *acidity*?

February 1, 2009 11:24 pm

Whoops, I forgot to add that one sure sign of junk science is the use of Principal Component Analysis. No logical inferences or testable hypotheses can be derived from PCA. None. The “dynamics of orthonormal eigenvectors in k dimensions” and similar stat-babble gibberish should be a red flag. Alchemy, not science.
Just because it appears in journal doth not make it science. Sorry to burst anybody’s bubble, but (sadly) most of what appears in science journals is more or less junk.

February 1, 2009 11:25 pm

Robert S (21:11:53) :
I am sorry you are confused Tall Bloke, but as many have pointed out here (Bill D, Peter, Marcus), acidification is any drop in pH regardless of whether it starts out as alkaline, neutral, or acidic.

And I’m sorry you are the willing dupe of propagandists Robert, but as you’ve seen, the journalists and the general public are more easily confused than either of us.
Regardless of the ‘correctness’ of terminology, the aim of science’s pronouncements to the public should always be to inform and educate, not mislead. Sadly, the agenda of the alarmista is to do just that.

Admin
February 1, 2009 11:31 pm

On this use of the term acidification. This argument is silly. The term is correct and is used correctly in these these articles whether or not you agree with the content or tone of the articles. It would be silly to use dealkanilinization as an alternative.
Do people find the word acid scary? Yes. But people also find the word chemical scary and tell you they don’t want to eat food with chemicals in it. Simply because these same people do not know what these words mean does not mean they are being used incorrectly.
My favorite rhetorical device when discussing, “natural” or “raw” food is to ask the proponents of such: “What is the definition of an enzyme?” since they are always going on about how these foods have more enzymes or some such. I have never found one that knew what an enzyme actually was or that it would be unlikely to survive the digestive process.

J. Peden
February 1, 2009 11:58 pm

Bill D (23:01:37)
It doesn’t take a “peer reviewed” article to see that ipcc-related temperature reconstructions do/did not involve checking the quality of the surface station sites and the status of the temperature-sensing devices [upon which the reconstructions are based] and are therefore not themselves based upon even the most basic of scientific practices: seeing if/that your equipment is working properly.
And it doesn’t get any better from there for the ipcc-related “science” – including, of course, the idea that a “peer reviewed” article delivers the given truth or at least the current state of knowledge.

anna v
February 2, 2009 12:03 am

jeez (23:31:13) :
On this use of the term acidification. This argument is silly. The term is correct and is used correctly in these these articles whether or not you agree with the content or tone of the articles. It would be silly to use dealkanilinization as an alternative.
The effect is really like discussing the angels on the head of a pin. It is the angels that catch the imagination.
Or, “the sky is falling” was a good description for “Chicken Little”, because something fell from above, that was her definition of sky. Now with good PR linguistics she could defend herself and all her followers.

Glenn
February 2, 2009 12:03 am

Jeez,
I don’t think it is silly. I’ve read through dozens of articles, including journal articles that use the word. All seem to use acidification to refer to a process resulting in an acidic solution. The only discipline that appears to use the word to describe a change in ph is connected with global warming.
http://depts.washington.edu/mpanews/MPA103.htm
“A lesser-known impact of the rise in carbon dioxide levels will be “ocean acidification”, a term coined just five years ago.”
My first post referred to the Nature article of five years ago. Now perhaps because a new term was coined and is used by AGWers means the usage is “correct”.
I happen to think it not correct, bad word usage, misleading, and that it was coined to be used as a tool to frighten. I was, until I found out that that the oceans are not acidic, nor is there any indication that the *oceans* could ever be acidic. I don’t know much chemistry, but am not scared of the word.

Alan Wilkinson
February 2, 2009 12:51 am

Bill D (23:01:37) : [in scientific debates] only peer reviewed publications really count

Twaddle. The only thing peer reviewed publications matter for is academic promotion. Most of them are never read by anyone except their authors.
What matters in scientific debates is understanding how and why things work. Brains and honest and diligent studies are what count and it doesn’t matter a fig how the results are disseminated.

Alan Wilkinson
February 2, 2009 12:53 am

It would be silly to use dealkanilinization as an alternative.
No, it would be honest.

Alan Wilkinson
February 2, 2009 12:57 am

It would be silly to use dealkanilinization as an alternative.
No, it would be honest – preferably spelt right.

HasItBeen4YearsYet?
February 2, 2009 1:04 am

From “thefreedictionary.com”
aĀ·cidĀ·iĀ·fy (-sd-f)
tr. & intr.v. aĀ·cidĀ·iĀ·fied, aĀ·cidĀ·iĀ·fyĀ·ing, aĀ·cidĀ·iĀ·fies
To make or become acid.
You have NOT “acidified” anything until you bring it’s pH BELOW 7. In fact, if you are adding acid and the buffer’s pH is going down, you could just as easily say I’m “neutralizing” it, which would be true if you stopped at 7. Calling the process of decreasing the pH of a solution “acidification” is an example of changing the meaning of a word to advance a specific agenda.

E.M.Smith
Editor
February 2, 2009 1:09 am

Jeff L (08:32:25) : So, if in equilibrium, at 1490 ppm atmospheric CO2, the oceans reach a ph of 7.0. Of course, based on my last post & the initial plot, CO2 ratio have been higher in the geologic past. Possible implications:
[…]
2) There are other buffering mechanisms in the ocean that keep the ph above 7.0, regardless of atmospheric CO2.

I think this is more the point…
Earlier I noted the 500 Billion tons of manganese nodules on the ocean fllor. This is an example of a chemical agent presently precipitating from solution that would react with an acid. The typical problem in aquaria is accumulation of ammonia; the CO2 will help the oceans avoid their alkaline fate…
What happens when acid rain hits rocks? Some neutralization… I would expect the same in the ocean. The fact is that CO2 does not just dissolve in the ocean, it reacts. Your calculations establish the extreme limit case, reality will be much milder…
Finally, as soon as a reacting agent hits a biological system, it is dominated by enzyme chemistry, not by simple chemistry. Somehow the AGW folks miss this. The coral will do what coral enzymes do, not what naked coral skeletons do… This isn’t a physical chemistry problem, it’s a biochemistry problem; and for that I’ll take the aquarium evidence over worry and panic from a hypothetical case…

Jari
February 2, 2009 1:17 am

At least somewhere the corals are growing fast:
“Scientists have reported a rapid recovery in some of the coral reefs that were damaged by the Indian Ocean tsunami four years ago.
It had been feared that some of the reefs off the coast of Indonesia could take a decade to recover.
The New York-based Wildlife Conservation Society (WCS) found evidence of rapid growth of young corals in badly-hit areas.
http://news.bbc.co.uk/2/hi/asia-pacific/7800796.stm

Bill DeMott
February 2, 2009 1:18 am

My comment above on science requiring grants missed one important group of scientists who usually do not need competitive grants. These are scientists who work for government agencies such as NIH, NASA, EPA and NOAA. So, if you want to limit valid science to people not funded by grants, you would be limiting scientific debate largerly to work by government scientists and eliminating mostly university researchers.
Of course, scientists and engineering working for corporations also do important research. However, since they are often not encouraged to publish and are often prohibited from publishing their research, it does not contribute much to scientific debates.

Mary Hinge
February 2, 2009 1:37 am

There seems to be no shortage of theories about how rising CO2 levels will destroy the planet, yet the geological record shows that life flourished for hundreds of millions of years with much higher CO2 levels and temperatures. This is a primary reason why there are so many skeptics in the geological community. At some point the theorists will have to start paying attention to empirical data.

You have heard of evolution over there haven’t you? Corals have shown to be resiliant in geological time scales, they evolve as they adapt to the changing conditions. Like rainforests the intense competition of coral reefs man that most of the organisms function well at their optimum conditions but poorly (become less fit) once conditions stray from the optimum. It is sudden increases in sea temperatures and chemistry that cause the problems. Rapid changes will have the effect of reducing biodiversity as there will be some species that cope better with the changes (are fitter) and will reproduce more rapidly at the expense of those speciea less able to adapt to rapid changes. Once the diversity of the coral is reduced this has major effects on other marine organisms, especially fish breeding grounds.

Steven Goddard (23:24:20) :
Yet we know that atmospheric CO2 levels were much higher when corals and many species of shellfish appeared in the oceans. The physical properties of aragonite have not changed.

As discussed above the properties of the coral do change as they evolve.

David Porter
February 2, 2009 1:43 am

Bill D (14:33:58) :
Sorry I’m late in coming back to you but it was night time over here.
Obviously I cannot accept your logic. IMO it is pedantic and a lame excuse to use the more frightening and agenda driven term.
For my part I think the post above by Glenn (23:07:54) sums up exactly my feelings.

E.M.Smith
Editor
February 2, 2009 1:51 am

Richard Sharpe (10:00:02) :
Bill D asks an interesting question:
Do you assume that medical science, for example is equally unreliable?
H pylori?

And many others. Which is why after a long and sometimes shoddy history the medical field adopted very strict methods. The state of ‘climate science’ is worse than that of medicine back when they were having folks stand in puddles with magnets and sniff ether. And it needs the same formal discipline.
Help me understand what is going on here. I like to understand all the causal chains. Perhaps I have one of the links wrong.
So you are looking for the missing link šŸ˜Ž
CO2 is not going to react with a living system the same way it reacts with rocks. While there will be some acid / base neutralization inorganic chemistry going on, the wild card is all those millions of square kilometers of enzyme studded surface area on zillions of algae and microbes. There is just no way you can predict how that will turn out.
Also, on the issue of speed of change: I’ve set up more aquariums than I car to think about. The key thing is the bacteria. At first the pH goes way alkaline as the ammonia builds up, then various bacteria get established and it all settles down. In about 3 weeks. Same thing will happen with CO2. It is a scarce and rate limiting nutrient for plants. As soon as it starts rising into ‘abundant’ range in the ocean there will be a ‘bloom’ of plants and bacteria to suck it out. And never underestimate the pH adjusting power of bacterial soup…
Frankly, all I see so far is yet another research area dancing in the error bands of measurement. We have a pH that is 8.x where x can bounce around quite a bit in normal oceans. Now there is a claim of the sky falling because someone measured something somewhere and calculated a 0.1 pH unit drop? This is just silly. More averages of averages playing in the error band. Sound and fury signifying nothing.
Think the pH doesn’t change when a fish pees or poops on a coral? Where are all the white spots from this assault? How about all the acidity when the sun goes down and all those hosted algae start emitting CO2 instead of absorbing it? The corals respire. In and out. The pH at the surface is not going to be unaffected by this.

Alan Wilkinson
February 2, 2009 2:30 am

Mary Hinge: Rapid changes will have the effect of reducing biodiversity as there will be some species that cope better with the changes (are fitter) and will reproduce more rapidly at the expense of those speciea less able to adapt to rapid changes.
The planet has had many rapid climate changes in its past and the ultimate outcome seems a continuing increase in both the biodiversity and the skills of its inhabitants.

February 2, 2009 2:39 am

Coral bleaching is caused by warming sea temps?….not exactly. There are many causes, and the major cause is a sudden change in sea temperature up or down.
Not something generally associated with the AGW process, but more a part of the natural ENSO cycle. This is just another example of twisting the facts to suit a cause. Might be time to look at some facts.
Here is a marine Biology report that states:
“Coral species live within a relatively narrow temperature margin, and anomalously low and high sea temperatures can induce coral bleaching. Bleaching events occur during sudden temperature drops accompanying intense upwelling episodes, (-3 degrees C to ā€“5 degrees C for 5-10 days), seasonal cold-air outbreaks. Bleaching is much more frequently reported from elevated se water temperature. A small positive anomaly of 1-2 degrees C for 5-10 weeks during the summer season will usually induce bleaching.”
http://www.marinebiology.org/coralbleaching.htm
On the Great Barrier Reef there is no indication of the oceans warming.
http://mclean.ch/climate/GBR_sea_temperature.htm

papertiger
February 2, 2009 3:54 am

Horseshoe crab – this little bugger was crawling around the shallow coastal oceans at least 100 million years before the dinosaurs arrived. Climate changes, he has been there done that.
Floor Anthoni mentions that ocean upwelling brings stored deep water co2 to the surface making places like the Galapogos and Monterey Bay the most “acidic” parts of the ocean. These are also the most productive food locations in the seas.
Strange – I spent the better part of three hours trying to find a quoted figure for ocean pH in Monterey Bay. It’s hidden like a national defence secret – better even because the New York Times hasn’t even leaked it.
You would think that the Monterey Aquarium, USC Monterey Bay, the National Marine Sancuary with NOAA monitoring water quality 24/7, that somewhere among that seathing cesspool of climate change and ocean acid propaganda, that there would be at least one person who dipped a pH meter in the water.
It says something I think. about the results that they are not mentioned {at least anywhere I can find}.
It shows religious ferver.

papertiger
February 2, 2009 4:14 am

Also there are plenty of pristine corals in the Monterey Bay, 4,100 to 12,000 (1250 to 3660 meters) below the ocean surface. Because they’re so deep a comprehensive survey of the various species hasn’t been done.
Here are the best pictures.

Jari
February 2, 2009 4:42 am

Papertiger:
here is Monterey Bay Aquarium Incoming Seawater pH Spot Measurements during 1994 – 2007. No bad news here so maybe it is not news. pH increased from about 7.85 in 1996 to about 8.05 at the end of 2006 (if I read the data correctly).
http://sanctuarymonitoring.org/regional_docs/monitoring_projects/100240_167.pdf

carlbrannen
February 2, 2009 5:17 am

Fascinating topic. This was the one part of global warming I was at all worried about, as I didn’t know anything about it. Still don’t but it seems less worrisome.

Bill D
February 2, 2009 5:30 am

Alan Wilkinson (00:51:23) :
Bill D (23:01:37) : [in scientific debates] only peer reviewed publications really count
Twaddle. The only thing peer reviewed publications matter for is academic promotion. Most of them are never read by anyone except their authors.
What matters in scientific debates is understanding how and why things work. Brains and honest and diligent studies are what count and it doesnā€™t matter a fig how the results are disseminated.
Alan–I assume that you do not publish in science. You are mistaken on this one. What are the altenatives to publishing in a legitimate scientifiic journal?
I can post my research on the internet, present it at a scientific meeting, send copies of a manuscript to experts, write it up in a thesis, or perhaps put it in a government report. In all of these cases, the research will be largely ignored by the scientific community, it will not be cited by other scientists in their work and it will be soon forgotten by everyone, probably in a year or less.
If I publish in a scientific journal, the work will be read, discussed and cited by other scientists. If the work is important it will be read by graduate students training in the field. In any case, it will be listed on search engines such as google scholar.
When I go to meeting and institutions around the world, scientists who don’t know me personally know who I am by my journal publications. For example, right now I am working at a research institution in Europe for six months and this morning I was introduced to several young scientists working in my field who were familiar with publications that are relevant to their experiments.
As Alan correctly points out, many peer reviewed articles are hardly read or cited. The best work is well cited by other scientists. For example, when you
do a search on http://scholar.google.com/
Try searching under “coral bleaching” and the first paper listed is by O. Hoegh-Guldberg (1999). Toward to bottom of the entry you can learn that this paper was cited by 722 other scientific articles. Click on this link to get a list of the 722 articles. Reading a portion of the 722 articles will give an idea why this paper by Hoegh-Guldberg is considered so important by other scientists. One can assume that anyone interested in coral bleaching should be very familiar with this paper (which you can download as a PDF). It is also listed first by Google because it is well cited and influencial.
Most scientific papers are not influencial and are only cited by a handful of other articles. You can be sure that a paper cited by over 700 other papers is very important. It takes a while for a scientific paper to accumulate citations. If you disagree with conclusions of a scientific paper, you can check out whether and how the paper has been cited by other scientists. Do their results contradict or support this earlier study?

Bruce Cobb
February 2, 2009 5:36 am

“Ocean Acidification” is just one more in the long line of Climate-Speak, which are (mostly) 2-word phrases invented for the sole purpose of propagandizing the AGW ideology, and keeping people in an alarmed state, including the following: climate chaos, climate disruption, climate catastrophe, climate emergency, climate criminal, carbon pollution, carbon footprint, ecological footprint, and terracide.
If you can control the language, you control thought to a great degree.

pkatt
February 2, 2009 5:44 am

“E.M.Smith (18:09:27) :
Any tropical underwater volcano growing corals?
Nothing like an existance proof if you can find it.”
*Raises hand*… Um the Hawaiian islands. If it werent for volcanic activity creating the islands the ocean would be too deep to support coral growth and since each island is “built” from the ocean floor to the surface (tallest mtn on earth) creating places for the coral to grow, Id say thats pretty good proof of a tropical underwater volcano growing corals..
Does it seem strange to anyone but me that they measure Co2 near a live volcano? What a curious world we live in.
PS I too own a reef tank and while it has an optimal temp range, growth of corals depend more on the chemistry of the water, light and circulation. Our system does not have a cooler so in the summertime at times the temp of my tank is higher than it should be by a degree or two, it has yet to bleach my pretty coral and I have a population that is quickly outgrowing my tank.

Jon
February 2, 2009 5:46 am

The Bikini “Castle Bravo” 15 Megaton was at the time the worlds largest, but since then the Russians have tested far larger weapons, like the “Tsar” more than 3 times the power 8 years later.
As far as coral, it is and will be fine.

Sekerob
February 2, 2009 5:51 am

From a different corner, the Christian Science Monitor:
How air imperils the sea
Continue ;D

Bill D
February 2, 2009 6:14 am

nobwainer (Geoff Sharp) (02:39:15)
Geoff: You state that the temperature has been stable in the Great Barrier Reef and link to graphs that show only small changes.
If you look at the O. Hoegh-Guldburg (1998) paper that I mention above, on page 24 (I think) you can learn that 1998 experienced the warmest SST (sea surface temperatures) in the 95 years of instrumental data at the Great Barrier Reef. You can also learn that 1998 saw the biggest coral bleaching and die off that had been recorded up to that time. This does not look a much of a temperature change, but a one or two degree increase can be enough to cause a coral die-off. Many readers of this blog probably know that 1998 was a very warm year in many places on earth.
Added note: The Hoegh-Guldberg (1998) paper is listed as a “book” and is available as a doc file not a PDF or a journal article as I state above. Most other papers under “coral bleaching” are journal articles.

Mary Hinge
February 2, 2009 6:23 am

Alan Wilkinson (02:30:34) :
The planet has had many rapid climate changes in its past and the ultimate outcome seems a continuing increase in both the biodiversity and the skills of its inhabitants.

All a question of time scales, the immediate time frame, for instance the human life span) diversity will be greatly reduced. In the longer time frame, (100,000’s of years ) then you’re right. care to wait that long?

pkatt
February 2, 2009 6:42 am

“Steven Goddard (19:28:25) :
Iā€™m not trying to construct an argument that corals or shellfish can survive in acidic water. Because they canā€™t.”
I think you are misinformed here. Lately some deep dives have been discovering life that depends on deep ocean volcanic vents. To quote from the dive record in the link on the 2nd picture of the dive summary: Closeup of tube worms and long neck barnacles that colonize volcanic vents on the seafloor. They live by metabolising the hot, acidic, mineral laden fluids being pumped out of the vents.
http://data.gns.cri.nz/hazardwatch/2004/10/nz-scientist-explores-underwater.html
Isnt Nature marvelous:)

Robert
February 2, 2009 7:20 am

Bruce Cobb (05:36:20) :
as in Newspeak?

Eric
February 2, 2009 7:35 am

Alan wilkinson said
“This is a misrepresentation of the basic chemistry.
There are two aqueous dissociation constants involved:
(1) H2CO3 ā† K1 ā†’ H+ & HCO3- ā† K2 ā†’ 2H+ & CO3ā€“
as well as the solubility reaction involving Henryā€™s Law at the surface:
(2) H20 + CO2 ā† Ks ā†’ H2CO3
Adding more CO2 to the sea whether by increasing atmospheric CO2 or by cooling the water which modifies Ks can only drive equation 1 to the right, increasing the amount of CO3ā€“ in the water.
Likewise, increasing the amount of CO3ā€“ in the water (by dissolving Calcium Carbonate can only drive equation (1) to the left (incidentally making the water more alkaline.)
In this scenario the only way the ocean can be made more acidic without also increasing carbonate concentrations is to remove the carbonate by forming more shells and coral, not less.
So the alarmists are actually complaining that the increased coral and shell productivity over the last two centuries is going to slow down because of the decreased alkalinity it has caused. That is the real message of Feeny et al., in basic chemistry stripped of its spin.”
The story told by the experts in this field is
http://ioc3.unesco.org/oanet/FAQacidity.html
“When CO2 dissolves in seawater, carbonic acid is produced via the reaction:
This carbonic acid dissociates in the water, releasing hydrogen ions and bicarbonate:
The increase in the hydrogen ion concentration causes an increase in acidity, since acidity is defined by the pH scale, where pH = -log [H+] (so as hydrogen increases, the pH decreases). This log scale means that for every unit decrease on the pH scale, the hydrogen ion concentration has increased 10-fold.
One result of the release of hydrogen ions is that they combine with any carbonate ions in the water to form bicarbonate:
This removes carbonate ions from the water, making it more difficult for organisms to form the CaCO3 they need for their shells. ”
A more detailed exposition of the Chemistry can be found at
http://www.realclimate.org/index.php?p=169
“The pH of seawater is buffered by the chemistry of carbon, just as is the chemistry of blood and cellular fluids. The buffering action arises from the fact that the concentrations of the various carbon species are much higher than is the concentration of H+ ions. If some process tries to add or remove H+ ions, the amount of H+ ions required will be determined by the amount of the carbon species that have to be converted from one form to another. This will be an amount much higher than the actual change in H+ concentration itself.
Most of the carbon in seawater is in the form of HCO3-, while the concentrations of CO32- and dissolved CO2 are one and two orders of magnitude lower, respectively. The equilibrium reaction for CO2 chemistry in seawater that most cogently captures its behavior is
CO2 + CO32- + H2O == 2 HCO3-
where I am using double equal signs as double arrows, denoting chemical equilibrium. Since this is a chemical equilibrium, Le Chatlierā€™s principal states that a perturbation, by say the addition of CO2, will cause the equilibrium to shift in such a way as to minimize the perturbation. In this case, it moves to the right. The concentration of CO2 goes up, while the concentration of CO32- goes down. The concentration of HCO3- goes up a bit, but there is so much HCO3- that the relative change in HCO3- is smaller than the changes are for CO2 and CO32-. It works out in the end that CO2 and CO32- are very nearly inversely related to each other, as if CO2 times CO32- equaled a constant.

Tim Clark
February 2, 2009 8:13 am

Bill D (05:30:49) :
do a search on http://scholar.google.com/
Try searching under ā€œcoral bleachingā€ and the first paper listed is by O. Hoegh-Guldberg (1999). Toward to bottom of the entry you can learn that this paper was cited by 722 other scientific articles. Click on this link to get a list of the 722 articles.

I would like to find that paper but I cannot use Google (company policy).
Could you please just give me the publisher, ie. Science.mag or Elshivier etc.
Thanks.

Richard Sharpe
February 2, 2009 8:42 am

Bill D is still at it:

If you look at the O. Hoegh-Guldburg (1998) paper that I mention above, on page 24 (I think) you can learn that 1998 experienced the warmest SST (sea surface temperatures) in the 95 years of instrumental data at the Great Barrier Reef. You can also learn that 1998 saw the biggest coral bleaching and die off that had been recorded up to that time. This does not look a much of a temperature change, but a one or two degree increase can be enough to cause a coral die-off. Many readers of this blog probably know that 1998 was a very warm year in many places on earth.

So, how is this increase in temperature (which I believe is nicely explained by a couple of natural things) related to human produced CO2 and acidification?
Those two things are really the topic of this thread, no matter how much you want to derail the thread.

papertiger
February 2, 2009 8:48 am

Here is a passage from Bill D’s
most cited peer reviewed paper.
Like their terrestrial counterparts -rainforests- coral reefs are
being endangered by a diverse range of human-related threats.
Eutrophication and increased sedimentation flowing from dis-
turbed terrestrial environments, over-exploitation of marine
species, mining and physical destruction by reef users are the
main causes of reef destruction (Sebens 1994). Mass coral bleachingā„¢ is yet another major contributing factor to decline of coral reefs.
Although reef building corals are not likely to not become extinct in the long term, their health and distribution will be severely compromised for many hundreds of years unless warming is mit-
igated. The implications of this ā€šfutureā„¢ are enormous and
should be avoided with all the resources at our disposal.

We just found out that rainforests aren’t all that endangered, and that biologists were keeping it hush hush.
Eutrophication – I looked that up and it means pumping sewage into rivers.
Not good but not climate change either. And it’s the city county muni governments who are our primary polluters. Whens the last time you heard of a pol saying that? It’s easy to mouth the climate change mantra but do something real like modernize sewers which is one of the basic government functions anyhow? Congressman Doolittle was setting up small scale tests of various new water treatment plants. But he got kneecapped by the SAC Bee and decided not to run again. Besides Doolittle I haven’t heard anything more concrete then “Where are all the Salmon?” from the other pols.
Global warming isn’t a factor.

MartinGAtkins
February 2, 2009 8:48 am

“The declaration, supported by Prince Albert II of Monaco.”
I presume the good Prince will lead by example and ban the Grand Prix.

papertiger
February 2, 2009 8:50 am

http://www.publish.csiro.au/?act=view_file&file_id=MF99078.pdf
Climate change, coral bleaching and the future of the worldā„¢s coral reefs
Ove Hoegh-Guldberg
There you go Tim.

foinavon
February 2, 2009 9:01 am

Just to reinforce Eric’s account: Eric (07:35:24)
The oceans, much like our blood, are buffered by carbonic acid (H2CO3) -bicarbonate (HCO3-) – carbonate (CO3–) equilibria of the form:
CO2(aq) + H2O == H2CO3 == H+ + HCO3- == H+ + CO3–
where “==” denotes equilbrium dissociations.
The positions of the equilibria depend on the pH and the proton affinity of the acids (H+ donors) and bases (H+ acceptors). The latter can be defined by the pKa of each conjugate acid-base pair, which is equivalent to the pH at which there is equal amounts of the acid and base component of the conjugate pair. More quantitatively the concentration of any of the species can be easily determined using the equation (Henderson-Hasselbalch):
pH = pKa + log[base/acid]
so if the pKa for the bicarbonate – carbonate equilibrium is 9.1 in seawater (can’t remember the exact value) then at pH 8.1 the carbonate concentration is around 10% of the bicarbonate concentration. If the ocean pH drops by 0.3 pH units (say), the carbonate concentration drops to 5% of the bicarbonate concentration…and so on…
So it’s straightforward that acidification of the oceans results in a decrease in the concentration of carbonate even if the acidification is the result of enhanced CO2 in the oceans. Bicarbonate which is already in large excess as Eric stated, doesn’t change that much. The reduction in carbonate concentration is a problem for sea animals that “fix” CO2 in the form of carbonates to make shells, exostructures (corals) or skeletal parts.

Allen
February 2, 2009 9:10 am

Coral reefs in the Ordovician were of a 100% different composition, rugose corals, which are extinct. Modern corals (scleractinians) did not evolve until hundreds of millions of years later. They are not comparable in any way. Please get your facts straight before posting this nonsense.

pablo an ex pat
February 2, 2009 9:14 am

Eric
It looks as if the system of buffering works to nullify any significant impact of CO2 on pH. There maybe local effects that force the pH outside the norm but the oceans will naturally correct as they mix. And mix they do, consider as evidence the spread of the Tritium from the Pacific to the deep Atlantic.
Pushing the equation to the right means that extra Bicarbonate is being produced by the action of Carbonic Acid on Calcium Carbonate. As the supply of Calcium Carbonate vastly outstrips the available supply of CO2 so we’re safe for many many centuries, phew !
Oh my goodness, the planet has checks and balances already built in that prevent excursions. Wow. : )

MartinGAtkins
February 2, 2009 9:31 am

“Oceans May Soon Be More Corrosive Than When The Dinosaurs Died”

The last time the oceans endured such a drastic change in chemistry was 65 million years ago, at about the same time the dinosaurs went extinct. Though researchers do not yet know exactly what caused this ancient acidification,

The Chicxulub meteor must have been made of dry ice.

Steven Goddard
February 2, 2009 9:31 am

Neven,
As far as the “pace of change” goes, what pace are you referring to? Corals and shellfish are not exposed to the atmosphere, and are not directly impacted by changes in atmospheric CO2.
Reading through some of the literature people have posted about the modeled relationships between atmospheric CO2 and ocean pH, it would appear impossible for aragonite based shellfish and corals to have existed at most times in the past – yet they did. If people fail to consider the buffering of the ocean, they will probably reach some very poor conclusions.

MartinGAtkins
February 2, 2009 9:34 am

Oops!
Link to the last my post.
http://tinyurl.com/c55ta7

Steven Goddard
February 2, 2009 9:35 am

Allen,
You said “Coral reefs in the Ordovician were of a 100% different composition”
That is incorrect. They are all CaCO3 based and respond in the same way to pH. Chemistry has not changed.

HasItBeen4YearsYet?
February 2, 2009 9:59 am

“GLOBAL WARMING, FISH, AND SUNSPOTS””
There are cycles in the ocean, and like climate above the water that below the water is determined in part by the sun.
The warmeres don’t take those cycles into account, and hence misinterpret changes in things like fish population in a given area to “overfishing” when the fish have just moved temporarily.
Some sanity in the literature, this on in “Nature” in 2001,

Ecosystems: Reef corals bleach to survive change
Andrew C. Baker1
Top of page
Abstract
The bleaching of coral reefs, in which symbiotic algae are lost from reef-building invertebrates, is usually considered to be a drastic and damaging response to adverse environmental conditions1, 2. Here I report results from transplant experiments involving different combinations of coral host and algal symbiont that support an alternative view, in which bleaching offers a high-risk ecological opportunity for reef corals to rid themselves rapidly of suboptimal algae and to acquire new partners. This strategy could be an advantage to coral reefs that face increasingly frequent and severe episodes of mass bleaching as a result of projected climate chang

The BBC reports on the resilience of coral…

Coral springs back from tsunami
Scientists have reported a rapid recovery in some of the coral reefs that were damaged by the Indian Ocean tsunami four years ago.
It had been feared that some of the reefs off the coast of Indonesia could take a decade to recover.
The New York-based Wildlife Conservation Society (WCS) found evidence of rapid growth of young corals in badly-hit areas.

Funny, isn’t it, how those scientists who tell us they know everything keep getting blind-sided by reality.

Richard M
February 2, 2009 10:02 am

Allen (09:10:00) :
“Coral reefs in the Ordovician were of a 100% different composition, rugose corals, which are extinct. Modern corals (scleractinians) did not evolve until hundreds of millions of years later. They are not comparable in any way. Please get your facts straight before posting this nonsense.”
Whether this is correct or not, just why should we care what the compostion is of the coral reefs? For some reason many people want to forget our world is all about “survival of the fitest”. That doesn’t mean we shouldn’t understand the effect of our lifestyles. However, knee-jerk reactions are uncalled for.

Richard M
February 2, 2009 10:07 am

HasItBeen4YearsYet? (09:59:34) :
Excellent!
Isn’t it strange how reports like these are ignored. It reminds me of the way forest fires were viewed years ago. Now, we understand they are “healthy”.
So much is not understood or misunderstood that will eventually fill libraries.

TJ
February 2, 2009 10:07 am

Can anybody point me to a clear explanation of how PH change over the past two hundred years was measured?

J. Peden
February 2, 2009 10:09 am

Eric (07:35:24), from Real Climate:
“The equilibrium reaction for CO2 chemistry in seawater that most cogently captures its behavior is
CO2 + CO32- + H2O == 2 HCO3-
[…]
It works out in the end that CO2 and CO32- are very nearly inversely related to each other, as if CO2 times CO32- equaled a constant. ā€œ

I don’t think so. From a simple inorganic chemistry standpoint, here’s what happens when CO2 interacts with H2O in the presense of Ca:
CO2 + H20 = H2CO3 = H + HCO3
HCO3 = H + CO3
CO3 + Ca = CaCO3
So right at the beginning, there is no obvious way that adding more CO2 to the H2O will decrease CO3, despite what RC thinks is a “most cogent” equation.
Otoh, if there is a way, then RC should show the equations, etc., not simply summarize/make pronouncements as per its “most cogent” offering.
“Most cogent” is not a term from inorganic chemistry, where words have been replaced by equations for a reason. Chemical symbols and quantitative reactions replace the inferior qualitative words.

Bill D
February 2, 2009 10:29 am

pkatt (06:42:22) :
ā€œSteven Goddard (19:28:25) :
Iā€™m not trying to construct an argument that corals or shellfish can survive in acidic water. Because they canā€™t.ā€
I think you are misinformed here. Lately some deep dives have been discovering life that depends on deep ocean volcanic vents. To quote from the dive record in the link on the 2nd picture of the dive summary: Closeup of tube worms and long neck barnacles that colonize volcanic vents on the seafloor. They live by metabolising the hot, acidic, mineral laden fluids being pumped out of the vents.
http://data.gns.cri.nz/hazardwatch/2004/10/nz-scientist-explores-underwater.html
Isnt Nature marvelous:)
Pkatt:
Steven who you quote above specifically states that “corals and shellfish” are adversely effected by acid conditions.
How does your quote on “tube worms and barnacles” relate to corals and “shellfish”? Clearly corals are not going to survive in deep acidic waters. Shellfish is not a valid taxonomic term, but barnacles are not usually included.

Allen
February 2, 2009 10:34 am

Steven,
I know you are not that bright, but surely you can understand that organisms which are entire family levels apart, would respond to things like ph in a different manner? Do you really think that all ocean organisms process calcium carbonate in the exact same way? The truth is; the ability to secrete calcium carbonate is a convergent feature, it evolved many many times, as an adaptation to living in an ocean full of dissolved Ca ions. Each time it evolved slightly different, which is why corals are very sensitive to ph, while other CaCo3 secreting organisms react differently. Your article shows a complete lack of understanding about how this process works. You should be ashamed of yourself.

pablo an ex pat
February 2, 2009 10:35 am

Here’s an interesting piece that talks about the beneficial effects of extra CO2 on some important classes of marine organisms when it comes to building their exoskeltons.
http://oceanacidification.wordpress.com/2008/04/24/can-seashells-save-the-world/

Bill D
February 2, 2009 10:36 am

Richard Sharpe (08:42:16) :
Bill D is still at it:
Richard:
My point is that conditions in Australia and accross the tropics are hot enough to kill off corals. I don’t see why it is necessary that one be concerned about the cause of the warm water, only that it’s warm enough now to threaten corals. The article that I quoted noted that the sea surface temperature in 1998 was the highest recorded until that time in the 95 year record of thermometer data. I think that it’s important to know that corals are now theatened by the recent or current conditions. If the oceans cool during the next decades they should be ok, as long as acidification does not increase.

Frediano
February 2, 2009 10:42 am

accuracy, precision, resolution, and most of all, uncertainty and significance.
All terms glaringly missing from the AGW religion, which behaves not as science, but cargo cult science. it is, purely political science.
The politicization of science has been a giant leap backwards for mankind, which let’s face it, is an integral part of the politics.

Bill D
February 2, 2009 10:45 am

Richard Sharpe–
It will be interesting to learn whether the record hot weather in Australia during the past month will heat the ocean enough to cause further coral bleaching and death. Surely we can study the effect of warm temperature even if we are unsure about the cause or causes. I thought that the topic of this posting was about the effect of ocean acidification and warm temperatures on corals? Scientists studying these problems may have their concerns about the local or global climate, but one does not need to know any about causes to gather lab and field data about effects of these factors on coral survival and growth.

Simon Evans
February 2, 2009 10:47 am

Steven Goddard (09:31:48) :
If people fail to consider the buffering of the ocean, they will probably reach some very poor conclusions.
Exactly so – for example, they might think that the fact of corals having existed at times when atmospheric CO2 was higher is evidence of their immunity to changing concentrations of CO2. That would be a very poor conclusion.
The issue is one of acidification (I don’t have any difficulty in understanding that word). If the production of carbonic acid outpaces the rate of deep ocean carbonate release then pH will fall (and is falling). By all means make a scientific challenge as to whether or not that is happening, or make a scientific challenge to the evidence suggesting that coral calcification will be severely affected by such acidification, but unless you can give us evidence of the pH being lower during the Ordovician Era then what understanding does your reference to it add?

foinavon
February 2, 2009 10:53 am

MartinGAtkins (09:31:46) :

ā€œOceans May Soon Be More Corrosive Than When The Dinosaurs Diedā€
The last time the oceans endured such a drastic change in chemistry was 65 million years ago, at about the same time the dinosaurs went extinct. Though researchers do not yet know exactly what caused this ancient acidification,
The Chicxulub meteor must have been made of dry ice.

You’re not far off Martin!
There is uncertainty over whether the Chicxulub impact made much of an impact on the end-Cretaceous extinction/global warming/ocean anoxia/acidification. The evidence indicates that it predates the K/T boundary event by around 300,000 years.
However there is better evidence for rising CO2 cocentrations during a long, long period resulting from the massive prolonged tectonic events that gave rise to the Deccan Traps in what is now India. This seems to have been supplemented by a massive rapid rise of CO2, quite possibly due to the K/T boundary impact that blasted into carbonate-rich deposits and vapourised humungous amounts of carbonate back into CO2. So not quite “dry ice”….but still a very solid source of massive amounts of CO2.
e.g.
Beerling DJ et al. (2002) An atmospheric pCO(2) reconstruction across the Cretaceous-Tertiary boundary from leaf megafossils Proc. Natl. Acad. Sci. USA 99 (12): 7836-7840
This group determined CO2 concentrations (plant stomatal pore proxies) right through the K/T boundary (KTB) event and concluded:
…..Our record shows stable Late Cretaceous/ Early Tertiary background pCO(2) levels of 350-500 ppm by volume, but with a marked increase to at least 2,300 ppm by volume within 10,000 years of the KTB. Numerical simulations with a global biogeochemical carbon cycle model indicate that CO2 outgassing during the eruption of the Deccan Trap basalts fails to fully account for the inferred pCO(2) increase. Instead, we calculate that the postboundary pCO(2) rise is most consistent with the instantaneous transfer of approximate to 4,600 Gt C from the lithic to the atmospheric reservoir by a large extraterrestrial bolide impact. A resultant climatic forcing of +12 W(.)m(-2) would have been sufficient to warm the Earth’s surface by approximate to7.5degreesC, in the absence of counter forcing by sulfate aerosols. This finding reinforces previous evidence for major climatic warming after the KTB impact and implies that severe and abrupt global warming during the earliest Paleocene was an important factor in biotic extinction at the KTB.”
In general many of the major extinction events in the deep past are associated with massive and prelonged tectonic events resulting in enhanced greenhouse warming, ocean anoxia (reduced pH…reduced oxygen). In fact the end-Cretaceous extinction is still not fully-defined due to the problem of dating of the Chicxulub impact (it was too early), the absence of a crater that properly coincides with the K/T boundary, and the relative contributions of tectonics (Deccan Traps) and impacts in the rather horrible events 65 million years ago…
…mind you, as mammal descendants of the plucky survivors, we came out of it rather well…

Bob Coats
February 2, 2009 10:57 am

Tim Clark (19:54:38)
Tim,
The problem with Wilkinson’t formulation of the carbonate-bicarbonate equation is that he omitted solid-phase CaCO3, which dissolves in the presence of carbonic acid to form Ca++ and HCO3-. So if you add CO2 to the system, (thru respiration, dissolution of atmos. CO2), pH drops, and CACO3 dissolves; if you take it out (outgassing, photosynthesis), pH increases, and CACO3 precipitates. You can see the evidence of this yourself in streams or lakes in limestone terrain, where CaCO3 deposits as a crust on macrophytes, periphyton, etc.

HasItBeen4YearsYet?
February 2, 2009 10:58 am

MUGGED BY REALITY
Corals Flourish at ”Nuked” Atoll

“I didn’t know what to expect, some kind of moonscape perhaps. But it was incredible, huge matrices of branching Porites coral had established, creating thriving coral reef habitat,” Zoe Richards, from Australia’s James Cook University, said of the trip to the atoll in the South Pacific.

Scientists Stunned By Coral Growth At Bikini Atoll

Bikini Atoll was the site of nearly two dozen nuclear tests from 1948 until 1958. The recent finding of extravagant coral growths have stunned the scientists who recently dove at Bravo Crater.

Another scare fades – Warming does not kill coral

The Great Barrier Reef is far more resilient to rising water temperatures than scientists feared, with less than 1 per cent of its coral affected by bleaching after the hot summer.

Bob Coats
February 2, 2009 10:59 am

Bill D (10:29:28)
Bill D,
Who are you?
Bob C

Robert S
February 2, 2009 11:03 am

Glenn
Do you think ā€œacidificationā€ means ā€œto make more acidicā€? If so, is a ph of 8 acidic or not? Is 8 more acidic than 9? Does a drop from 9 to 8 signify an increase in *acidity*?
No, that’s not what it means. Acidification is the process of becoming acidic. And no, that does not mean it actually has to become acidic.
TallBloke,
And Iā€™m sorry you are the willing dupe of propagandists Robert…Regardless of the ā€˜correctnessā€™ of terminology, the aim of scienceā€™s pronouncements to the public should always be to inform and educate, not mislead. Sadly, the agenda of the alarmista is to do just that.
This is just nonsense. Clearly, the BBC piece is shoddy journalism (specifically the title “Acid Oceans”), but the word acidification was not created as propaganda. Frankly, this is a dumb argument.

E.M.Smith
Editor
February 2, 2009 11:09 am

George E. Smith (19:55:13) : So just where has it been tried out; growing Corals in acid that is.
And it can’t be just any acid. The ‘logic flaw’ in the acidification argument is that it’s the hydronium that matters. If I may ‘tag on’ to your point:
To the organism, the carbon dioxide is food. Put in a common pH adjusting mineral acid like sulphuric or hydrochloric in your test and show the coral die, so what? Attack by Cl- does not ‘make their day’. Put in CO2 + HCO3- instead and they will eat it spitting out O2 in the process and the electron that gives it the “-” is absorbed by neutralization with an H+ in making H2O.
The more carbonate there is the more ‘things grow’ and the less H+ is left. Unless you can ‘spike’ the pH instantly to the lethal range or use a toxic negative ion, life is good with carbon dioxide and carbonate. This is why the corals in the tank grow better with added CO2.
Sidebar: There is a bit that needs to be considered about carbon dioxide vs carbonic acid. MOST (by far) of the CO2 in the ocean will be dissolved, it will not be forming hydronium ions as carbonic acid. From the wiki:
Carbon dioxide dissolved in water is in equilibrium with carbonic acid:
CO2 + H2O ā‡Œ H2CO3
The hydration equilibrium constant at 25Ā°C is Kh= 1.70Ɨ10āˆ’3: hence, the majority of the carbon dioxide is not converted into carbonic acid and stays as CO2 molecules. In the absence of a catalyst, the equilibrium is reached quite slowly. The rate constants are 0.039 sāˆ’1 for the forward reaction (CO2 + H2O ā†’ H2CO3) and 23 sāˆ’1 for the reverse reaction (H2CO3 ā†’ CO2 + H2O

This means that the naive calculations of pH based on straight mass done by some folks above are just that, naive. They need adjustment for the fact that most of the CO2 stays CO2 and makes no hydronium ions, thus no change in the ‘pressure of hydrogen’ pH.
Sidebar2: Then there is the fact that living systems use CO2 chemistry as a buffer (yes, CO2 is a buffer in blood… again from the wiki):
Role of carbonic acid in blood
Carbonic acid is an intermediate step in the transport of CO2 out of the body via respiratory gas exchange. The hydration reaction of CO2 is generally very slow in the absence of a catalyst, but red blood cells contain carbonic anhydrase which both increases the reaction rate and disassociates a hydrogen ion (H+) from the resulting carbonic acid, leaving bicarbonate (HCO3-) dissolved in the blood plasma. This catalysed reaction is reversed in the lungs, where it converts the bicarbonate back into CO2 and allows it to be expelled.
Carbonic acid also plays a very important role as a buffer in mammalian blood. The equilibrium between carbon dioxide and carbonic acid is very important for controlling the acidity of body fluids, and the carbonic anhydrase increases the reaction rate by a factor of nearly a billion to keep the fluids at a stable pH.

Now the wiki talks about mammalian blood, but do yah think maybe an organism that bases it’s whole structure around a carbonate skeleton might have a decently evolved carbonate metabolism? Maybe?
http://www.jbc.org/cgi/content/abstract/283/37/25475
Oh golly, I guess it does… and almost the same enzyme too… (Clue #1!)
So these corals that we’re all worked up about take the solution of CO2 and deliberately turn it into HCO3- to use it (i.e. react it with Ca+ to make a skeleton). Gee, they don’t seem to be very scared of raising the carbonate forming reaction rate by billions of times and raising the level inside there bodies! (Clue #2).
Life likes and depends on CO2 and expects high levels of carbonate inside the body. It is a fundamental factor in the metabolism of living things from primitive plants and corals all the way up to mammals. The enzyme systems evolved very early in the process. It is not a horrible toxin, it is a fundamental building block of all life at the cellular and enzyme level.
With insufficient carbonate, we, and corals, die. We have deliberate systems inside our body to make more ‘acid’ from CO2 as a way of preventing the pH shifting too much to the alkaline side and we excrete as waste products compounds like urea that turn to ammonia. (Clue #3)
These folks: http://oceanacidification.wordpress.com/2008/08/05/coral-calcification-responds-to-seawater-acidification-a-working-hypothesis-towards-a-physiological-mechanism/
postulate that since the corals grew better with HCO3- but not so well in ‘acidified’ water that maybe, just maybe it was because the acidification used drove the CO2 reaction away from having HCO3- available to the corals. More CO2 makes the corals grow better (tested in a pH range from 7.6 to 8.2 btw… corals don’t just up and die at pH 8.0) but more non CO2 acidification slowed the corals. So just don’t dump sulphuric acid in the ocean and add more CO2 if you want to grow great corals… (Clue #4)
Everything in this process says that we (corals and humans) evolved in a world with plenty of CO2 and want more, but do not particularly want a more alkaline world (and try at every turn to keep our metabolism from becoming alkaline). The pH of blood is about 7.4 (Clue #5)
Take a few minutes to think about the clues and string them together. Now ask yourself: Do I really think a move of 0.1 pH toward a less alkaline environment, especially by a mechanism that raises HCO3- availability, would be harmful to corals?

Tim Clark
February 2, 2009 11:11 am

papertiger (08:50:34) :
http://www.publish.csiro.au/?act=view_file&file_id=MF99078.pdf
Climate change, coral bleaching and the future of the worldā„¢s coral reefs
Ove Hoegh-Guldberg

Thanks!

February 2, 2009 11:22 am

I do not accept “coral bleaching” as being the result of either CO2 or warming: click
As we can see, while CO2 rises, the planet’s temperature is falling. Yet the worldwide “coral bleaching” scare is blamed on higher temperatures.
[charts source] [scroll down; this is a great page with lots of good info.]
And it is unreasonable to attribute “coral bleaching” to global warming, since much greater warming took place a thousand years ago: click
“Coral bleaching” appears to be the next “drowning polar bears” scare. It seems that fatigue would set in from the alarmists constant arm-waving over natural events like this.

Ron de Haan
February 2, 2009 11:40 am

AGW
Climate Change
Melting Glaciers
Melting Ice Caps
Melting Sea Ice
Ocean Acidification
Human induced CO2
Runaway Global Temperatures
Drowning Polar Bears
Coral Bleaching
Hurricanes
Kaiser Penguins
The list of subjects taken hostage by the AGW doctrine are endless.
The red line running through all the horror stories is for humanity to cut back on CO2 emissions at any price.
But who speaks for the plants and the trees?
http://canadafreepress.com/index.php/article/8110

Steven Goddard
February 2, 2009 11:49 am

Allen,
The saturation point of CaCO3 (which controls the ability of sea creatures to precipitate aragonite shells) is a chemical property and has nothing to do with biology. You aren’t being so clever as you think you are.
A good explanation of how buffering works in the ocean from Wikipedia:
http://en.wikipedia.org/wiki/Ocean_acidification
Leaving aside direct biological effects, it is expected that ocean acidification in the future will lead to a significant decrease in the burial of carbonate sediments for several centuries, and even the dissolution of existing carbonate sediments.[28] This will cause an elevation of ocean alkalinity, leading to the enhancement of the ocean as a reservoir for CO2 with moderate (and potentially beneficial) implications for climate change as more CO2 leaves the atmosphere for the ocean.[29]

foinavon
February 2, 2009 11:53 am

Bob Coats (10:57:15)
Yes, and one can extend that somewhat further in a pertinent direction.
precipitated carbonates (e.g. Ca++ carbonate) are also in equilibrium with dissolved carbonate (as you indicated). How does this relate to ocean chemistry and biochemistry? Much of the precipitated carbonate is in sediments on the ocean floor. On 1000’s of years timescale involved in deep ocean mixing this sedimented carbonate can help “buffer” the loss of dissolved carbonate from acidification of the surface layers, and it’s thought to do just that during periods of slow CO2 buildup or other acidification events in the deep past. However on the short term (100’s of years) it’s poorly effective, because the oceans don’t mix quickly enough.
Is there a source of precipitated carbonate in the oceans? Yes there is. Corals, shells and exoskeletal parts of sea animals that “fix” carbonate as integral parts of their structures. What happens if the oceans acidify faster than deep ocean mixing can buffer the loss of aqueous carbonate? Those animals/corals start to leach their “fixed” carbonate back into solution.
Incidentally, the Royal Society did a report on ocean acidification due to greenhouse gas emissions and the consequences which can be downloaded as a pdf from here:
http://royalsociety.org/document.asp?id=3249

Steven Goddard
February 2, 2009 12:01 pm

One more point. Consider how the oceans are continuously bombarded with rainwater at pH 5.2 or less, yet they steadily maintain a pH greater than 8. The simple-minded models which automatically correlate carbonic acid formation with lower pH are clearly deficient. It is carbonic acid which makes rainwater acidic.

Bruce Cobb
February 2, 2009 12:05 pm

Robert S (11:03:35) :
Acidification is the process of becoming acidic. And no, that does not mean it actually has to become acidic.
Really? How interesting! Would that be from the AGWers reference guide or the Climate Catastrophe encyclopedia?
So, it’s the process that’s important then, regardless of what actual state is attained? So, if you cool water down the process would be called freezing, or if you warm it, boiling? Or, when I heat my house to keep the vicious arctic cold away, I am actually burning it? I think I see now. So, this is why, in AGWer land, a .7C rise in temp over the course of a century is described as a planet that is on fire. It is all becoming extraordinarily clear now.

E.M.Smith
Editor
February 2, 2009 12:06 pm

Neven (20:19:08) : Are they the same shellfish as todayā€™s shellfish?
Depending on which time periods, in many cases, yes. Evolution has been going on for a long time and still happens today, so in theory you could say that a razor clam of today is not the same as a razor clam from a million years ago, but in fact most of our metabolic processes were laid down at the beginning of life and stay substantially unchanged. We find almost the same enzyme promoting the production of carbonic acid from CO2 in us as we find in corals, for example. Corals and humans last shared a common ancestor rather a long time ago…
Did these corals and other shellfish in the distant past have to cope with a rate of change that is a hundred times bigger than natural variability? If so, how did they do?
The problem with the ‘rate of change’ argument is that the pH changes seasonally by several 0.1 pH units. It also changes between day and night (especially at the ‘skin’ of the coral) as the algae shift from consuming CO2 to emitting it. The problem is not that 0.1/century is a fast rate of change, but that it is an almost immeasurable change in a system with such larger, faster, changes happening daily and seasonally.
This is the problem with averages of averages of averages… they hide more than they reveal. They tell us to panic over a hypothetical centuries long trend that might not even exist but to ignore far larger variations in shorter time periods. The ‘unprecedented rate of change’ evaporates as soon as you remove the veil of averaging.

nvw
February 2, 2009 12:06 pm

I am a little late to the tread but have noticed Bill D seems to have an objection about evidence from an aquarium owner that increased CO2 aids coral growth. Apparently only ā€œpeer-reviewedā€ articles in selected publications are acceptable.
Perhaps this article would pass the grade?
Iglesias-Rodriguez, M. D., Halloran, P. R., Rickaby, R. E. M., Hall, I. R., Colmenero-Hidalgo, E., Gittins, J. R., Green, D. R. H., Tyrrell, T., Gibbs, S. J., von Dassow, P., Rehm, E., Armbrust, E. V. Boessenkool, K. P. 2008. Phytoplankton calcification in a high-CO2 world. Science 320:336-340.
Although the authors do not perform the experiment on corals, the data do support what Fraizer (22:11:28) was saying that increased CO2 causes larger shells.
Redneck (01:53:09) made an interesting point about the CCD (Carbonate Compensation Depth) which is the depth below which shells composed on CaCO3 dissolve. Geologists have long known that deep sea oozes are dominated by organisms built from silica, present now in the rock record as cherts, largely because the more common carbonate-forming shells dissolve in deep waters. The geologic record does show fluctuations in the depth of the CCD ā€“ whether this is caused by changes in water depth or water chemistry should be a good place to study the effects of ocean chemistry changes.
Surprised nobody has yet mentioned the studies showing sunblock is implicated in coral mortality ā€“ the delicious irony of those do-gooder ecotourists trying to save the coral reefs are in fact agents of destructionā€¦
http://www.treehugger.com/files/2008/01/sunscreens_bleaching.php

E.M.Smith
Editor
February 2, 2009 12:18 pm

Neven (09:04:36) :
Hereā€™s a quote from the BBC article with the inaccurate ā€˜Acid Oceansā€™-title:
ā€œIt says pH levels are changing 100 times faster than natural variability. ā€
Now pray tell me, if this is true, how can creatures adapt to changes that are 100 times faster than natural variability? That would be a problem, wouldnā€™t it?

Only if it were true. Neven, I would suggest turning off the BBC.
Unfortunately they are largely just playing on the excellent reputation built up in prior decades. They no longer have a decent grasp of science and only a weak hold on truth in journalism. I don’t know why it happened, but it is a travesty. (I have fond memories of listening to the BBC on a tube shortwave decades ago – and the veracity they brought to the world… then.)
As pointed out in my prior posting, the ‘unprecedented change’ is a fiction based on averaging away vastly more rapid changes that corals already deal with just fine. (The mechanism is at the basis of all life, homeostasis via changing how much of which enzymes we make. This can be done in minutes, and is. Daily; corals shift from CO2 destruction to CO2 creation and back, with all the attendant acid / base shift that implies, as the sun rises and sets.)

February 2, 2009 12:21 pm

Globalwarming causes coral bleaching? Well, I have it on good authority that it causes other things, too: click
[enjoy the ‘hot’ music!]

Simon Evans
February 2, 2009 12:25 pm

Steven Goddard (11:49:13) :
A good explanation of how buffering works in the ocean from Wikipedia:
http://en.wikipedia.org/wiki/Ocean_acidification
Leaving aside direct biological effects, it is expected that ocean acidification in the future will lead to a significant decrease in the burial of carbonate sediments for several centuries, and even the dissolution of existing carbonate sediments.[28] This will cause an elevation of ocean alkalinity, leading to the enhancement of the ocean as a reservoir for CO2 with moderate (and potentially beneficial) implications for climate change as more CO2 leaves the atmosphere for the ocean.[29]
(your bold)
What you fail to mention, of course (either conveniently or else because your level of research really is limited to looking things up on Wikipedia) is that the full compensation effect is anticipated only after thousands of years, with the prospect of a recovery process not beginning before 2700. Read the paper, which can readily be sourced from the Wiki reference [29]:-
http://plankt.oxfordjournals.org/cgi/content/full/30/2/141
It’s a very good paper, making clear the near-term concerns regarding acidification.
Either your approach to research is to think that a link to Wikipedia’s gloss is good enough or else you have read this paper and chosen to misrepresent it here. Which is it?

E.M.Smith
Editor
February 2, 2009 12:33 pm

Neven (11:13:11) : The idea that someone rather believes some guy with an aquarium (God knows what he did and if he tells the truth) than thousands of peer-reviewed papers by scientists who spend a life time studying the oceans, makes my stomach churn. Smokey, you kill all the hope I have for humanity.
It ought not. The guy doing what I like to call ‘kitchen science’ is very valuable. Like Feynman dunking a chunk of rubber in ice water at a shuttle crash enquiry, they ask the basic question that is being ignored in the 1000’s of academic studies by ‘more learned’ folks. They are the bearers of ‘common sense’ to the debate and ask the questions that were in some cases ‘educated out’ of the specialists. Where are the clothes?…
A friend just last night shared a story. He is a mensan, retired, and teaches a robotics class for fun. One of his students wanted to use a particular approach to speed determination using a laser. He did some research that turned up papers showing it could not be done; but let the girl proceed anyway (she is very very bright…). The result? A working system for speed determination. Yes, she made it work. Why? Because he chose not to tell her it could not be done, to let her take a fresh approach. Our formal system squelches that type of thinking. That is what ‘kitchen science’ brings back to the table. It ought to give you more hope for humanity, not less.
So we have a bunch of ‘peer reviewed’ papers saying CO2 will kill coral. Yet reality says ‘add CO2 and get happy coral’. I’ll take the reality, thank you, and go looking for what the paper guys missed. Time to pick up that chunk of rubber and a glass of ice water…

Steven Goddard
February 2, 2009 12:39 pm

Simon Evans,
Try pouring some vinegar over limestone and see how long it takes for the buffering reaction to begin. It happens instantly, which is one reason why 5.2 pH rainwater can fall into the oceans continuously for hundreds of millions of years, and not lower the pH below 8.
Did you look at the Monterey Bay pH data someone linked to above? It showed pH steady or increasing during the last ten years.

pablo an ex pat
February 2, 2009 12:42 pm

Dear Foinavon and Simon Evans
You are unfortunately laboring under a false understanding of deep ocean circulation. The Royal Society did indeed say that this is a multi century process but this is not borne out by the facts.
If it is such a long process why is Tritium from 1950 and 1960’s Atomic testing in the Pacific currently being detected in the deep water of the North Atlantic ?
There is only one answer the mixing process is obviously much more rapid than it has been assumed to be. And if that’s the case the entire ocean acidification house of cards falls down.
And with rapid mixing the upwelling of Calcium Carbonate to the surface will negate any “acidification” the buffering mechanism will continue to do its job.

SteveSadlov
February 2, 2009 12:50 pm

I remain to be convinced there has been any drop at all, en masse.
If ever there was a perfect scenario for “producing” something reputed to be data, this is it.
From an objective standpoint, the task of monitoring ocean pH in any meaningful sense is a MSA / Gage R and R nightmare. But of course, from the standpoint of “proving” so called “disastrous” ppCO2 (and ergo, ocean acidification) it is the most tempting ever.

hunter
February 2, 2009 12:51 pm

CO2 caused by AGW is magic CO2.
When the oceans get warmer, more, not less CO2 is uptaken.
And AGW CO2, unlike the billions of years of CO2 in the past, cuases acids that only attacks living things, but never gets neutralized, sort of like acid blood in cheesy scifi movies.
And AGW scientists are magic, too:
They can determine clear and present signals from changes far less than the accuracy of the equipment in use, AGW scientists can look at a graph that is shwoing no change, and find in it the AGW signal tha shows the apocalypse is at hand..

HasItBeen4YearsYet?
February 2, 2009 12:51 pm

CORAL CAN’T SURVIVE EXTREME COLD?
Yes, I know they aren’t the same coral, but it’s to show that there is diversity, and almost certainly a lot more than the warmers want to admit is there. The Earth WILL survive. Even they and the harm they seek to do in the name of “saving the planet” too will pass.

Alan Wilkinson
February 2, 2009 12:57 pm

Chemical balderdash from Eric, foinavon, RC, and Bob Coates.
The equations I gave apply irrespective of any other contributions such as solid CaCO3. Obviously (well, certainly to any chemist with half a brain) if calcium carbonate dissolves there is more carbonate in the system, not less. You cannot create more bicarbonate without also creating more carbonate because of the equilibrium I gave above in equation (1).
I repeat, the only way CO2 can cause a reduction in carbonate is by carbonate being taken out of the water – eg by creation of MORE shells, coral, fishbone etc.
The rest of the blather above is just that – total ignorance of basic solution chemistry.

HasItBeen4YearsYet?
February 2, 2009 1:08 pm

@RobertS
“Acidification is the process of becoming acidic. And no, that does not mean it actually has to become acidic.”
Wrong. Adding acid to a buffer above pH 7 is called “TITRATION,” not “acidification.” If you stop at 7, you have “neutralized” the solution, not “acidified” it. It is only “acidified” once you bring the pH below 7.
In order to “acidify” the ocean, you would have to add a bolus of acid sufficient to change the pH from basic to acidic. In the case where the ocean pH is being reduced, by whatever means, it would be proper to say “reducing the alkalinity,” not “acidification.” Sorry, but they do deliberately misuse the word in order to deceive, as is done in this modern age of doublespeak on many other occasions (like Leftists calling themselves “Liberals” when they are, in the extreme, much closer to fascists, who are about as far from “liberal” as one can get.)
Also, I have given references above to show that the pH of the ocean varies widely from location to location, as well is with temperature and depth.

E.M.Smith
Editor
February 2, 2009 1:10 pm

Simon Evans (12:25:44) :
Either your approach to research is to think that a link to Wikipediaā€™s gloss is good enough or else you have read this paper and chosen to misrepresent it here. Which is it?

Logic error of false dichotomy.
He, like me, may simply like to use Wikipedia because it is available to everyone, typically written in a style readable by most, has no copyright infringement risks, and is a good cause to support. Unless their content is wrong, there is no reason to avoid them. (Though, yes, you do have to keep a check on the quality; their AGW content is seriously flawed… but you seem to know that judging from your attitude about Wiki šŸ˜‰
You also assert that his providing a readable wiki explanation of things is equivalent to a ‘research’ behavour (and further seem to assert that reading peer reviewed papers is research but anything else is not…). Lighten up! Some of us here are more interested in learning what’s really going on in a readable way than we are about “Pedagogy Wars, Part V, Revenge of the Peers!”

SteveSadlov
February 2, 2009 1:17 pm

RE: Frediano (10:42:01) :
accuracy, precision, resolution, and most of all, uncertainty and significance.
——–
Yep! My thoughts as well. If ever there was a branch of science in need of Quality 101, climate science, as well as, investigators in other natural sciences crafting their hypothesis based on its tenets, are it. Talk about Gage R & R and either they start running like vampires from a cross, or, immediately resort to ad hom.

Alan Wilkinson
February 2, 2009 1:19 pm

Bill D, I have in a previous life as a research chemist published science in peer reviewed journals and taught and been taught at graduate level.
As you mention there are many ways of recording and disseminating scientific information and research, both public and private. Writing books, creating databases, maintaining archives are some others.
In business, what matters is what works and what is true. That is the sole consideration. Formal journal peer review adds very little value if any to that equation.

Bill D
February 2, 2009 1:21 pm

Bob Coats (10:59:54) :
Bill D (10:29:28)
Bill D,
Who are you?
Bob C
Bob–we seem to be on the same wave length. I’m an American biology professor on sabbatical at the Centre for Limnology, Dutch Institute for Ecological Research, Royal Dutch Academy of Sciences. I am setting up a mesocosm lab experiment to start next week, so I will soon be too busy on research to pay so much attention to blog. You can find my publications at Google Scholar, under “W. R. DeMott” Perhaps doing scientific research for the last 30 years, some of which has been supported by grants from the National Science Foundation, makes me very suspect as a source of information in the aquatic sciences. My current project is supported by the Dutch Academy of Sciences. None of the papers that I’ve published deals with climate change, but I have a manuscript under review on how the food chain of a deep lake changed during 21 years of warmer temperatures and altered thermal stratification regime.
I place a big emphasis on having my undergraduates and graduate students read , discuss and criticize original scientific papers, rather than just reading the condensed and simplified versions found in college text books. As you have probably noted, I have been encouraging readers of this science blog to take the same approach and look at the original science data and papers. Some of my more recent papers published in Limnology and Oceanography are available in PDF format for anyone to read and for everyone to criticize. Unlike many of the people who post on this blog, I feel proud about the accomplishments of American scientists and our standing among scientist from around the world.
Bob–what’s your position/background?

E.M.Smith
Editor
February 2, 2009 1:25 pm

HasItBeen4YearsYet? (20:22:49) :
THIRD OF THREE, TAKE TWO
Reply:[…]
FYI, posts here are moderated, so they donā€™t show up until approved. ~charles the moderator

Most of the time you make a post, it shows up instantly on your own screen with a line saying it is ~”awaiting moderation”. But every so often that feedback to you simply disappears. Yet the original is still in the ‘in basket’ of the moderator who doesn’t know that you have no feedback. This is a bug in the software somewhere.
So when you post something and it ‘disappears’ just wait. It isn’t some magic sauce in your text deleting things nor moderator error. It’ just the feedback to you that is missing and your posting will show up when the moderator sends it on.
Thankfully, this bug is rare. It’s only hit me two or three times in several months; and once you know what it is, it’s easy to ignore. (I *think* it happens when you cause a refresh of the panel before the ‘awaiting moderation’ feedback shows up in the posting step; i.e. you hit submit, then cause a re-load of the page before the submit does. But that is till speculative on my part.)

Tim Clark
February 2, 2009 1:44 pm

Simon Evans (12:25:44) :
What you fail to mention, of course (either conveniently or else because your level of research really is limited to looking things up on Wikipedia) is that the full compensation effect is anticipated only after thousands of years, with the prospect of a recovery process not beginning before 2700. Read the paper, which can readily be sourced from the Wiki reference [29]:-
http://plankt.oxfordjournals.org/cgi/content/full/30/2/141

Now this gentlemen, illustrates a few points about the CO2 is bad proponents and the continual mantra of peer-review. Simon here, and you must read his post to get the full effect of the disconnect, is stating something or other about the CCD or carbonate reduction and uses this paper as AGW reference.
What we learn is either:
He didn’t even read the paper, or he hoped no-one else would either, or both.
In the last few years, evidence has accumulated that calcifying organisms are likely to be affected by ocean acidification. Therefore, the production of calcium carbonate will probably decline, although conversely global warming, increasing stratification and sea level rise may also stimulate increases in global calcification. As acidification reaches the deep ocean, it will cause pronounced shallowing of the lysocline depths for calcite and aragonite, leading most probably to an almost complete cessation of deep-sea calcium carbonate burial for some centuries. Here, I briefly review the consequences of these and other changes on future ocean calcium carbonate cycling, and the consequences of this for future climate. Associated climate impacts are not likely to be significant over the next few centuries, but will become increasingly important thereafter. After the carbonate compensation response to acidification has run its course, extra CO2 is expected to be left behind in the atmosphere, protecting against future ice ages.
Now there’s a reference I can really sink my teeth into. :<}
Better practice your critical analysis, there Simon.

Richard Sharpe
February 2, 2009 1:45 pm

HasItBeen4Years said:

CORAL CANā€™T SURVIVE EXTREME COLD?
Yes, I know they arenā€™t the same coral, but itā€™s to show that there is diversity, and almost certainly a lot more than the warmers want to admit is there. The Earth WILL survive. Even they and the harm they seek to do in the name of ā€œsaving the planetā€ too will pass.

If there have been no peer-reviewed papers, then those corals are a myth!

E.M.Smith
Editor
February 2, 2009 1:46 pm

paminator (22:21:45) :
Prof Tim Wootton (Dept. Ecology & Evolution,
ā€œOver the entire span of the data, ocean pH is clearly declining as atmospheric CO2 increases, but at a rate an order of magnitude faster than predicted by current physical models.ā€
Sounds like we yet more worthless models.

Yes. Or the declining pH is from other causes than CO2 so of course the CO2 change is disconnected from the pH change to some large extent.
Coincidence, Correlation, Causality is the mantra.
There is no causality shown.
There is a broken correlation shown (way off model / predictions).
That says to me that CO2 is most likely a coincidence and that the true driver for ocean pH is elsewhere. Perhaps in the megatons of sulphate, nitrate, etc. that are the real pollutants? Perhaps in the megatons of ammonia no longer produced in the oceans from all the animals we haul out each year?
Who knows. But as long as we are tilting at the windmill of CO2 we will never find out.
Sidebar: Genentech just cut short a lung cancer study because the two drugs being used in combination were so effective it was not moral to continue (with some folks dying from lack of the drugs…) Avastin was one of them, I think. This is Good News! Lung cancer is one of the ‘biggies’. Just heard this on CNBC and will need to look into it more.

Neil Crafter
February 2, 2009 1:49 pm

Bill D (10:45:49) :
Richard Sharpeā€“
It will be interesting to learn whether the record hot weather in Australia during the past month will heat the ocean enough to cause further coral bleaching and death. Surely we can study the effect of warm temperature even if we are unsure about the cause or causes. I thought that the topic of this posting was about the effect of ocean acidification and warm temperatures on corals? Scientists studying these problems may have their concerns about the local or global climate, but one does not need to know any about causes to gather lab and field data about effects of these factors on coral survival and growth.”
If you had bothered to check you would see that where the hot weather has been in southern Australia where there are no coral reefs to kill. The weather in north east and north west Australia, where the coral reefs are, has been fairly cool. Sorry, no alarmist threat to corals here.

Steven Goddard
February 2, 2009 1:51 pm

Bill D,
Can you point us to some measured ocean pH data from the last 20 years? Monterey Bay does not support the contention that pH is declining. Is there other raw data which does? In order to see a 150% increase in acidity over the remainder of the century (as the IPCC has reportedly claimed,) we would need to see greater than 15% increase per decade.
TIA

Simon Evans
February 2, 2009 1:56 pm

E.M.Smith (13:10:12) :
Simon Evans (12:25:44) :
“Either your approach to research is to think that a link to Wikipediaā€™s gloss is good enough or else you have read this paper and chosen to misrepresent it here. Which is it?”
Logic error of false dichotomy.

Hmm. Just possibly. As a matter of fact, though, which anyone can follow up, the Wiki quotation Steven Goddard made makes a total hash of representing the papers it references.
Now, do you think Al Gore was being alarmist in suggesting potential sea-level rises without giving any sense of how long it might be before they could come about? I do.
Do you think, if you look at the papers Wiki references, that S.G’s post was being misleading in suggesting a recovery process without giving any sense of how long it might be before it comes about? I do.
Credibility works both ways. It’s motes and planks, you know. In my opinion, the self-proclaimed ‘sceptics’ will not gain any credibility until they can demonstrate an objectivity that is at least equal to that which they demand (entirely properly) from others. S.G.’s post was misleading. I do not know whether or not he knew that.

Steven Goddard
February 2, 2009 2:02 pm

Neil Crafter,
The coral reefs in Australia are in the north, where they have been having unusually cool weather this summer.
http://www.bom.gov.au/cgi-bin/silo/temp_maps.cgi?variable=maxanom&area=nat&period=month&time=latest

Steven Goddard
February 2, 2009 2:03 pm

Neil – sorry I didn’t see that you were quoting someone else and saying the same thing.

E.M.Smith
Editor
February 2, 2009 2:07 pm

Bill D (23:01:37) : only peer reviewed publications really count.
Sorry Bill D, but I must disagree. Peer reviewed publications are a very very important part of the process, but there is much more that ‘really counts’.
I would put truth and accuracy high on that list. I’d add a dose of ‘kitchen science’ as a cross foot sanity check. I’d even hold out that reality is the ultimate ‘peer reviewer’ and an existence proof trumps all other ‘peers’.
Peer reviewed publications are not the be-all and end-all of science, they are at most the gatekeeper on what makes it to widely published and add a tiny bit of quality control (unless you think all peer reviewed papers are guaranteed to be truth…). Nothing more.
Oh, and look at the history of Energy Conversion Devices Corporation for a modern example of a guy doing research in his kitchen and changing what science knew…
http://en.wikipedia.org/wiki/Stanford_R._Ovshinsky
I lived through the time when all the ‘peers’ were saying he was a fraud, quack and lier and that his claimed effect ‘could not exist’. He was rejected by ‘peer reviewed journals’ then beaten over the head with the fact of that rejection. He was also right. Even when he had demonstrated devices, ‘peers’ accused him of fraud (ignoring the value of existence proofs). Peer review is not the be-all and end-all and is often a large impediment to advance.
I won’t bother trying to cite some peer reviewed science that was wrong; there is just too much of it…

Steven Goddard
February 2, 2009 2:09 pm

Nothing ever changes. People will always protect their territory.
During Wegener’s lifetime, his theory of continental drift was severely attacked by leading geologists, who viewed him as an outsider meddling in their field.[12]
http://en.wikipedia.org/wiki/Continental_drift

HasItBeen4YearsYet?
February 2, 2009 2:19 pm

@ Richard Sharpe (13:45:49)
“If there have been no peer-reviewed papers, then those corals are a myth!”
How’s NOAA?

John W.
February 2, 2009 2:33 pm

A couple of points.
1. A coworker sat on the particle physics panel for a prominent science journal. One of his co-panelists was a VERY prominent scientist who rubber stamped any submission from a source he approved of politically, and rejected most else.
2. REAL science, as opposed to quackery, can take place as easily in a kitchen as in a zillion dollar lab. What matters is the quality of the experimental/test set up, how carefully environmental conditions are monitored, the accuracy (NOT precision) of the measurements/ observations, etc.
The focus on ā€œpeer reviewā€ and sneering at ā€œkitchenā€ science is nothing more than a red herring intended to keep us from noticing a ā€œgood old boyā€ peer review network rubber stamping publications, especially the ones based on dodgy science coming from the zillion dollar labs.

SteveSadlov
February 2, 2009 2:40 pm

Ovshinky’s merry band were of a similar stripe as their big boss. True innovators. Much of the tech revolution owes itself to these folks. Some of them went on to great effect in the realm of CMOS integrated circuits.

SteveSadlov
February 2, 2009 2:40 pm

Sorry, typo, Ovshinsky.

February 2, 2009 3:08 pm

Bill D (06:14:22) :
Geoff: You state that the temperature has been stable in the Great Barrier Reef and link to graphs that show only small changes.
If you look at the O. Hoegh-Guldburg (1998) paper that I mention above, on page 24 (I think) you can learn that 1998 experienced the warmest SST (sea surface temperatures) in the 95 years of instrumental data at the Great Barrier Reef. You can also learn that 1998 saw the biggest coral bleaching and die off that had been recorded up to that time. This does not look a much of a temperature change, but a one or two degree increase can be enough to cause a coral die-off. Many readers of this blog probably know that 1998 was a very warm year in many places on earth

I think you are missing my point Bill, the NOAA graphs I linked to, clearly show a rise in sea temp at 1998 from the ENSO event, and then came back to the normal flat level (its not increasing overall). The ENSO event is a major bleacher of coral because of the SUDDEN temp change. Its a natural cycle.
There is no point getting lost in the chemical composition discussion….the rate of change is minuscule.

E.M.Smith
Editor
February 2, 2009 3:10 pm

Oh Drat! I’m being forced into an “Appeal to Authority” argument…. I hate appeal to authority… but for things that require a shared standard, like word definitions, we do need some sort of shared authority. Sigh.
Robert S (11:03:35) :
Glenn
Do you think ā€œacidificationā€ means ā€œto make more acidicā€? If so, is a ph of 8 acidic or not? Is 8 more acidic than 9? Does a drop from 9 to 8 signify an increase in *acidity*?
No, thatā€™s not what it means. Acidification is the process of becoming acidic. And no, that does not mean it actually has to become acidic.

Will the OED do?
Acidification: The act or process of acidifying: Conversion into an acid.
Acidifying: Forming an acid: That combines so as to form an acid.
Acidify: To make acid or sour. Chem: to convert into an acid by combination with any substance.

At least to the extent that the OED represents usage by the normal people expected to listen to the BBC, turning a pH 8.2 in to a pH8.1 does not form an acid nor a sour stuff and is not properly called ‘acidification’. No acid end point, not acidification. QED via OED šŸ˜‰
The BBC needs a copy of the OED. If we all chipped in and bought them one, do you think they would read it? (Mine is well used šŸ˜‰

February 2, 2009 3:15 pm

Your argument of the inaccuracy of the term ā€œocean acidificationā€ is quite reasonable. Your argument that geological history shows that todayā€™s corals can survive increasing CO2 is not. I recommend reading a bit about the geological history of corals and evolution of todayā€™s coral species (brief summary and links here)

J Lo
February 2, 2009 3:20 pm

Alan Wilkinson:
You are wrong. Think of it this way:
Coral reefs are built from limestone by the reaction Ca2+ + CO32- == CaCO3, where Ca is calcium. Acidifying the ocean decreases the concentration of CO32- ions, which by le Chatlierā€™s principal shifts the equilibrium toward the left, tending to dissolve CaCO3. Note that this is a sort of counter-intuitive result, that adding CO2 should make reefs dissolve rather than pushing carbon into making more reefs. Itā€™s all because of those H+ ions.
It took me a while to figure out too.

E.M.Smith
Editor
February 2, 2009 3:26 pm

nvw (12:06:20) :
Surprised nobody has yet mentioned the studies showing sunblock is implicated in coral mortality ā€“ the delicious irony of those do-gooder ecotourists trying to save the coral reefs are in fact agents of destructionā€¦
http://www.treehugger.com/files/2008/01/sunscreens_bleaching.php

Gotta love it! I especially like this bit:
“They experimented on more than half a dozen species from various sites with a range of brands, SPFs and concentrations; in all cases, they found that the sunscreens bleached the corals. By their calculations, close to 10% of all of the world’s reefs could be at risk from the 4,000-6,000 metric tons of sunscreen that wash off on an annual basis.”
Gee, wonder how well sunscreen correlates with warmer weather … might start to explain some of those ‘heat related bleaching’ events šŸ˜‰

J Lo
February 2, 2009 3:35 pm

Alan Wilkinson:
So, in essence, you’re looking at it like this:
(1) H2CO3 ā† K1 ā†’ H+ & HCO3- ā† K2 ā†’ 2H+ & CO3ā€“
And it is correct that if you add CO2, you should have more CO3-.
But you’re missing the is ADDITIONAL reaction of HCO3- H+ & CO3-. The H+ ion is “fungible” in the oceanic chemistry.

Ellie in Belfast
February 2, 2009 3:44 pm

Steven Goddard (11:49:13) :
“Allen,
The saturation point of CaCO3 (which controls the ability of sea creatures to precipitate aragonite shells) is a chemical property and has nothing to do with biology.”
Actually, biology can influence precipitation significantly. Most people are thinking of bulk solution chemistry, but biological surfaces have big influences at on local solution chemistry at the molecular level. Two examples:
1. Organisms can excrete or cause a local concentration of ions (e.g. calcium) which causes a local increase in the solubility product of the ionic constituents and can drive precipitation. Not the clearest , but try this ref. as an example:
http://jsedres.sepmonline.org/cgi/content/abstract/75/2/190
2. Organisms can have a direct effect on nucleation – often fortuitously, but in some cases by evolutionary ‘design’. Nucleation is the process by which a crystal (or pure precipitate) begins. Biological surfaces are not smooth at a molecular level, but are like a forest sticking up into the solution. Some molecules, often proteins, bind ions (e.g. Ca2+) ‘nucleation sites’ and help to begin the processes such as shell building.
For example – nucleation in molluscan shell formation: http://www.ncbi.nlm.nih.gov/pubmed/16413789
Calcium is actually supersaturated in the oceans, yet precipitation does not readily ocurr without these biologicially accelerated processes.
If CO2 in the atmosphere is complicated, there are probably two orders of magnitude of additional complications in the ocean when you add chemistry and biology to the mix.

E.M.Smith
Editor
February 2, 2009 3:59 pm

@HasItBeen4YearsYet? (12:51:41) : CORAL CANā€™T SURVIVE EXTREME COLD?
fascinating link. And while we panic over a theoretical maybe someday CO2 issue, that link pointed out very real problems.
from http://www.cdnn.info/news/article/a040813.html
“Biologists undertook their own cruises to get a good look at this marvel. A band more than 13 kilometers long bristled with pale, crisscrossing branches of a stony coral, the ivory tree coral Lophelia pertusa. Some of these corals reach 35 m in height. This thicket ranked as the largest Lophelia reef then known.
“What really got attention in Norway was that [the reef] was being destroyedā€”well, smashed to smithereens,” says Watling. The scientists’ cameras showed swaths of rubble or just bald ocean floor as a result of fishing fleets dragging weighted nets through the area.
These images of destruction were particularly upsetting because researchers calculated that the Sula Ridge coral structure represents some 8,000 years of growth.”
So next time you are at a “CO2 is Evil Save The Planet” meeting and Orange Roughy is on the menu; well, you will know what the priorities are…
(I like Orange Roughy, but try to order farmed fish when possible and pelagic species when not. Bottom trawls, especially around sea mounts, are horrific destroyers – but out of sight, out of mind…)

Eric
February 2, 2009 4:01 pm

Steven Goddard (11:49:13) :says,
Allen,
The saturation point of CaCO3 (which controls the ability of sea creatures to precipitate aragonite shells) is a chemical property and has nothing to do with biology. You arenā€™t being so clever as you think you are.
A good explanation of how buffering works in the ocean from Wikipedia:
http://en.wikipedia.org/wiki/Ocean_acidification
Leaving aside direct biological effects, it is expected that ocean acidification in the future will lead to a significant decrease in the burial of carbonate sediments for several centuries, and even the dissolution of existing carbonate sediments.[28] This will cause an elevation of ocean alkalinity, leading to the enhancement of the ocean as a reservoir for CO2 with moderate (and potentially beneficial) implications for climate change as more CO2 leaves the atmosphere for the ocean.[29]

Looking at the link you have provided in context, what it says is in the first paragraph of the section on future impacts is:
“Although the natural absorption of CO2 by the world’s oceans helps mitigate the climatic effects of anthropogenic emissions of CO2, it is believed that the resulting decrease in pH will have negative consequences, primarily for oceanic calcifying organisms. These use the calcite or aragonite polymorphs of calcium carbonate to construct cell coverings or skeletons. Calcifiers span the food chain from autotrophs to heterotrophs and include organisms such as coccolithophores, corals, foraminifera, echinoderms, crustaceans and molluscs. ”
So the first step is acidification and killing off certain types of organisms.
After all this is accomplished a slower process the dissolution of CaO3 sediments will reverse the process of acidification.
So in the long run we have a silver lining. How long will this take? I think the answer is thousands of years based on what I have read of this.
Do you really believe we should regard acidification as no problem, because the problem will be reversed at some later time thousands of years later, or are you just trying to put one over on us?

Glenn
February 2, 2009 4:03 pm

Robert S (11:03:35) :
Do you think ā€œacidificationā€ means ā€œto make more acidicā€? If so, is a ph of 8 acidic or not? Is 8 more acidic than 9? Does a drop from 9 to 8 signify an increase in *acidity*?
“No, thatā€™s not what it means. Acidification is the process of becoming acidic. And no, that does not mean it actually has to become acidic.”
The authors who coined “acidification” to refer to a minor change in base ph *in* the Nature article used “becoming more acidic” to refer to this process of “acidification”. You claim acidificatiion does not mean it doesn’t actually have to become acidic. So either you or the AGW crowd has a problem, or “becoming more acidic” can actually not mean acidic, but rather a base value moving toward an acid.
Or maybe you will claim that “becoming acidic” is the same thing as “more acidic”?
Do a google search and show me one reputable definition or example of a change of alkalinity referred to as “more acidic”. Excuding of course the hundreds of thousand of AGW articles that do just that, including the original Nature article reposted below.
http://antalya.uab.es/icta/activitats/doc_seminaris_06_07/Seminaris_Master/2007_02_05_Caldeira_and_Wickett_2003.pdf
“When carbon dioxide dissolves in the ocean it
lowers the pH, making the ocean more acidic.”

Syl
February 2, 2009 4:09 pm

Best quote of the thread:
E.M.Smith (01:51:05)
Frankly, all I see so far is yet another research area dancing in the error bands of measurement.
—–
Mary Hinge (06:23:05) :
“All a question of time scales, the immediate time frame, for instance the human life span) diversity will be greatly reduced. In the longer time frame, (100,000ā€™s of years ) then youā€™re right. care to wait that long?”
But the time scales you are referring to depend on other scales such as the rise in global temperature which is turning out to be not nearly as much nor as rapid as originally projected. The problem is that many scientists have based their conclusions in their peer-reviewed papers on the original assumptions as put forth by the IPPC. In fact, in many cases, the entire reason for the research is to determine what would happen if those projections come to pass.
I think if you look at several peer-reviewed papers, you’ll see the ‘consistent withs’ and all the ‘ifs’ that lead to the conclusions when the researchers actually do due diligence.
The rhetoric in the media and on many blogs, however, is much different. The ‘alarmists’ take the conclusions at face value omitting the ‘ifs’ from their statements. The conclusions are given far more certainty than the research does. And when we find peer-reviewed papers that are not so honest in outlining the uncertainties it’s a bad mark against not only the researcher but the entire peer-review process as well.
There are many hypotheticals and uncertainties we are all dealing with here and the minimum we should all expect from every participant is to admit to them.

E.M.Smith
Editor
February 2, 2009 4:14 pm

Alan Wilkinson (12:57:13) :
I repeat, the only way CO2 can cause a reduction in carbonate is by carbonate being taken out of the water – eg by creation of MORE shells, coral, fishbone etc.
The rest of the blather above is just that – total ignorance of basic solution chemistry.

Here Here! (Hear hear?!)
I though about responding to it (the ‘blather’) but, frankly, was overwhelmed by the brokenness in their postings and just didn’t feel ready to start into it. I like teaching chemistry, but … The idea of equilibrium equations seems lost on them. And thinking about bringing up all the other ions in the ocean; that you needed to consider their chemistry as well for a real equilibrium solution… Decided it was better to just pass by quietly and hope it isn’t contagious…
When you have 500 Billion Tons of reduced metal on the surface of the ocean floor you will not be dealing with an acid condition any time soon. The ocean is deeply stabilized at a mild alkaline condition.

Glenn
February 2, 2009 4:31 pm

E.M.Smith (15:10:14) :
“Oh Drat! Iā€™m being forced into an ā€œAppeal to Authorityā€ argumentā€¦. I hate appeal to authorityā€¦ but for things that require a shared standard, like word definitions, we do need some sort of shared authority. Sigh.”
I say go straight to the source or origin, if possible, of a word usage, and interpret meaning in context, rather than resorting to putting words in people’s mouths. A word can be used anyway a person wants, as long as the meaning is defined and adhered to. And that is what I did, to the authors that coined “ocean acidification”. They refer to it as ā€œWhen carbon dioxide dissolves in the ocean it lowers the pH, making the ocean more acidic.ā€
So now we have to determine what they meant by “more acidic”, and it is inferred clearly from the above quote; adding CO2 to the ocean makes the ocean “more acidic”. Yet their own “scenario” shows that the ocean ph has not, and will not reduce to an actual value below 7 until sometime around 2250 AD.
So they are predicting real acidic ocean conditions in the future, as “in the process of becoming acidic” definition of acidification.
Yet they use the term “more acidic” to explain current changes in ocean ph, as another definition of acidification.
In other words, they refer to what they think will happen in a couple hundred years, to what is happening today. More than bold and enabling. And wrong. Predicting and knowing are different things. It’s pure propaganda.
Bruce Cobb (12:05:51) got it:
“So, if you cool water down the process would be called freezing, or if you warm it, boiling? Or, when I heat my house to keep the vicious arctic cold away, I am actually burning it? I think I see now. So, this is why, in AGWer land, a .7C rise in temp over the course of a century is described as a planet that is on fire. It is all becoming extraordinarily clear now.”

E.M.Smith
Editor
February 2, 2009 4:47 pm

Alan, you have cheered me up enough that I think I will add a pitch to the game…
Alan Wilkinson (17:08:36) :

John Philip (12:01:09) : The acidification (or de-alkalinisation) is a concern because it will make it harder for calcifying organisms to make hard structures. This requires seawater to be supersaturated with calcium and carbonate ions to ensure that once formed the CaCO3 does not dissolve.


So by this logic, it is not possible to have fresh water muscles, clams, etc. since fresh water is not even remotely near saturated with calcium and carbonate… I’ll have to tell my buddies to stop using fresh water clams for catfish bait since they don’t exist. Oh, and tell the folks in the Great Lakes that zebra muscles are no longer a problem… (Yes, it’s that darned non-peer reviewed existence proof thing again; too bad you can’t make it go away…)
This is a misrepresentation of the basic chemistry.
There are two aqueous dissociation constants involved:
(1) H2CO3 ā† K1 ā†’ H+ & HCO3- ā† K2 ā†’ 2H+ & CO3ā€“
as well as the solubility reaction involving Henryā€™s Law at the surface:
(2) H20 + CO2 ā† Ks ā†’ H2CO3
Adding more CO2 to the sea whether by increasing atmospheric CO2 or by cooling the water which modifies Ks can only drive equation 1 to the right, increasing the amount of CO3ā€“ in the water.

And what does the intermediary HCO3- and the CO3- do?
From: http://oceanacidification.wordpress.com/2008/08/05/coral-calcification-responds-to-seawater-acidification-a-working-hypothesis-towards-a-physiological-mechanism/
“Coral nubbins were incubated for 8 days at three different pH (7.6, 8.0, and 8.2). To differentiate between the effects of the various components of the carbonate chemistry (pH, CO32āˆ’, HCO3āˆ’, CO2, Ī©), tanks were also maintained under similar pH, but with 2-mM HCO3āˆ’ added to the seawater. The addition of 2-mM bicarbonate significantly increased the photosynthesis in S. pistillata, suggesting carbon-limited conditions. ”
So what does that mean? It means that more HCO3- (bicarbonate ion) makes coral happier and gets them growing faster because they are no longer ‘carbon-limited’. Think about it… I’ll wait …
Now if you start taking the HCO3- out of the middle, both the CO3– and the H2CO3 will be trying to ‘fill in the middle’. The bottom line is that coral growth is ‘carbon limited’ to what washes up from the bottom (ancient CO3– side) or what comes from the air via dissolved CO2.
And that is why the aquarium with added CO2 and happy corals speaks more volumes than all the Revenge of the Peers ever will.

Simon Evans
February 2, 2009 4:54 pm

So this is the best some of you have got? You wish to challenge the definition of ‘acidification’? Do you really wonder why so many would be inclined to dismiss your actions as nothing more than propagandising after that? Truly, very deeply feeble and pathetic, if that is what you choose to emphasise in your commentary! Call it de-alkalinasation if you prefer, I couldn’t care less! For goodness sakes, try to talk about the science rather than pursuing these silly point-scoring ventures – you just make yourselves seem ridiculous and petty (which does rather suit my POV, I have to say – by all means make yourselves seem ridiculous and petty!).

Pragmatist
February 2, 2009 4:56 pm

“I recommend reading a bit about the geological history of corals and evolution of todayā€™s coral species…”
It should be noted that one of the references here is to a Ken Anthony, research fellow at University Queensland. Anthony is the beneficiary of some $15 million dollars in research grants from NOAA, Packard Foundation, Australian government and ARC. Anthony describes his own work as: “A large part of my work is based on experimental analyses coupled with the development of mathematical models.”
As even the lay person is coming to understand, the ability of the computer models to approach a margin of accuracy in eco-systems and climate prediction is doubtful. Given the (unwritten) intent of the massive funding to establish an AGW link to ocean acidification – the entire body of work remains suspect.

E.M.Smith
Editor
February 2, 2009 4:59 pm

Eric (07:35:24) :
Alan wilkinson said
ā€œThis is a misrepresentation of the basic chemistry.
One result of the release of hydrogen ions is that they combine with any carbonate ions in the water to form bicarbonate:
This removes carbonate ions from the water, making it more difficult for organisms to form the CaCO3 they need for their shells.

And this is the broken bit. As noted in my prior posting a real world lab test with growing corals found that they wanted more bicarbonate… That the process drives toward more bicarbonate is a good thing.

J. Peden
February 2, 2009 5:04 pm

J Lo:

So, in essence, youā€™re looking at it like this:
(1) H2CO3 ā† K1 ā†’ H+ & HCO3- ā† K2 ā†’ 2H+ & CO3ā€“
And it is correct that if you add CO2, you should have more CO3-.
But youā€™re missing the is ADDITIONAL reaction of HCO3- H+ & CO3-

J Lo, no one is missing the “additional” right side of the equation, which proceeds in dynamic equilibrium with the left – which itself actually starts with:
CO2 + H2O = H2CO3….. then, etc..
If you add more CO2, more CO3 results by virtue of “mass action”. That’s why there are “equations” to begin with. On adding more CO2, the ratios involving the components of each side of the equation will remain the same, but the quantities/concentrations of each constituent will increase, including CO3.
This is simple inorganic chemistry 101. You simply can’t get less of the right side by adding more of the left side.

pablo an ex pat
February 2, 2009 5:12 pm

Dear Simon Evans
As I wrote to you personally plus your cohort Foinavon a little while back to point out the obvious, rapid ocean recirculation means that acidification or delakalinization is a completely busted flush.
And there has been no response then I have to presume that you can’t find a way to disagree with me but on the contrary like to argue for arguments sake. Not a new tactic and not an effective one but a tactic nonetheless.
I have to presume that you prefer to labor under misaprehension than to discover truth.
Good night old boy, sleep well.

SteveSadlov
February 2, 2009 5:29 pm

During the deep past, the oceans were indeed very rich. What was the partial pressure of CO2 in those ancient times? Of course, much, much higher than it is (or ever could possibly be) today. The coming crisis is not one of too much CO2, it is one of too little. Terraforming is looking better and better all the time.

Bob Coats
February 2, 2009 5:33 pm

Bill D (13:21:02)
Bill,
Yes, we do seem to be on the same wavelength! I enjoy your posts; I must say there are an awful lot of thick-headed and opinionated contributors to this site.
My background is in hydrology and water quality; I have collaborated over the years with a research group at Lake Tahoe (I am a “visiting scholar” at U.C. Davis, but make my living as a consultant). I had a paper in Climatic Change a couple of yrs ago on “The Warming of Lake Tahoe” which showed that increasing thermal stability is a major impact of the long-term warming trend (you can download a copy at http://www.hydroikos.com). I have a follow-up paper in review at the same journal on regional trends, impacts and drivers of climate change in the Tahoe basin. And we have some interesting on-going research on the effects of climate change on the Lake.
I would love to hear more about your work on climate change and deep lakes. You should have come to the Chapman Conf. at Tahoe last spring, on “Lakes and Reservoirs as sentinels of climate change”.
We should continue this conversation “off-line”. My e-mail is: coats(at)hydroikos.com
Bob Coats

Richard Sharpe
February 2, 2009 5:34 pm

HasItBeen4YearsYet said:

@ Richard Sharpe (13:45:49)
ā€œIf there have been no peer-reviewed papers, then those corals are a myth!ā€
Howā€™s NOAA?

Perhaps your sarcasm detectors are not working, or perhaps you are simply enabling those species of coral to pop into existence now that they have been vouchsafed by peer-reviewed papers.

Glenn
February 2, 2009 5:39 pm

Simon Evans (16:54:23) :
“So this is the best some of you have got? You wish to challenge the definition of ā€˜acidificationā€™? Do you really wonder why so many would be inclined to dismiss your actions as nothing more than propagandising after that? Truly, very deeply feeble and pathetic, if that is what you choose to emphasise in your commentary! Call it de-alkalinasation if you prefer, I couldnā€™t care less! For goodness sakes, try to talk about the science rather than pursuing these silly point-scoring ventures – you just make yourselves seem ridiculous and petty”
100% innuendo, ad hominem and baseless opinion. Should have been moderated IMO.
AGW propaganda seems to be a rather frequent consideration in the skeptical crowd, and I see no reason why reasoned arguments to show the existence of propaganda should be considered silly, ridiculous, petty, feeble or pathetic.
“(which does rather suit my POV, I have to say – by all means make yourselves seem ridiculous and petty!).”
Whats this, some kind of hopeful self-fulfilling prophecy about your intimations that these claims of propaganda are propaganda themselves?
LOL.

Eric
February 2, 2009 5:46 pm

E.M.Smith (16:59:35) said
Alan wilkinson said
ā€œThis is a misrepresentation of the basic chemistry.
One result of the release of hydrogen ions is that they combine with any carbonate ions in the water to form bicarbonate:
This removes carbonate ions from the water, making it more difficult for organisms to form the CaCO3 they need for their shells.”
And this is the broken bit. As noted in my prior posting a real world lab test with growing corals found that they wanted more bicarbonateā€¦ That the process drives toward more bicarbonate is a good thing.

So explain why the following scientists found that more CO2 hurts corals:
http://www.redorbit.com/news/science/666546/growing_acidity_of_oceans_may_kill_corals/index.html
“Growing Acidity of Oceans May Kill Corals
By Juliet Eilperin, Washington Post Staff Writer
“… Scientists have conducted a few ocean acidification experiments in recent years. All have shown that adding carbon dioxide to the water slows corals’ growth rate and can dissolve pteropods’ shells.
Langdon, who conducted an experiment between 1996 and 2003 in Columbia University’s Biosphere 2 lab in Tucson, concluded that corals grew half as fast in aquariums when exposed to the level of carbon dioxide projected to exist by 2050. Coupled with the warmer sea temperatures that climate change produces, Langdon said, corals may not survive by the end of the century.
“It’s going to be on a global scale and it’s also chronic,” Langdon said of ocean acidification. “Twenty-four/seven, it’s going to be stressing these organisms. . . . These organisms probably don’t have the adaptive ability to respond to this new onslaught.”
Stanford University marine biologist Robert B. Dunbar has studied the effect of increased carbon dioxide on coral reefs in Israel and Australia’s Great Barrier Reef. “What we found in Israel was the community is dissolving,” Dunbar said.
Caldeira has mapped out where corals exist today and the pH levels of the water in which they thrive; by the end of the century, no seawater will be as alkaline as where they live now. If carbon dioxide emissions continue at their current levels, he said, “It’s say goodbye’ to coral reefs.”
These people are genuine researchers not hobbyists. They have subjected their publications to peer review. I doubt that your experiments have been done as carefully.

February 2, 2009 5:58 pm

It has been shown pretty conclusively that atmospheric and oceanic CO2 don’t harm coral, but rather, that CO2 spurs coral growth.
And the oceans are not warming nearly enough to heat coral the several degrees necessary to kill it. It is arguable whether the oceans are warming at all.
So “coral bleaching,” as another AGW argument, fails.
It’s unfortunate that this must be repeated so often: it is not the responsibility of skeptics to prove that AGW exists or doesn’t exist. It is the responsibility of AGW proponents to show conclusively that the climate and ocean are behaving unnaturally, and as a direct result of human activity; specifically, due to the emission of carbon dioxide.
So far, the AGW hypothesis has failed completely. The climate is well within its normal, natural historical parameters. CO2 is rising while the planet is cooling, thus falsifying the AGW/CO2 hypothesis [and don’t show us your always-inaccurate models, they don’t prove anything; they can’t even model today’s climate when all historical climate data is programmed in].
Complaining about which term to use for ocean pH is just an impotent fallback position when the AGW/coral argument fails.

E.M.Smith
Editor
February 2, 2009 6:08 pm

Simon Evans (13:56:27) :
Hmm. Just possibly. As a matter of fact, though, which anyone can follow up, the Wiki quotation Steven Goddard made makes a total hash of representing the papers it references.

Fair enough. Then might I suggest a bit more attack the message and a bit less attack the messenger? (And if it really bugs you, get on Wiki and ‘clean up’ the hash!)

envirochiq
February 2, 2009 6:08 pm

You’ve said things such as,
“One also has to wonder how they measured the pH of the ocean to 4 decimal places in 1751, since the idea of pH wasnā€™t introduced until 1909.”
before, referring to how measurements such as pH can be recorded for an era preceding the invention of such concepts.
Just so you know, there are ways to measure pH, temperature, carbon levels, etc. for earlier periods in time based on the soil cores, ice cores, fossil samples, and other pertinent geological data that is of that time.

Steven Goddard
February 2, 2009 6:11 pm

Bob Coats,
Perhaps you can enlighten some of us “thick headed” people about how shellfish flourished in the ocean when CO2 levels were greater than 4,000 PPM. Reading through some of the theoretical scientific literature, what actually happened should have been impossible.
Also, if you have links to any raw ocean pH data over the last few decades that would be much appreciated.

HasItBeen4YearsYet?
February 2, 2009 6:26 pm

@Glenn (16:03:31) :
“The authors who coined ā€œacidificationā€ to refer to a minor change in base ph *in* the Nature article used ā€œbecoming more acidicā€ to refer to this process of ā€œacidificationā€.”
THE OPERATIONAL TERM THERE IS “COINED,” MEANING THAT’S A TERM WHOSE USAGE THEY INVENTED BECAUSE THAT IS NOT THE WAY IT WAS USED IN THE PAST, AND THEY DID THAT IN ORDER TO DECEIVE.
ALSO, JUST BECAUSE SOMEONE ELSE USES THE INCORRECT TERMINOLOGY DOESN’T MAKE IT RIGHT, EVEN IF IT’S FROM THE PROPAGANDISTS AT “NATURE.”
SOMETIHNG CAN NOT BECOME “MORE ACIDIC” UNLESS IT ALREADY IS ACIDIC TO BEGIN WITH, PERIOD.

Glenn
February 2, 2009 6:30 pm

Do these studies of ocean ph actually detect and measure acids, or is CO2 and carbonic acid just assumed to be the reason for changes in ph?
The latest study by Wootton in Washington State was published by PNAS, and I only have access to the abstract. The reason why I wonder about this is that the area studied has suffered much pollution, runoff, waste, oil and such, and all contain various acids, and it looks to me, acidic in general. There are many articles on this pollution, and it appears that the Canadian city of Victoria continues to dump millions of liters of untreated sewage into the Straits there.
http://www.pnwlocalnews.com/sanjuans/isj/news/20129379.html
“Now, everyday, 120 million liters of raw sewage and toxic chemicals are dumped into our shared waters, creating pollution hazards for human and marine health,” the letter notes.

HasItBeen4YearsYet?
February 2, 2009 6:41 pm

For those of you who won’t accept something because it doesn’t appear in a refereed journal, Frank J. Tipler has a word for you

If one reads memoirs or biographies of physicists who made their great breakthroughs after, say, 1950, one is struck by how often one reads that ā€œthe referees rejected for publication the paper that later won me the Nobel Prize.ā€ One example is Rosalyn Yalow, who described how her Nobel-prize-winning paper was received by the journals. ā€œIn 1955 we submitted the paper to Scienceā€¦. The paper was held there for eight months before it was reviewed. It was finally rejected. We submitted it to the Journal of Clinical Investigations, which also rejected it.ā€

Peer review ain’t what it’s cracked up to be, and frequently a lot less.

E.M.Smith
Editor
February 2, 2009 6:49 pm

Ellie in Belfast (15:44:29) : Actually, biology can influence precipitation significantly. Most people are thinking of bulk solution chemistry, but biological surfaces have big influences at on local solution chemistry at the molecular level.
The also have active transport processes. One extreme example is how salt is handled. Some fish (and even some non-fish like the Iguana of Easter Island) can excrete salt.
In humans it is widely known that when lost at sea you will die if you drink salt water (due to the inability of your kidneys to excrete a stronger salt concentration than sea water). Less widely known is that you can take a ‘sea water enema’ and survive. The colon has active transport of water (to solidify feces) and can extract fresh water from sea water. I know of at least one scandinavian family lost at sea that survived using this trick.
If CO2 in the atmosphere is complicated, there are probably two orders of magnitude of additional complications in the ocean when you add chemistry and biology to the mix.
A point I was wandering around earlier that you have made far more eloquently. h/t

Steven Goddard
February 2, 2009 6:55 pm

envirochiq,
Are you suggesting that there is a way to use proxies to measure the average worldwide ocean pH from the year 1751 to four digit precision? I’m keen to hear about how such wondrous magic can be performed.

Robert S
February 2, 2009 6:55 pm

Interesting…
Bruce Cobb (12:05:51):
So, if you cool water down the process would be called freezing, or if you warm it, boiling? Or, when I heat my house to keep the vicious arctic cold away, I am actually burning it?
Why do you think the definition of one word would apply to all other words as well? Since when is that standard practice in the english language?
HasItBeen4YearsYet? (13:08:15):
Wrong. Adding acid to a buffer above pH 7 is called ā€œTITRATION,ā€ not ā€œacidification.ā€ If you stop at 7, you have ā€œneutralizedā€ the solution, not ā€œacidifiedā€ it. It is only ā€œacidifiedā€ once you bring the pH below 7.
I’m sorry, but you don’t understand what titration means. Nor acidification. There are many good undergraduate texts on the subject out there. I suggest you take a look.
E.M.Smith (15:10:14) :
Will the OED do?
Sure. The first definition:
“The act or process of acidifying: Conversion into an acid.”
Like I have been saying, acidification is the process. No, it does not actually have to become acidic. Yes, it may be confusing to the general public.
Glenn (16:03:31) :
Or maybe you will claim that ā€œbecoming acidicā€ is the same thing as ā€œmore acidicā€?
Nope. I don’t believe the ocean is becoming more acidic, but it is acidifying. I believe the 2003 article to be wrong in that respect.
Oh, and the 2003 Nature article did not “coin” the word acidification–it has been in use for a good 30 years.

Marcus
February 2, 2009 7:06 pm

“This is simple inorganic chemistry 101. You simply canā€™t get less of the right side by adding more of the left side.”
Darn. I knew all those extra semesters of inorganic chemistry I took while getting my chemistry major would make me forget the basics!
Actually, simple thought experiment:
You have one atom of Ca++ and one molecule of CO3–.
Now we add one molecule of H2O and one molecule of CO2.
CO2 + H2O H2CO3.
H2CO3 HCO3- + H+
H+ + Ca++ + CO3– HCO3- + Ca++
Sum all the individual reactions:
CO2 + H2O + Ca++ + CO3– 2HCO3- + Ca++
Huh. Look at that. I add H2O and CO2 and I get less CO3–. Perhaps you should retake your inorganic 101.
Going back to the acidification: no one seems to care that I found a medical reference where alkalinization was used for an acidic solution.
ā€œAlkalinization of the urine with potassium citrate to a pH of 6.5 to 7 is recommendedā€
Here’s another one:
“We also demonstrated that acrosomal antigens detected by monoclonal antibodies MN7 and MC41 did not dissolve following the acrosome reaction in pH 5.3 media, but dissolved at pH 6.2. These data suggest that acrosomal alkalinization during incubation conducive for sperm capacitation may function to alter acrosomal contents and prepare them for release during the acrosome reaction.”
On the acidification side, how about: “Anoxia induced a cytoplasmic acidification from pH 7.6 (aerobic) to 7.4 as measured by 31P-NMR”
or “In the normal Krebs-Ringer solution of pH 7.4, lidocaine significantly reduced these relaxations in a concentration-dependent fashion. Alkalinization of pH 7.6 augmented the inhibitory effect of lidocaine on these relaxations, whereas acidification of pH 7.2 substantially abolished this effect.”
(all of the above sentences can be found by google if you want the original sources)
I _think_ that 7.2 and 7.4 are both greater than 7. Or have us AGWPers brainwashed the medical community too?

Admin
February 2, 2009 7:08 pm

This is worse than a Monty Python skit.
Being in the skeptic camp, it is painful for me to watch. Can we please focus on substantial issues and not play linguistic games which make us look foolish?
An alternative to acidification would likely be debasing? Will that be better?
CO2 DEBASING THE OCEANS!

HasItBeen4YearsYet?
February 2, 2009 7:10 pm

@ E.M.Smith (15:59:34)
“(I like Orange Roughy, but try to order farmed fish when possible and pelagic species when not. Bottom trawls, especially around sea mounts, are horrific destroyers – but out of sight, out of mindā€¦)”
YOU JUST CAN’T WIN…
Fish farming killing Israel’s coral reefs
The real “horrific [are there any other kind?>/em>] destroyers” are the Leftists who want to shut down human activity on the planet at the alter of “Mother Earth”

Glenn
February 2, 2009 7:14 pm

“In humans it is widely known that when lost at sea you will die if you drink salt water (due to the inability of your kidneys to excrete a stronger salt concentration than sea water). Less widely known is that you can take a ā€™sea water enemaā€™ and survive. The colon has active transport of water (to solidify feces) and can extract fresh water from sea water. I know of at least one scandinavian family lost at sea that survived using this trick.”
I’ll have to remember to pick up an enema kit (or several, come to think about it) to throw in the boat for the next time out. Thanks for the life saving info! I can only wonder why that family happened to have the means in hand, so to speak, when the time came to add water, stir and.. hold that thought.

February 2, 2009 7:18 pm

Eric,
Thanx for that link with all the frightening scare quotes. Do you honestly believe that article is unbiased? Do you believe there is no agenda apparent? There is so much wrong with that link it’s embarrassing.
Langdon might as well have been using a computer model to “project” his year 2050 concentrations of CO2. Note that the article quotes these scientists that coral is “dissolving” right before our eyes off the coast of Israel! Why would someone need to inject huge amounts of CO2, if today’s oceans are “dissolving” coral at today’s oceanic pH?
Those quotes are reminiscent of the scary global warming quotes originally pronounced by Al Gore and people from the IPCC: “20 meter sea level rises!” Eeek!! “Climate catastrophe!” Eeek!! “All arctic ice gone!” Eeek!! “Runaway global warming!” Eeeek!! “Polar bear extinction!” Eeeeeek!! [Note that every original IPCC scare has been debunked.]
Langdon’s experiment is surely rigged with an eye to getting grant money. Read all those scary quotes that the WaPo staff writer gets from Langdon and others, who are far from being impartial scientists. They are the reason that the inbred climate science community is so distrusted. A hobbyist who wants to see the effect of CO2 on coral growth out of curiosity is more impartial than a grant-seeking scientist with an AGW agenda and preconceived results, no?
Buried way down in the article is a peer-reviewed study refuting the “dissolving” coral situation. It’s interesting that twenty other scientists sucking at the public teat immediately monkey-piled on that one scientist who didn’t toe the globaloney line. But as Einstein retorted to 100 writers who’d said his theory of relativity was wrong: ”To defeat relativity one did not need the word of 100 scientists, just one fact.”
It’s doubtful that those 20 other nay-sayers did any CO2/coral experimenting on their own — and they apparently failed to write a refutation of the one scientific study that debunks the current CO2/coral meme: click
As Prof. Freeman Dyson said:

“The real world is muddy and messy and full of things that we do not yet understand. It is much easier for a scientist to sit in an air-conditioned building and run computer models, than to put on winter clothes and measure what is really happening outside in the swamps and the clouds. That is why the climate model experts end up believing their own models.”

So who are you gonna believe, someone on the Heinz money bandwagon [the same Heinz foundation that shoveled hundreds of thousands of dollars into James Hansen’s pockets], or an experimenter who just wants to see how coral reacts to higher CO2 levels, with no thought of profiting financially?

J. Peden
February 2, 2009 7:19 pm

Eric:
So explain why the following scientists found that more CO2 hurts corals
By this time in the course of my observation of AGW “science”, it’s the AGW “scientists” themselves who need to explain to me why I should believe a thing they say.
I started looking at AGW about 8 years ago and was literally stunned to progressively see and find out for myself that the ipcc, enc., is simply not doing science. They can’t even measure temperatures scientifically – h/t Anthony Watts – or handle data and “peer reviewed” articles correctly, but I was onto it well before that simply by looking at the TAR and how the ipcc has conducted itself therein, especially in the light of the Kyoto Protocols, which exclude countries containing 5 billion of the Earth’s 6.5 billion people from having to follow them. Some emergency, some impending distaster, eh!
And it only gets worse the more you look at it. For a recent example, check out the Nature Steig/Antarctic Warming fiasco being dissected by Steve McIntyre as we speak at Climate Audit.

E.M.Smith
Editor
February 2, 2009 7:19 pm

Glenn (16:31:55) :A word can be used anyway a person wants, as long as the meaning is defined and adhered to.
Fine. Then I hereby define “Climate Change” as “I, the speaker, enter a contract to pay Anthony Watts $100 monthly.”
From here on out, all users of “Climate Change” can send their checks or paypal payments to Anthony…
Is there really no basis for shared understanding? Apparently not with the AGW true believers… Are there really no shared truths of fundamental science nor of language? … Then maybe it is time to abandon all hope for them…

HasItBeen4YearsYet?
February 2, 2009 7:19 pm

@eez (19:08:09)
You don’t want us to “…play linguistic games which make us look foolish?”
In other “words,” Let’s talk substance, but just don’t get too specific.
Don’t you know that “words matter?” Even O’Bunko, knows that. Only a fool doesn’t care, and only a bunko artist tells them not to care (and a really talented bunko artist will twist meanings while at the same time insisting that “words have meaning”).

Admin
February 2, 2009 7:23 pm

No–get specific about substantive items.

E.M.Smith
Editor
February 2, 2009 7:30 pm

I thought that: “a word can be used anyway a person wants” line gave me a bit of an ‘Alice in Wonderland’ feeling… A quote from the other side of the looking glass that sounds painfully familiar:
‘When I use a word,’ Humpty Dumpty said, in a rather scornful tone,’ it means just what I choose it to mean, neither more nor less.’
‘The question is,’ said Alice, ‘whether you can make words mean so many different things.’
‘The question is,’ said Humpty Dumpty, ‘which is to be master – that’s all.’
Alice was too much puzzled to say anything; so after a minute Humpty Dumpty began again. ‘They’ve a temper, some of them – particularly verbs: they’re the proudest – adjectives you can do anything with, but not verbs – however, I can manage the whole lot of them! Impenetrability! That’s what I say!’
‘Would you tell me, please,’ said Alice, ‘what that means?’

Glenn
February 2, 2009 7:31 pm

Jeez, just read the OP, and the emphasis on certain words. I can’t help it if you think the subject is foolish. But the public reads “acid oceans”, and the scientists say “oceans are more acidic” and use “acidification” to implant the belief that the oceans will soon become acid baths, killing everything, unless we do something about that bad CO2 in the next two days.
Instead of “CO2 killing everything in the oceans”, how about “research finds declining ocean pH”?
http://www.pnas.org/content/early/2008/11/24/0810079105.abstract

Mike Bryant
February 2, 2009 7:32 pm

Peden…
It really is sad that Mr. McIntyre can explain the study and the errors in the study better than the authors or the journals that accepted the error filled studies can. We live in a new world in which the prevaricators have seized the pursestrings. We pay them to further an agenda that will result in our own harm. We deserve what we get if we cannot fire these apathetic laggards who feed at the trough of our mercy.

Admin
February 2, 2009 7:41 pm

I’m not going to be drawn into this debate. There is nothing scientifically incorrect about the use of the word in this context. That is the substantive point. The word may be tempting as a scary word, but it is being correctly used, so no victory may be won here even if alternatives are available.
Focus on the science, the data, and the methods, not the motivations. This is my last post on the subject. I suggest you reread my first on the subject.

Glenn
February 2, 2009 7:42 pm

Jeez,
I don’t understand why you think exposing propaganda isn’t substantive with regard to the subject of global warming and alarmism. Do you think it not productive to expose alarmism, whether it is psychological, political or under the guise of scientific knowledge?

Steven Goddard
February 2, 2009 7:45 pm

jeez,
The BBC article which this story is about is titled “Acid oceans need urgent action.”
“Just when you thought it was safe to go back in the water.”

E.M.Smith
Editor
February 2, 2009 7:46 pm

Simon Evans (16:54:23) :
So this is the best some of you have got? You wish to challenge the definition of ā€˜acidificationā€™?

No, Simon, we are not challenging anything about the definition. We are trying to establish the true meaning of the word so that we can know:
1) What is actually being said.
2) What is actually happening.
3) What is correct about both.
4) What was said that is a lie.
If you wish to join the Alice in Wonderland folks and speak in words of your own devising, feel free, but please do us the courtesy of pointing out those Global Substitution parameters in a #DEFINE block at the top of each posting…

Admin
February 2, 2009 7:48 pm

ok, one more post.
“Acid oceans need urgent action”
That is clearly incorrect usage and hyperbole, and therefore objectionable, but Ocean acidification as normally used is correct usage and not particularly objectionable.

Glenn
February 2, 2009 7:50 pm

Jeez,
You’ve only claimed that the word is used correctly, but you haven’t even attempted to back that up, nor have you made any attempt to refute my claims and research about the word being used incorrectly (or in a non-standard way) or the arguments for why it was coined and what the effect is of it’s use.
The substantive point is that the word was coined and used to mean that the oceans are becoming *more acidic*. And that *is* scientifically incorrect, since acidic in any dictionary or any use means an acid becoming stronger. Which by the way, was explained in the OP. I didn’t originate the OP, only expanded on the thesis with regard to AGW terminology which from where I sit, stands alone from other fields of science.

jarhead
February 2, 2009 7:58 pm

Re: envirochiq (18:08:53)
Envirochiq wrote
ā€œJust so you know, there are ways to measure pH, temperature, carbon levels, etc. for earlier periods in time based on the soil cores, ice cores, fossil samples, and other pertinent geological data that is of that time.ā€
I donā€™t think so. There are ways to ESTIMATE various items of interest, but theses are not measurements, they are model output. In addition, the exact year (1751) may also be an estimate depending on the method of estimation. To make matters more interesting, different models may give different estimates for the same item of interest. There is a major difference in quality between a measurement and an estimate.

Mike Bryant
February 2, 2009 8:00 pm

Jeez,
I looked on Google books and it seems that you are correct. The usage before 1950 seems to be “acidification” even if it has not moved below neutral. Also it seems that the term “Deacidification” has been used for slight movements in the opposite direction…
Mike

Glenn
February 2, 2009 8:02 pm

ā€œAcid oceans need urgent actionā€
“That is clearly incorrect usage and hyperbole, and therefore objectionable, but Ocean acidification as normally used is correct usage and not particularly objectionable.”
Why is “acid oceans” any less objectionable then “the oceans are turning to acid”? Because the oceans haven’t got there yet, but they will?

E.M.Smith
Editor
February 2, 2009 8:22 pm

Robert S (18:55:32) :

E.M.Smith (15:10:14) :
Will the OED do?

Sure. The first definition:
ā€œThe act or process of acidifying: Conversion into an acid.ā€
Like I have been saying, acidification is the process. No, it does not actually have to become acidic. Yes, it may be confusing to the general public.

It’s not the public that seems confused to me… They seem to know a sour taste in their mouth when they get one…
There was a reason I included all the chain of definitions… OK, you want to be walked through them all long hand. So what does ‘acidifying’ mean?
“Acidifying: Forming an acid: That combines so as to form an acid.”
So did your ‘process’ “form an acid”? No? Did it combine to “form an acid”? No? Then it isn’t acidifying and therefor not acidification.
Still confused? OK, I’ll do the nested substitutions for you.
Acidification.
The act or process of acidifying. <== substitute definition of acidification.
The act or process of forming an acid. <== substitute definition of acidifying.
Now try again: Exactly what acid was formed that allows you to say : "The act of process of forming {foo}"
[ Just to head off the inevitable: HCO3- or CO3– are not the definition of an acid. The H+ concentration is (thus the pH).
Dissolving HCl into dilute NaOH results in dilute salt solution, not dilute chloride acid ion solution… just to put a fine point on it. ]
Since the pH never got to 7.0, no acid. No acid, so no acidifying. No acidifying so no acidification.
I think it’s time for a tea party… Anyone know a hat maker? 8=}

Alan Wilkinson
February 2, 2009 8:34 pm

J Lo, if you add some other acid (not CO2) to the ocean, yes, you will reduce carbonate ion levels. But if you add CO2 you won’t because you are adding carbonate ion with the acid.
Marcus, you certainly have forgotten the basics. Carbonate is an ion not a molecule. And your equations are nonsense because you have simply ignored the equilibria that apply.

E.M.Smith
Editor
February 2, 2009 8:40 pm

HasItBeen4YearsYet? (19:10:28) :
@ E.M.Smith (15:59:34)
YOU JUST CANā€™T WINā€¦
Fish farming killing Israelā€™s coral reefs

How could you! Now I’m going to be stuck choosing between the rubber chicken and the mad cow burger šŸ˜‰
I did find it interesting that the article stated that nitrate was a real killer for coral and they only grew well when the ocean was strongly depleted in it. That’s an addition to the discussion.
Maybe that’s a big clue right there… Since both sewage and agricultural runoff are very heavy in nitrogen. I’m all for sewage plants and proper fertilization methods (and retention ponds for farm runoff… you can make very nice prawn and tilapia farms in nitrogen rich ag runoff. Algae blooms feet the bugs that feed the food … er, fish.. šŸ˜‰
It would be interesting to see a map of coral die off vs. nitrogen runoff…

J Lo
February 2, 2009 8:45 pm

J. Peden:
You are wrong.
You fail to understand what RC, I, and others have been saying. It IS counterintuitive upon first glance. Like I said, I had trouble with it at first. So think of it this way:
How do you deplete CO3(-2) from the ocean in this equation? Basically, add H+.
H+ & CO3(-2) HCO3(-1)
What is the whole equation of CO2 addition?
H2CO3 ā† K1 ā†’ H+ & HCO3(-) ā† K2 ā†’ 2H+ & CO3(ā€“2)
Note that 2 H+ atoms can be generated from this reaction. Do you need 2 H+ with CO3(-2) to generate the back reaction to HCO3-? No, you only need one:
H+ & CO3(-2) HCO3(-1). So there is an “extra” H+. So now you have to consider this: what is more favorable: the H+ reacting with HCO3- to form the highly unstable H2CO3, or H+ reacting with another/different CO3(-2) to form another HCO3(-)?
So what is the probability that this “extra” H+ will stably bind with HCO3(-1) to regenerate H2CO3? Not very high. What is the probability that this “extra” H+ will bind with CO3(-2)
Secondly, do you really think such a major and elementary flaw would be found in a peer reviewed paper?

E.M.Smith
Editor
February 2, 2009 8:46 pm

Glenn (19:14:37) :
Iā€™ll have to remember to pick up an enema kit (or several, come to think about it) to throw in the boat for the next time out. Thanks for the life saving info! I can only wonder why that family happened to have the means in hand, so to speak, when the time came to add water, stir and.. hold that thought.

You are welcome. BTW, the Dad knew about the effect and was, er, prepared (though they had to improvise part of the ‘stuff’… plastic bag and bit of plastic tubing from part of the boat, I think it was).
I’d also heard a story of an American Indian who survived by soaking in salt water pools, but can not verify it (nor can I tell if it was via, er, colonal intrusion or just reduced evaporation, or not …)
Sidebar: I’m abandoning the ‘what is is’ part of this thread. There is no hope…

Glenn
February 2, 2009 8:49 pm

Jeez,
Read through all your references, and appreciate the effort. But you don’t seem to understand, the problem is not with the definition of acidification, the problem is with the correct application of that definition. Acidification *is* the process of turning a base into an acid. From what I can gather from your references, they all refer to that process – going from a base to an acid. But going from say 8.2 to 8.1 does not represent a process of going from a base to an acid. If there is a process by which an acidic ph is achieved, then it will have been indeed an “acidification”.
Perhaps I missed something in those refs that did refer to acidification as for example adding an amount of acid to a base but not enough to cause the end result to be an acid. That’s what I asked for earlier.
Some of your refs use the definition of acidification to refer to an acid substance becoming even more acidic. However, that is somewhat different than using the word to mean a base moving closer to acid but not reaching an acidic state.

J Lo
February 2, 2009 8:58 pm

Alan Wilkinson & J. Peden:
If you don’t believe me, e-mail a chemistry professor. It makes sense once you think about it.
Let’s say you have 1 molecule of H2CO3, and an additional molecule of CO3(-2).
What is the resulting major reaction for these three molecules?
H2CO3 is HIGHLY unstable when pH is neutral, right?
HCO3(-1) is the dominant form right? So you have HCO3(-1) & H(+), correct?
So what is this H+ doing? If it is just in solution, then pH lowers, right? ([H+] increasing). If it is reacting, what can it react with?
Either HCO3(-1) to form H2CO3 (highly unlikely at such a high pH) OR our “extra” molecule of CO3(-2) to form HCO3(-1). Which reaction will it most likely favor in near neutral pH? The second reaction is much more likely. Thus, [CO3(-2)] is dropping.

HasItBeen4YearsYet?
February 2, 2009 9:04 pm

@ Marcus (19:06:35)
“no one seems to care that I found a medical reference where alkalinization was used for an acidic solution.”
Absolutely right! I couldn’t care less. I refuse to make myself crazy over the many misued terms in the literature. Just because they use a word incorrectly doesn’t mean I have to.
As to your chemical calculations, …I feel your instructor’s pain.
________________________________________________________________
@Smokey
Freemon Dyson, a real scientist.

J Lo
February 2, 2009 9:08 pm

Frankly, I think that acidification debate is stupid. I think the description is fine: I associate lowering of pH, even if it remains above 7, to be acidification. To me, a lower pH = more acidic. pH just stands for [H+] in a solution.

HasItBeen4YearsYet?
February 2, 2009 9:14 pm

@jeez (19:23:25) :
“Noā€“get specific about substantive items.”
The point is that you can’t if the terms you use to describe them are as slippery as a Clinton dodging a question about sexual impropriety You can’t “get specific” using words that havek no specific meaning.

Glenn
February 2, 2009 9:33 pm

Robert S (18:55:32) :
“Like I have been saying, acidification is the process. No, it does not actually have to become acidic. Yes, it may be confusing to the general public.”
That makes no sense. The process *of going from base to acid* does actually mean it has to become acid. If it doesn’t, there is no process.
Glenn (16:03:31) :
Or maybe you will claim that ā€œbecoming acidicā€ is the same thing as ā€œmore acidicā€?
“Nope. I donā€™t believe the ocean is becoming more acidic, but it is acidifying. I believe the 2003 article to be wrong in that respect.”
Acidifying means the same thing as acidification, the process of going from base to acid. You may believe the oceans are going to become acid, but they haven’t got there yet, and going from 8.2 to 8.1 or whatever isn’t acidification or acidifying, and isn’t evidence that the oceans will at some point go lower than 7.
I’m astounded that you regard a change in base toward acid as acidification, but reject that same event as “more acidic”. They both make as much sense or nonsense, depending on your POV.
Oh, and the 2003 Nature article did not ā€œcoinā€ the word acidificationā€“it has been in use for a good 30 years.
I meant of course the term “ocean acidification”.

E.M.Smith
Editor
February 2, 2009 9:34 pm

@jeez (20:12:18) : (and others in the ”what is is tea party”)
FWIW, I’m not hung up on the OED as god, nor do I really care if a word changes usage over time (they all most all do); but I do care that we have a basis of shared understanding; from whatever common source.
It was only with this thread & discussion that I realized the claim made was only that the pH was going to be 8.something and not 6-7.0 and had a combined reaction of “Oh, that’s not a problem” mixed with “Wait, they said what??” and I think that does matter, that it is substance. It was for me.
You cited many folks with a particular usage. Fine. The argot is gaining currency. But does the ‘average man’ know this? I think that is the point…
So y’all want to use it to mean something else from the OED: I just put a #DEFINE in my head for this context. I’d be a bit happier with a dictionary of some repute so I could simply change my global understanding, but such is life.
Heck, every programmer I’ve run into knew what “crufty” meant and it startled the heck out of me to find out it was jargon…. and don’t get me started on trying to talk with my British and Irish relatives (speaking of people separated by a common language…) Fair dinkum. But just remember that in The Empire it means something quite different when they ask if you “Want to be knocked up in the morning?” than it does in America (The first is “Do you want a wake up call?”…) So I do think words matter…
I’m off to tip a cuppa, shake hands with me wife’s best friend, and roust the main squeeze for bit ‘o randy andy…

Glenn
February 2, 2009 9:40 pm

J Lo (21:08:43) :
“Frankly, I think that acidification debate is stupid. I think the description is fine: I associate lowering of pH, even if it remains above 7, to be acidification. To me, a lower pH = more acidic. pH just stands for [H+] in a solution.”
Perhaps you are right. As I said at the first, I don’t retain much chemisty.
But your view is in conflict with other poster’s views. Maybe they are stupid and you are smart.

E.M.Smith
Editor
February 2, 2009 9:47 pm

E.M.Smith (21:34:49) : Iā€™m off to tip a cuppa, shake hands with me wifeā€™s best friend, and roust the main squeeze for bit ā€˜o randy andyā€¦
Oh, and in addition to my cup of herb tea, visit to the washroom, and kissing my spouse good night, I’ll be putting my moggy out.
(Moggy is what I was raised with as the term for the ally cat that adopted our living room as his home…)

E.M.Smith
Editor
February 2, 2009 9:53 pm

Dang it… just had to look back…
J Lo (20:45:28) :
Basically, add H+.

That’s a joke right? Isn’t it? You sure? šŸ˜‰
FWIW, last time I looked adding enough H+ to CO2 solution drove the CO2 out of solution, but it’s been a while and maybe I’ve forgotten something…

Steven Goddard
February 2, 2009 9:59 pm

Interesting how some here are attempting to hijack the discussion.
So far, none of the naysayers have offered any explanation of how shellfish could have existed at 4,000 PPM atmospheric CO2, offered any explanation for the lack of correlation between CO2 and temperature, or offered any raw data showing that ocean pH is dropping.
And no, the ocean is not acid as the BBC headline stated. Please read the article again – carefully this time.

HasItBeen4YearsYet?
February 2, 2009 10:11 pm

J Lo (20:58:59)
“H2CO3 is HIGHLY unstable when pH is neutral, right?
HCO3(-1) is the dominant form right? So you have HCO3(-1) & H(+), correct?
So what is this H+ doing?”

If you have a neutral solution in which there is H2CO3, it will contain about 20 percent of the Carbon, while the HC03- will contain about 80%. There won’t be any CO3–. Now, at neutral pH you have no excess H+ ions, so your assumption that there are is wrong. What will be the Cation that will balance the Anions, if not H+? The answer is that you can’t have a neutral solution of those ions without a buffer, so you would have some monovalent metal like Na+, or K+ from the buffer to fill in for the H+. The H+ reacts with whatever the Anion of the Buffer is, effectively removing it.

HasItBeen4YearsYet?
February 2, 2009 10:15 pm

@E.M.Smith (21:53:14) : “adding enough H+ to CO2 solution drove the CO2 out of solution”
That’s correct.

Alan Wilkinson
February 2, 2009 10:16 pm

J Lo, I don’t need to email a chemistry professor. I have a PhD in physical organic chemistry specialising in reaction mechanisms and rates.
When you add CO2 to water some of it becomes H2CO3, some of it becomes bicarbonate ions and some of it becomes carbonate ions. End of Story. There is more carbonate in the water than before you started. Irrevocably, undeniably and without question.
Confusing yourself hopelessly as you and RC and others have done above makes no difference. The aqueous equilibria don’t care. They continue to do what they’re good at – distributing CO2 between the various states according to the relative energy levels of those states.

Pragmatist
February 2, 2009 10:16 pm

More probably the entire usage issue is moot in light of the term’s exploitation by media scarifiers. The lay person conjures up images of acidified oceans in which a big toe will burn, waft smoke, and blacken to a spongy pulp.
As oceans become slightly less alkaline it behooves the AGW clan to shriek about acid. A simple refutation for the lay person – a more appropriate and ACCURATE definition is “becoming less alkaline.” I am lay. I know how my ignorant fellows think. Therefor the pragmatic skeptic is urged to adopt nomenclature easily absorbed by the general public. It is they who will phone the Congress to stop the madness.
“Becoming less alkaline,” is the ticket. Followed quickly with some geologic references to the relative stability of ocean pH across centennial/relevant time. AGWs think in extreme visuals, e.g. “sea level rise,” “ice melt,” “species extinction,” etc. The effective counter is moderate language – realistically demonstrating the minority of occurrence and magnitude, e.g. “CO2, a trace gas making up less than 4 hundredths of one percent of Earth’s atmosphere.”

J. Peden
February 2, 2009 10:18 pm

J Lo:
If you donā€™t believe me, e-mail a chemistry professor. It makes sense once you think about it.
J Lo, the constituents and interactions you are “thinking about” are completely contained in the equations, which show what happens. They do the “thinking” for you. That’s why they exist.
CO3 does not do anything more “logical” with H just because you think it should, that is, in defiance of the dynamic equilibria shown by the equations. Or if it does, show the equations which say that adding CO2 on the left will not result in an increase in CO3 on the right – as well as an increase in H.

J Lo
February 2, 2009 10:23 pm

It is stupid because it is not important.
You can associate acidification with changing pH from >7 to <7, but honestly, that has, as far as I know, there is really NO scientific basis for associating it this way. When the pH lowers, [H+] concentrations increase and [OH-] levels decrease. The only thing that is really significant at pH seven is that [OH-] = [H+], and that physiologically isn’t particularly important at all.
This is like arguing that there should be a special term for when you subtract one number from another and get a negative number. Yes, you could make up a term, but it really doesn’t mean anything in the big picture.
For all I care, we can call it "pH lowerification." Acidification is correct enough. Its calling a spade a spade.

J Lo
February 2, 2009 10:39 pm

E.M.Smith:
Basically, add H+.
Thatā€™s a joke right? Isnā€™t it? You sure? šŸ˜‰

Well, it wasn’t intentionally a joke, but after I was editing my post I was like “huh, I wonder if anyone will get this.”
I hope you understood my argument about how CO2 removes CO3(-2) from solution.
Towards your earlier comments about the aquarium keeper, it makes perfect sense that more CO2 dissolved in water could increase the amount of CO3(-2) in the ocean water. All you would have to do is adjust the final pH with a base like NaOH to drive the reaction to the right HCO3(-1) H+ & CO3(-2), thus “removing” free H+ atoms.
But strict CO2 addition in the illustration I gave, ceteris paribus, will lower [CO3(-2)]. The chemistry makes sense.

Alan Wilkinson
February 2, 2009 10:48 pm

J Lo, you flunk Chem 101 for sure. Come back when you’ve earned a pass mark.

J Lo
February 2, 2009 11:05 pm

Alan Wilkinson:
No offense, but your explanation is not one at all. In a solution with no CO3[-2], you would be correct. Adding CO2 to only H20 would create [CO3(-2)] because there was none to begin with. But if you have an initial concentration of [CO3(-2)], which there is in the ocean, you need to think about how the H+ generated by the dissociation of H2CO3 -> H+ & HCO3(-1) affects the reaction of excess [CO3(-2)] & H+ -> HCO3(-1)
Email your damn former thesis adviser and have him explain it to you. Then have him take away your PhD. Seriously though, think about it very carefully. Like I said, it is counterintuitive until you think about it very carefully.

February 2, 2009 11:10 pm

Steven Goddard (13:51:58) :
Bill D,
Can you point us to some measured ocean pH data from the last 20 years? Monterey Bay does not support the contention that pH is declining. Is there other raw data which does? In order to see a 150% increase in acidity over the remainder of the century (as the IPCC has reportedly claimed,) we would need to see greater than 15% increase per decade.

So an decrease of 0.2 in pH over the next 90 years, ~0.02/decade.

Neil Crafter
February 2, 2009 11:13 pm

Simon Evans (16:54:23) :
So this is the best some of you have got? You wish to challenge the definition of ā€˜acidificationā€™? Do you really wonder why so many would be inclined to dismiss your actions as nothing more than propagandising after that? Truly, very deeply feeble and pathetic, if that is what you choose to emphasise in your commentary! Call it de-alkalinasation if you prefer, I couldnā€™t care less! For goodness sakes, try to talk about the science rather than pursuing these silly point-scoring ventures – you just make yourselves seem ridiculous and petty (which does rather suit my POV, I have to say – by all means make yourselves seem ridiculous and petty!).”
Nice little rant Simon. Forgot your blood pressure pills today?

Bill D
February 2, 2009 11:16 pm

E.M.Smith (16:47:43) :
Alan, you have cheered me up enough that I think I will add a pitch to the gameā€¦
Alan Wilkinson (17:08:36) :
John Philip (12:01:09) : The acidification (or de-alkalinisation) is a concern because it will make it harder for calcifying organisms to make hard structures. This requires seawater to be supersaturated with calcium and carbonate ions to ensure that once formed the CaCO3 does not dissolve.
So by this logic, it is not possible to have fresh water muscles, clams, etc. since fresh water is not even remotely near saturated with calcium and carbonateā€¦ Iā€™ll have to tell my buddies to stop using fresh water clams for catfish bait since they donā€™t exist. Oh, and tell the folks in the Great Lakes that zebra muscles are no longer a problemā€¦ (Yes, itā€™s that darned non-peer reviewed existence proof thing again; too bad you canā€™t make it go awayā€¦)
E.M.–This is a great point and this is an area where I have some expertise (limnology). Since lakes vary in pH and carbonate chemistry (alkalinity, “water hardness”) much more than oceans, we can see strong effects on snails and mussels by comparisons between lakes. In general, these organisms are less sentive than corals, because they live in chemically more variable environments.
The zebra mussel situation is a good case in point. Freshwater scientists are very interested in predicting which lakes can be invaded by zebra mussels and how this relates to water chemistry. The short story is zebra mussels can invade lakes with limestone bedrock in their basins and water sheds, but they cannot invade “softwater” lakes. These lakes are often on granite formations and have naturally lower pH.
As zebra mussels have extended their range in North America, there is a very clear and direct correspondance between their invasion success and lake carbonate chemistry. As far as I know, just about all lakes in the US mid-west are suitable, in terms of chemistry for zebra mussels. Zebra mussels also do better when there is suitable rocky bottom within the epilimnion.
More generally, freshwater scientists can predict which freshwater systems have suitable carbonate chemistry for snails and freshwater bivalves (clams). Freshwater bivalves are also senstive to sedimentation and water pollution. There is no contradiction in the observation natural water chemistry, human caused acidification, sedimentation and other forms of pollution can all be important for these organisms. Some people on this block seem to argue that sentivity to pollution or even nuclear bombs mean that carbonate chemistry and pH are not also important.
Check “google scholar” under “zebra mussels and alkalinity” to access the peer-reviewed scientific literature in this area. I am getter 648 hits in the peer reviewed literature. These studies, many of which are available as PDFs show the close link between lake water chemistry and zebra mussels.

Richard Sharpe
February 2, 2009 11:16 pm

Alan Wilkinson says:

J Lo, I donā€™t need to email a chemistry professor. I have a PhD in physical organic chemistry specialising in reaction mechanisms and rates.

So, J Lo, Alan has shown you his. How about you whack yours down now for us to see.

Chris J
February 2, 2009 11:41 pm

@ Steven Goddard,
“Interesting how some here are attempting to hijack the discussion.
So far, none of the naysayers have offered any explanation of how shellfish could have existed at 4,000 PPM atmospheric CO2…”
The problem here is that you don’t seem to understand the very basics of CaCO3 precipitation/dissolution in sea water…or you’re simply playing dumb. pCO2 in and of itself does not determine the saturation state (Omega) for calcite/aragonite in sea water nor the capacity for biomineralization by organisms. It is a very important part of the system because of its influence on inorganic carbon speciation, yes, but it is only one of several factors here.
Calcifying organisms alive hundreds of millions of years ago did just fine because Omega was almost certainly similar then as compared to the preindustrial, as can be demonstrated by the historical calcite compensation depth.
Also, importantly, those organisms are not remotely the same organisms that are alive today. For instance, the scleractinia, todayā€™s stony corals, donā€™t arise until the Triassic. Among the most important reef-builders today, the Acroporids did not become common on coral reefs until the Miocene. The rugosa and tabulata, common during much of the Palezoic, had fundamentally different physiology from the scleractinia, including a calcitic skeleton. They were not remotely the organisms we have today. If you think the differences are trivial, Iā€™d invite you to acknowledge that the differences in physiology between a human, a hagfish, and a tunicate are trivial. Suggesting that what worked for those long-extinct organisms should be just fine for todayā€™s organisms is on par with saying that since some species of lizards can survive body temperatures of over 120 F that a distantly related tetrapodā€”humansā€”should be able to do so as well. To call these claims ridiculous is an understatement.
Yes, pCO2 was higher in the geologic past, but so was calcium concentration and total alkalinity, and at times by perhaps more than double their current concentrations, counteracting the effects of the elevated pCO2 on Omega and biomineralization. Several times during the Phanerozoic magnesium concentration was also quite a bit lower, favoring calcite precipitation and calcitic shells/skeletons, which are less soluble than aragonite. Plenty of references are available, including many in Nature, Science, etc.ā€”how did you miss them???
It’s easy to get biomineralization when all three of pCO2, calcium, and total alkalinty are high, like we see during parts of the Paleozoic, Mesozoic, and early Cenozoic. The situation today is completely different because today only pCO2 is rising while calcium and total alkalinity are essentially stationary. Given known response rates of tens to hundreds of thousands of years for oceanic calcium and total alkalinity to change appreciably, on timescales of hundreds to thousands of years, the only parameter that is changing meaningfully is pCO2.
Hence the question of why shellfish could have calcified when pCO2 was ~4000 uatm hundreds of millions of years ago but would dissolve at lower pCO2 today is simple: you’re comparing apples and oranges.
Shellfish and other organisms calcified hundreds of millions of years ago with high pCO2 and HIGH calcium and HIGH total alkalinity. Today related organisms, but not remotely the same organisms, are stuck with high pCO2, LOW calcium and LOW total alkalinity. That explains how they existed then and why the release of anthropogenic CO2 today is a threat to organisms today.
Either you donā€™t understand this, and therefore shouldnā€™t be speaking on the subject, or do and are purposefully misleading everyone. Iā€™m not sure it much matters, but Iā€™m curious which of these possibilities it is.
“, offered any explanation for the lack of correlation between CO2 and temperature…”
That’s another issue entirely, and I’m quite certain I’d be wasting my breath (or fingers, I suppose) if I were to type anything, so I shan’t comment.
“, or offered any raw data showing that ocean pH is dropping.”
There are datasets available from the Hawaiian Ocean Time Series (HOTS) and Bermuda Atlantic Time Series (BATS) as well as data from NOAA for the tropical Western Atlantic and a variety of other sources that all document falling oceanic pH.
It’s not as though these data are hiding, they’re very widely cited and readily available. Honestly, if you’re not aware of them, why did you feel qualified to write on this subject?
In addition, anyone that has some sea water, CO2, and the capacity to measure pH can demonstrate the phenomenon all day long. Add a precisely measured quantity of CO2 to the water, the pH drops by a very precise amount. This chemistry is extremely well characterized and has been well understood for decades. There’s no serious question about how ocean chemistry is changing or will change for a given input of CO2ā€”those relationships are as well worked out as, for instance, Newton’s laws of motion. If you don’t believe me, get some sea water, some CO2, and good quality equipment to measure seawater pH and see for yourself. This chemistry is EXTREMELY easy to verify, with good quality equipment, of course.
“And no, the ocean is not acid as the BBC headline stated. Please read the article again – carefully this time.”
On this point I essentially agree: the wording by the BBC was sloppy. The ocean is not ā€œacidā€ (pH < neuatral, ~7) nor will it become acidic anytime soon. Rather an acid (carbonic acid) is being added to the ocean causing acidification, why the process is called ā€œocean acidificationā€. I fully agree that the media needs to be more careful with their wording. Semantics aside, the process is exactly the same and the take-home message is exactly the same. Precision is good, but spending so much time quibbling over semantics is, well, a bit silly. Suggesting that poor word choice by the BBC in some way negates the chemistry is laughable (I know I did).
Chris

J Lo
February 2, 2009 11:44 pm

Alan Wilkinson:
I don’t understand you.
I assume you understand that:
1. CO2 acidifies ocean,
2. H(+) & CO3(-2) -> HCO3(-1),
3. Le Chatelier’s principle states that if you add H(+) to a system, you’ll push the equilibria in a manner that depletes initial [CO3(-2)]
4. [CO3(-2)] is already present in the ocean probably from all the CaCO3 added to it.

papertiger
February 2, 2009 11:51 pm

Just one more thing.
Undersea eruptions, particularly in continental or oceanic intraplate settings, continental rifts, and subduction zones, are highly alkaline.
Extrusive carbonatites are particularly rare (only 330 known carbonatite localities on Earth) none are found in ancient rocks.
Many people think this is because of the very high solubility of sodium carbonate.
The mid Atlantic ridge and the Pacific ring of fire are in effect built in buffer systems hard at work 24/7.

J. Peden
February 3, 2009 12:33 am

Marcus, regarding your “counterintuitive” idea that adding Ca to a solution of dissolved CO2 will cause CO3 to combine with H, forming HCO3, thus decreasing CO3, allegedly proving that H from CO2 + H2O causes decreased CO3 in the presence of Ca. Given:
1] CO2 + H2O = H2CO3 = H + HCO3 = H + H + CO3, all in dynamic equilibrium with each other.
2] H + HCO3 = H + H + CO3
I’d ask you or anyone, why would adding Ca to the total solution drive 2 more in one direction than the other? Unless, of course, something precipitated out.
This is beside the point, anyway, which is instead that adding more CO2 on the left of equation 1 must result in more CO3 on the right.
“Intuition” has nothing to do with inorganic chemistry, or at least it didn’t back when I took it 45 years ago in the Pre-Postmodern Age.

John Philip
February 3, 2009 1:16 am

So far, none of the naysayers have offered any explanation of how shellfish could have existed at 4,000 PPM atmospheric CO2
Except that the calcite-forming corals from the Orcavidian disappeared, probably as part of the P-T mass extinction event, to be replaced by aragonite-forming corals from the Triassic onwards. [1-3,000 ppm, about 8x current levels max].
It is a little bit sad, in the 200th anniversary year of Darwin’s birth, and on a ‘science’ blog, that anyone is seriously arguing that the tolerences of a species today are comparable with its great, great, great, great, great, great [x 100,000] – grandfather, but that appears to be the case.
We have lost about 20% of coral reefs since the 1950s, causal factors include overfishing and pollution, but increasingly thermal stress as corals are pushed out of their fairly narrow thermal comfort zone by rising sea temperatures. Going forward, acidification is predicted to reduce the rate at which these organisisms can calcify.
Home aquarium experiments notwithstanding, I challenge you to find a professional marine biologist who is not extremely concerned about the state of the reefs – which are relatively small in area but host about 25% of all marine species. Here’s an extract from a document produced during the 11th international Coral Reef Symposium, held last summer…
2008 is a critical time for coral reefs. At the 11th International Coral Reef Symposium held in July, midway in the International Year of the Reef, over 3000 experts from 75 countries assembled to face some hard truths: coral reefs are teetering on the edge of survival and it is our fault. High levels of carbon dioxide in the atmosphere have produced a lethal combination of hotter and less alkaline seawater. Pervasive overfishing, pollution, coastal development, and physical damage further undermine reef health, and consequently, that of the people and ecosystems depending upon them. A brief overview of the 2632 papers presented can be found on http://www.nova.edu/ncri/11icrs/outcomes.html
Coral reefs feed, protect, and provide livelihoods for hundreds of millions of people around the world. They create homes for billions of fish and other animals, buffer coastlines from the ravages of storms, and provide rich economic opportunities through tourism and fishing. Their value to society has been estimated at more than $300 billion/yr. Reefs are the dynamic centers of the most concentrated biodiversity on Earth. Losing coral reefs would rob the world of one of nature’s most precious gifts.
Despite these challenges, it is not too late to save coral reefs. The 11th ICRS gave a renewed sense of purpose and hope for the future. A consensus emerged that society has both the knowledge and the tools to bring coral reefs back from the brink. The only question is – will we act?

To which the answer here seems to be … ‘No need! – stop worrying! Vanishingly distant ancestors of today’s species survived far worse !’
Responsible journalism?

Syl
February 3, 2009 1:24 am

I think it’s fine if scientists use the term acidification if that’s what they’re used to using and they are comfortable with it. The problem is not the scientists, it’s the media whose staff writers seem to be dumber than chert when it comes to science. THEY are the ones who don’t know what it means and some who, even worse, DO know and choose to use derivatives of the term for effect.
If I were a scientist I’d be upset and wary of how my research is being presented in the media. But, it seems, many scientists don’t care much. And some, those who are true believers, go along with it. And THAT to me is shameful.

Richard S Courtney
February 3, 2009 2:14 am

Dear Mr Watts:
Concerning the recent BBC article titled ā€œAcid oceans ā€˜need urgent actionā€˜, you may be interested in the following correspondence that occurred when the BBC was preparing the article.
Subsequent to the correspondence I copy here, I heard nothing from the BBC despite Ms Mathys writing “Iā€™ll be in touch on the phone in the next day or two”. But the BBC published the article titled ā€œAcid oceans ā€˜need urgent actionā€˜ā€ which does not mention ā€“ and completely ignores ā€“ the ā€œhelpfulā€ information which I provided.
It seems the BBC is immune to influence by any facts that might alter the BBCā€™s environmentalist propoganda campaign.
In a message dated 20/01/2009 12:27:46 GMT Standard Time, jo.mathys@bbc.co.uk writes:
Dear Mr Courtney,
Iā€™m working on a project for BBC News about ocean acidification with our environment analyst, Roger Harrabin.
I was interested to read a recent paper youā€™d written on upwelling deep ocean water, and the effect this has on acidity levels on the upper ocean layers.
Would you have time for a conversation on the phone at some point soon? Iā€™d be very grateful if so. Whatā€™s the best number to reach you on?
Many thanks!
With best wishes,
Jo
In a message dated 20/01/2009 19:13:21 GMT Standard Time, RichardSCourtney writes:
Dear Ms Mathys:
You ask me:
ā€œWould you have time for a conversation on the phone at some point soon? Iā€™d be very grateful if so. Whatā€™s the best number to reach you on?ā€
Of course you can. However, I am away from my base at the moment. If you want to phone me tomorrow (21 Jan.) I shall be obtainable at xxxxx
I will be there all day, but may not be contactable for some periods during the morning and evening.
All the best
Richard
In a message dated 23/01/2009 20:25:07 GMT Standard Time, RichardSCourtney writes:
Dear Ms Mathys:
I tried to send the following but it was returned as being too big. I am trying again without the attachments. If you want them then contact me. My phone number is 01326 211849
All the best
Richard
***************
Dear Ms Mathys:
Your message (below) said you wanted a phone conversation with me about ocean ‘acidification’. But, possibly because I was away from my base, that has not happened.
I did try to phone you yesterday morning but you were absent from your office. So, I now write to demonstrate that I have not been avoiding you.
Firstly, I understand that Sonja Bohmer-Christansen gave you a note of mine which explained the problem of ascribing cause and effect to recently observed changes to ocean alkalinity and atmospheric carbon dioxide (CO2) concentration.
The following sumarises my views on the risks and causes of ocean ‘acidification’.
Risks from increased ocean ‘acidification’.
There are no known risks from ocean ‘acidification’.
It is often asserted that ocean ā€˜acidificationā€™ could cause difficulties for the ability of oceanic creatures to form their calcareous exoskeletons. Clearly those who assert this have never heard of the White Cliffs of Dover: they are made of chalk.
Most chalks ā€“ including the famous White Cliffs – formed during the Cretaceous period, between 100 and 60 million years ago. Chalks from this period can be found around the world, and they consist of the microscopic skeletons of oceanic plankton.
The Coccolithophores are the major group of chalk forming plankton. Their individual spherical skeletons are called cocospheres and they consist of a number of calcareous discs called coccoliths. After death of the plankton, the skeletons settled to the bottom of the sea and most coccospheres and coccoliths collapsed, but they can be clearly seen using scanning electron microscopy (SEM). Indeed, back in my days working in a lab. I often used chalk as a demonstration of SEM to visiting parties of non-scientists because coccospheres are pretty.
Cretaceous chalks formed when global temperatures and atmospheric carbon dioxide concentration were higher than now. Indeed, global temperature was 5 to 6 deg.C higher than now and atmospheric carbon dioxide was 4 times higher than now
(see e.g. http://www.jstor.org/pss/57127).
But the calcerous skeletons of oceanic creatures from that time are so abundant that they now comprise many hills and mountains around the world.
So, I wonder why some people fear that slightly higher global temperatures and slightly higher atmospheric carbon dioxide concentration than now would hinder formation of such skeletons.
Similarly, it is asserted that corals could be harmed by ocean ‘acidification’, but that is also extremely implausible for the same reason: i.e. corals flourished when temperatures and atmospheric CO2 were much higher than now in times past.
Cause of ocean ‘acidification’
Determination of cause and effect relationships is a severe problem when attempting to evaluate every aspect of the anthropogenic global warming (AGW) hypothesis.
It is often claimed that ā€˜ocean acidificationā€™ (i.e. change to the pH of the ocean surface layer that is reducing the alkalinity of the surface layer) is happening as a result of increased atmospheric CO2 concentration. However, I have repeatedly pointed out that the opposite is also possible because the deep ocean waters now returning to ocean surface could be altering the pH of the ocean surface layer with resulting release of CO2 from the ocean surface layer. Indeed, no actual release is needed because massive CO2 exchange occurs between the air and ocean surface each year and the changed pH would inhibit re-sequestration of the CO2 naturally released from ocean surface.
Ocean pH varies from about 7.90 to 8.20 at different geographical locations but along coasts there are much larger variations from 7.3 inside deep estuaries to 8.6 in productive coastal plankton blooms and 9.5 in tide pools. The pH is lowest in the most productive regions where upwellings of water from deep ocean occur.
It is thought that the average pH of the oceans decreased from 8.25 to 8.14 since the start of the industrial revolution (Jacobson M Z, 2005). And it should be noted that a decrease of pH from 8.2 to 8.1 corresponds with an increase of the CO2 in the air from 285.360 ppmv to 360.000 ppmv at solution equilibrium between air and ocean (calculations not published).
In other words, the ocean ‘acidification’ (estimated by Jacobson) is consistent with the change to atmospheric CO2 concentration for the estimated change to the solution equilibrium between air and ocean.
Thus it is important to determine the cause/effect relationship between the changes to the atmospheric CO2 concentration and the pH of the ocean surface layer: i.e. which of these changes is causing the other to change.
The upwelling regions having lowest pH suggests that the ocean pH is changing to alter the atmospheric CO2 concentration. And the Vostock ice core data suggests a reason why this is likely.
I am very sceptical of the ice core data because I think they indicate falsely low and very smoothed values for past atmospheric CO2 concentrations. I base this opinion on the works of Jaworowski (indeed, at his request I presented his paper on ice core analysis to the 2008 Heartland Climate Conference because illness forced his absence). However, I do think the ice cores indicate long-term changes to past atmospheric CO2 concentrations. And the ice cores indicate that changes to atmospheric CO2 concentration follow changes to temperature by ~800 years. If this is correct, then the atmospheric CO2 concentration should now be rising as a result of the Medieval Warm Period (MWP).
This begs the question as to the cause of the ~800 year lag of atmospheric CO2 concentration after changes to temperature indicated by ice cores. And I suggest it is an effect of the thermohaline circulation.
The water now returning to the surface layer entered the deep ocean ~800 years ago during the MWP. Therefore, a release of oceanic CO2 in response to altered pH would concur with the ice core indications (assuming my acceptance of long-term trends in ice core data is correct). And this release could be expected to provide a steady increase in atmospheric CO2 concentration (of at least 1.5 ppm/year) as a result of the water now returning to the surface having entered deep ocean during the MWP.
Indeed, those who proclaim man-made global warming assert that heat from present global warming is going into the oceans and will return later. If so, then – for the same reasons – effects of the MWP must be returning now.
Several studies have shown that the recent rise in atmospheric CO2 concentration varies around a base trend of 1.5 ppm/year. A decade ago Calder showed that the variations around the trend correlate to variations in mean global temperature (MGT): he called this his ‘CO2 thermometer’. Now, Ahlbeck has submitted a paper for publication that finds the same using recent data. Reasons for this ‘CO2 thermometer’ are not known but they probably result from changes sea suface temperature.
So, there is strong evidence that MGT governs variations in the recent rise in atmospheric CO2 concentration but there is no clear evidence of the cause of the steady – and unwavering – base trend of 1.5 ppm/year.
It is often suggested (e.g. by IPCC) that the anthropogenic emission of CO2 is accumulating in the air, and this could be the cause of the steady base trend. However, a rise related to the anthropogenic emission should vary with the anthropogenic emission, but the steady rise does not.
Simply, in the absence of more information, the anthropogenic emissions vary too much for them to be a likely cause of the steady rise of 1.5 ppm/year in atmospheric CO2 concentration that is independent of a temperature effect.
Please note that the annual anthropogenic emissions data need not vary with the atmospheric rise. Some of the emissions may be accounted in adjacent years so 2-year smoothing of the emissions data is warranted. And different nations may account their years from different start months so 3-year smoothing of the data is justifiable. However, the 5-year smoothing applied by the IPCC to get agreement between the anthropogenic emissions and the rise is not justifiable (they use it because 2-year, 3-year and 4-year smoothings fail to provide the agreement).
So, other possible explanations than the anthropogenic emissions deserve investigation.
I argue that a response to the MWP provided in the present by the thermohaline circulation is an explanation that does concur with the empirical evidence. Water now returning to the surface having entered deep ocean during the MWP may be inducing release of oceanic CO2 in response to altered pH, and this release could be expected to provide the steady increase in atmospheric CO2 concentration (of at least 1.5 ppm/year) that is observed to be independent of temperature variations.
Additional information
I provide the attachments to give more insight to the cause(s) of the recent rise in atmospheric CO2 concentration. They are
(a) the cover page with title illustration of
(b) the verbatim text with the illustrations I used to present
(c) the paper I presented at the 2008 Heartland Institute Climate Conference in New York.
The paper (i.e. attachment c) is dry as dust, but I tried to present it in an entertaining way. A video of that presentation can be seen at
http://www.heartland.org/NewYork08/newyork2008-video.html
At that URL,scroll down to
Tuesday, March 4, 2008
8:45 – 10:15 a.m.
Track 2: Climatology
and click on my name
then scrollback to the top where the video will appear.
Unfortunately, the video does not show the illustrations, so I suggest that you follow it while refering to attachments a and b.
Also, it is sometimes suggested that carbon isotope analyses are supporting evidence for an anthropogenic cause for the recent rise in atmospheric CO2 concentration. In fact, they indicate that the bulk of the cause – and possibly all the cause – is natural (i.e. not anthropogenic). An explanation of this is probably beyond the purposes of this note but ask me about it if you want to.
I hope this note demonstrates that I have not been avoiding you and contains what you wanted.
All the best
Richard
PS If you want to see my presentation of Jawarowski’s paper (mentioned above) than go to
http://www.heartland.org/NewYork08/newyork2008-video.html
At that URL,scroll down to
Monday, March 3, 2008
4:00 – 5:30 p.m.
Track 1: Paleolimatology
and click on my name
then scrollback to the top where the video will appear.
In a message dated 26/01/2009 10:04:38 GMT Standard Time, jo.mathys@bbc.co.uk writes:
Dear Mr Courtney,
Many thanks for this information, itā€™s most helpful.
Iā€™ll be in touch on the phone in the next day or two, things are a little hectic at the moment!
With best wishes,
Jo
Richard

pkatt
February 3, 2009 2:34 am

Bill D (10:29:28) :
pretty obvious you didn’t read the link:)
another quote:The tube worms, limpets and lobsters were scarce, the shrimp, crab and scale worms the most commonly seen animals. Also, two types of starfish (red and another white) and anemones (white) plus 4 or 5 types of fish were noted as were some shells of a possible snail ~1-2 cm in length, near the end of the dive. :End quote
I seem to remember crab, and shrimp being qualified as shell fish. I did not attack Steven G. I was simply pointing out that definitively saying corals and shellfish cannot survive in acidic conditions was inaccurate. And it was also meant to show the diversity of life on this planet and the unusual ability of most organisms to adapt to environment, perhaps humans should try that?
On a side note: http://www.ecoearth.info/shared/reader/welcome.aspx?linkid=115822&keybold=
http://www.bloomberg.com/apps/news?pid=20601086&sid=aAFd0qbd9u1I
Can I say EEEK? Anyone wanna know what happens to corals when you get a plankton bloom??
http://www.int-res.com/articles/meps/60/m060p299.pdf
so I guess its ok to destroy it to save it huh?

foinavon
February 3, 2009 2:43 am

Alan Wilkinson (12:57:13)

Chemical balderdash from Eric, foinavon, RC, and Bob Coates.
The equations I gave apply irrespective of any other contributions such as solid CaCO3. Obviously (well, certainly to any chemist with half a brain) if calcium carbonate dissolves there is more carbonate in the system, not less. You cannot create more bicarbonate without also creating more carbonate because of the equilibrium I gave above in equation (1).
I repeat, the only way CO2 can cause a reduction in carbonate is by carbonate being taken out of the water – eg by creation of MORE shells, coral, fishbone etc.

Not really Alan. The positions of the equilibria in the dissociation reactions below are governed not only by mass action, but also by the proton affinities of the acids/bases; you canā€™t leave the latter out!
Incidentally, we’re not talking about dissolving more calcium carbonate. We’re talking about dissolving more carbon dioxide, its hydration to carbonic acid, and the production of protons (H+) which shift the equilibrium (see below) away from aqueous carbonate:
Consider the equilibrium again:
CO2(aq) + H2O == H2CO3 == H+ + HCO3- == H+ + CO3ā€“
where H2CO3 is carbonic acid, HCO3- is bicarbonate, and CO3– is carbonate, and == signifies an equilibrium.
the positions of these equilbria are defined by the pH (8.1, say) and pKa’s (proton affinities) of the acids.
The pKa’s for bicarbonate and carbonic acid in seawater are near 9.1 and 6.1, respectively (I’m using these values for convenience..they’re close to the real ones I believe).
If the total carbon concentration is 1 molar (1M), say, at pH 8.1 there is 0.9009 M bicarbonate, 0.0901 M carbonate and 0.009 M carbonic acid. That can be determined easily from the Henderson-Hasselbalch equation:
pH = pKa + log[base/acid] (where “base” and “acid” correspond to the acidic and basic components of the buffer).
Now add carbonic acid equivalent to a concentration of 0.02 M.
The carbonic acid essentially fully dissociates (since pH is well above pKa). The bicarbonate concentration rises to 0.9009 + 0.02 = 0.92M (more or less). However the proton concentration has also risen by 0.02 M. The pH doesnā€™t plummet because the solution is buffered by the equilibria above (largely the bicarbonate-carbonate equilibrium). What happens to the protons? They mostly protonate carbonate because carbonate has a higher affinity for protons than bicarbonate.
The new carbonate concentration is 0.07M. Itā€™s gone down. The new pH (calculated using the Henderson Hasselbalch equation) is 7.98.*
J Lo, RC, Bob Coats, Eric and Marcus (and me!) are correct and in perfect accord with the science and real world observations. It would be inconceivable that adding acid to a solution of any composition wouldnā€™t result in a drop in pH! Incidentally, since you are a chemist, why not test this yourself in the lab? Itā€™s a very easy experiment to doā€¦.
——————————–
* notice that there is a small approximation here since the full analysis is slightly more complex as weā€™ve not fully dealt with the mass action. The 0.02M increase in bicarbonate will dissociate slightly to carbonate. We could calculate that if the pH were to remain unchanged, the new carbonate concentration would be raised from 0.09M to around 0.092M. However the drop in pH will reduce the dissociation of bicarbonate to bicarbonate further, and so the in fact the mass-action component of the equilibrium is even less than this.

John Philip
February 3, 2009 2:55 am

Maybe Jo saw the name ‘Jaworowski’ and href=”took fright?

MAG
February 3, 2009 3:35 am

Climate science is full of assumptions and uncertainty and the coral literature is more uncertain than most. A close look at all the work by Hoegh-Guldberg and others leads one to the same conclusion as Baird and Maynard (Science 18 April 2008 p315) who state:
“the effects of temperature and acidification on even the most basic vital rates in corals, such as growth, mortality, and fecundity, are largely unknown, as are the physiological trade-offs among these traits. Consequently, the sensitivity of
population growth to climate-induced changes in vital rates remains almost completely unexplored. In the absence of longterm demographic studies to detect temporal trends in life history traits, predicting rates of adaptation, and whether they will be exceeded by rates of environmental change, is pure speculation”.
Much of climate science continues to be politics masquerading as science.

Richard S Courtney
February 3, 2009 3:42 am

John Philip:
As is usual with climate alarmists, you ignore all the points that have been made and respond with smear and inuendo.
Fact: Mathys asked to talk to me (I did not ask to talk to her).
Fact: Fearful that my absence from my base had given the impression that I was avoiding her, I sent an email that summarised my views.
Fact: Mathys replied to my email saying; “Many thanks for this information, itā€™s most helpful.
Iā€™ll be in touch on the phone in the next day or two.”
Fact: Mathys did not phone me about the “helpful” information (and nor did any other BBC representative) .
Fact: The BBC then published the article titled ā€œAcid oceans ā€˜need urgent actionā€˜ that was based on the premise:
“The worldā€™s marine ecosystems risk being severely damaged by ocean acidification unless there are dramatic cuts in CO2 emissions, warn scientists.”
Fact: That article’s premise is – at least – questionable in the light of the information I provided.
Fact: The article did not question the premise either during its preparation (as the failure to fulfil the intention to phone me demonstrates) or in its content.
Richard

HasItBeen4YearsYet?
February 3, 2009 3:52 am

J Loā€™s equations just donā€™t add up, something like this

foinavon
February 3, 2009 4:14 am

Richard S Courtney (02:14:18)

Several studies have shown that the recent rise in atmospheric CO2 concentration varies around a base trend of 1.5 ppm/year. A decade ago Calder showed that the variations around the trend correlate to variations in mean global temperature (MGT): he called this his ā€˜CO2 thermometerā€™. Now, Ahlbeck has submitted a paper for publication that finds the same using recent data. Reasons for this ā€˜CO2 thermometerā€™ are not known but they probably result from changes sea suface temperature.

That’s wrong on two counts as we discussed on the other thread.
ONE: Clearly the atmospheric Co2 doesn’t have a “base trend” of around 1.5 ppm/year. The trend is in accord with the rate of our greenhouse gas emissions. During the early part of the record when emissions were lower the rate of increase in atmospheric CO2 was near 0.7-0.9 ppm/yr. It’s now averaging around 2 ppm/yr. So there certainly isn’t a “base trend” whatever that might mean that is independent of our emissions. Here’s the data from Mauna Loa:
http://www.esrl.noaa.gov/gmd/ccgg/trends/
TWO: reasons for the interannual variability in atmospheric CO2 rises are in fact known quite well. They do relate to see surface temperature through the ENSO cycles, and the evidence indicates that they are a consequence of ENSO-related effects on tropical forest growth and productivity. During El Nino years thse forests are water-limited, grow poorly and thus don’t “pull down” CO2 from the atmosphere efficiently. They are also prone to forest fires and so tend to release CO2. Thus in and shortly after El Nino years our CO2 emissions are supplemented by CO2 from the terrestrial environment. In and shortly after La Nina years, the tropical forests are not moisture-limited and gropw productively, especially if a La Nina follows closely after an El Nino. Thus enhanced CO2 draw-down by the terrestrial environment subtracts from the emissions more than during average years. This is all quite well characterized. A recent paper on the subject provides a good starting point:
N. Zeng (2005) Terrestrial mechanisms of interannual CO2 variability. Global Biogeochemical Cycles 19, GB1016

It is often suggested (e.g. by IPCC) that the anthropogenic emission of CO2 is accumulating in the air, and this could be the cause of the steady base trend. However, a rise related to the anthropogenic emission should vary with the anthropogenic emission, but the steady rise does not.

In fact it does. See the Mauna Loa atmospheric CO2 data linked to just above.

It is often claimed that ā€˜ocean acidificationā€™ (i.e. change to the pH of the ocean surface layer that is reducing the alkalinity of the surface layer) is happening as a result of increased atmospheric CO2 concentration. However, I have repeatedly pointed out that the opposite is also possible because the deep ocean waters now returning to ocean surface could be altering the pH of the ocean surface layer with resulting release of CO2 from the ocean surface layer.

Since we know that CO2 is not being released by the oceans, but is being forced into the oceans in huge amounts, that proposal doesn’t accord with the real world evidence.

JamesG
February 3, 2009 4:18 am

I don’t think there’s anything intrinsically wrong with using acidification either as long as you add the reminder for the laypeople that the ocean isn’t actually acidic. Like it or not, acidic is scary, despite the fact that our skin is acidic and so is rainwater. So much of the discussion about semantics is completely missing the point. The use of the word without qualification is mostly designed to scare. No more, no less. It’s about context.
On those who have suggested reading the literature connecting bleaching events to CO2. Have you actually read it yourselves? I don’t think so because it doesn’t take too long to discover that the “link” is always an unfounded, unproven assumption. If I’m wrong please point me to the paper that proves the link. In the absence of said link though some of us tend to use our brain and try to eliminate other factors. To me the Cuba conundrum eliminates CO2 as a stress on coral because it is pristine while surrounded by Caribbean coral which is highly “stressed”. You don’t need to be a chemist or biologist to reach that conclusion but anyway, marine biologists say this pristine Cuban coral is due to other human factors and not due to a lack of acidification. If there is actually a particularly alkaline sea found around Cuba then again please point this out to me. However please do not point me to any papers or conferences by scientists who have not even apparently considered this gaping hole in their theory.
On a last note I’ve discovered that when I point out to peer-reviewed papers that show the earth is measurably greening – confirmed by satellite, those same people who always like to defer to scientific papers then become sudden disbelievers in science and say that it’s either not true or that it’s obviously only a temporary effect. they even attempt to deny the very well-established connection between CO2 and growth. So this tedious referral to authority is only highly active when it comes to bad news.

foinavon
February 3, 2009 4:24 am

Richard S Courtney (03:42:25)

Fact: That articleā€™s premise is – at least – questionable in the light of the information I provided.

Not really Richard. The article accords pretty well with the scientific view informed by the scientific evidence. Of course it’s a piece of informed journalism rather than a scientific report. Since there are very basic errors in the information that you seemed to have provided to the journalist [see foinavon (04:14:55)], the articles premises seem, in fact, not to be so “questionable”.

Fact: The article did not question the premise either during its preparation (as the failure to fulfil the intention to phone me demonstrates) or in its content.

The BBC are generally pretty good (not always perfect ‘though!) in obtaining informed scientific opinion on matters of science. Notice that the short BBC article is essentially conveying the findings and concerns of “More than 150 top marine researchers”. So perhaps the question is who these marine researchers are and what is the evidence that informs their thought on this matter…

Simon Evans
February 3, 2009 4:40 am

pablo an ex pat (17:12:54) :
Dear Simon Evans
As I wrote to you personally plus your cohort Foinavon a little while back to point out the obvious, rapid ocean recirculation means that acidification or delakalinization is a completely busted flush.
And there has been no response then I have to presume that you canā€™t find a way to disagree with me but on the contrary like to argue for arguments sake.

I’m afraid I became frustrated with the semantics of ‘acidification’ and then went to bed. Very well, you say:
“If it is such a long process why is Tritium from 1950 and 1960ā€™s Atomic testing in the Pacific currently being detected in the deep water of the North Atlantic ?
There is only one answer the mixing process is obviously much more rapid than it has been assumed to be.

Evidently that is not obvious to the Royal Society, etc. Perhaps you should let them know? The Monaco Declaration expresses concerns for severe damage on short timescales:
The current increase in ocean acidity is a hundred times faster than any previous natural change that has occurred over the last many millions of years. By the end of this century, if atmospheric CO2 is not stabilized, the level of ocean acidity could increase to three times the preindustrial level. Recovery from this large, rapid, human-induced perturbation will require thousands of years for the Earth system to reestablish ocean chemical conditions that even partially resemble those found today; hundreds of thousands to millions of years will be required for coral reefs to return, based on the past record of natural coral-reef extinction events.
Show me evidence that the oceans can mix completely to their total depth fast enough to avert acidification. Tritium traces obviously (to use your word) do not demonstrate that, since both vertical and lateral distribution is not even.
Glenn (17:39:19) :
Simon Evans (16:54:23) :
100% innuendo, ad hominem and baseless opinion. Should have been moderated IMO.
Frustration, Glenn. I agree with jeez.
Btw, I look forward to you even-handedly criticising the ad hominem comments that flow so readily in ‘the other direction’. I’m pretty bored with people on these threads claiming ‘ad hom’ whilst dishing it out copiously themselves (I’m not saying that you do, I don’t know, but if not then I trust your opprobrium will be applied evenly).

John Philip
February 3, 2009 4:54 am

Richard,
As is usual with climate alarmists, you ignore all the points that have been made and respond with smear and inuendo.
I beg to differ, as with Mr Goddard you are of the opinion that the fact that corals thrived in the distant past indicates they will be unaffected by [historically speaking] abrupt changes in CO2 now, thus calmly dismissing the work of Charles Darwin who tells us that – given sufficent time – a species will adapt by means of natural selection to a slowly changing environment. It is sheer nonsense to propose that the distant ancestors of Triassic organisms alive now would survive in the environmental conditions that were in place back then.
You then tell us that you base your scepticism of the ice core data ‘on the work of Jaworowski’. I would caution against this, as Ray Pierrehumber points out here (comment 109) Jaworowski has only published his observations in places where they are unlikely to get serious scrutiny, and such scrutiny as they have received has been unremittingly negative.
You will be aware, I am sure of the ‘Oeschger Counter’, a carbon dating device used in geophysics, and also of the Dansgaard-Oeschger events in glacial chronology. Both are named after the late Hans Oeschger. If anyone qualifies as a pioneering giant in the analysis of ice core data, it is Professor Oeschger. Perhaps I could invite you to comment on the substance of the flaws that Oeschger finds with Jaworoski’s work here .
Flaws that lead Oeschger to this conclusion: Based on my experience during decades of involvement in this field, I consider the chances as very small that the major findings from greenhouse gas studies on ice cores are fundamentally wrong; and I find the publications of JAWOROWSKI not only to be incorrect, but irresponsible.
I look forward to hearing from you.

MrPete
February 3, 2009 5:06 am

a) Politics and vocabulary aside, the acidification question is most definitely a topic of major interest. My question: are the concerns biased by the bad AGW work in other arenas?
b) The sunscreen/sunblock comments above are very apropos. My question: are there remote reefs (anywhere) unaffected by sunblock? How are those reefs responding?
c) My wife’s major scientific interest is marine biology. We’re quite interested in this topic and hope to follow through with conversations with folks at the lab where she studied.

Alan Millar
February 3, 2009 5:34 am

So which of the alarmists are right?
As AGW warms the planet the oceans warm and they start to outgass CO2 ( seawater cannot absorb and hold CO2 as well when it warms) which is an enhanced positive feedback to the already growing atmospheric CO2.
OR
Increasing CO2 will not only dramatically increase the earths temperature the oceans will acidfy as they hold more dissolved CO2.
Shouldn’t the planet cooling and seawater getting cooler put the corals at more risk as the oceans ability to absorb more CO2 increases? (not to mention that corals tend to do better in warmer waters than cooler ones!)
Perhaps some of our alarmist friends would like to explain.
Alan

Marcus
February 3, 2009 5:37 am

foinavon: Thanks for setting out the full chemical equilibrium maths for these people.
Alan Wilkerson: You really might want to go back to your PhD granting instituion and ask them for a rebate. You shouldn’t be able to get that far without developing some decent chemical intuition. Yes, any of us PhD holders (I have one in a vaguely chemistry-related degree, though I got my BS and MS doing organometallic chemistry and biochemistry respectively) can and do make simple mistakes, but usually we are able to recognize them when they are pointed out to us.
J Peden: Unfortunately, equations aren’t enough. You need chemical intuition to know how and when to use them. In this case, you need to be careful of your “floating ions” – charged molecules don’t just sit around in nature. Naked protons, especially. (ignoring certain plasmas in space) That’s why the equation doesn’t get driven to the right willy-nilly, and why some of us are careful to keep track of our calcium (or other cations).
Here’s another trio of thought experiments:
Experiment 1: Add HCl to a solution with an equilibrium mixture of calcium carbonate, bicarb, and carbonic acid. What happens? How much carbonate gets converted to bicarb per unit of HCl added?
Experiment 2: Add CaCO3 to your equilibrium mixture. How much extra carbonate will you have in your solution per unit of CaCO3 added?
Experiment 3: Add 2 units of HCl and one unit of CaCO3 to your mixture. Sum the above two thought experiments and compare to your intuition. (and 2HCl + CaCO3 is nearly equivalent to adding H2CO3)

Sandy
February 3, 2009 5:39 am

In the light of the fossil record the idea that higher CO2 and higher temperatures will adversely affect the biosphere flies in the face of evidence and basic biology.
It takes a wilful ignorance to believe it could be so and a cynical arrogance to attempt to stand up for the lunacy.
History will laugh at the warmistas and I will start now.

Richard S Courtney
February 3, 2009 5:59 am

Foinavon:
Sorry, but ā€“ as I said on the other thread – you are simply wrong.
You assert:
ā€œClearly the atmospheric CO2 doesnā€™t have a ā€œbase trendā€ of around 1.5 ppm/year. The trend is in accord with the rate of our greenhouse gas emissions.ā€
OK, as I accepted in the other thread, you are right that I oversimplified when I said the base trend is 1.5 ppmv per year. I should have said:
ā€œThe rise has a steady and unwavering increase in atmospheric CO2 concentration which is independent of temperature of 0.4 per cent per year and is about 1.5 ppmv per year since measurement began at Mauna Loa in 1958.ā€
Mea culpa.
But, as I have repeatedly explained to you on the other thread,
ā€œthere are two components to the recent rise in atmospheric CO2 concentration: viz. the variation that is directly related to mean global temperature (i.e. Calderā€™s ā€˜CO2 thermometerā€™) and the steady rise of 0.4 per cent per year. As you say, Calderā€™s CO2 thermometer seems to be ENSO-related. Hence, it is the steady rise that we need to understand.ā€
And, as I have also repeatedly explained to you on the other thread, that steady rise does not relate to the anthropogenic emission. It is an empirical fact that is does not relate to the anthropogenic emission. Indeed, how could it when that rise is steady and the anthropogenic emission is very variable?
Then you make a ludicrous assertion saying;
ā€œSince we know that CO2 is not being released by the oceans, but is being forced into the oceans in huge amounts, that proposal doesnā€™t accord with the real world evidence.ā€
Rubbish! The ā€œreal world evidenceā€ is that the oceans release an order of magnitude more CO2 than the anthropogenic emission each year and they take back almost all of it each year. At issue is why they donā€™t take back all of it.
As I said,
ā€œthe ocean ā€˜acidificationā€™ (estimated by Jacobson) is consistent with the change to atmospheric CO2 concentration for the estimated change to the solution equilibrium between air and ocean.
Thus it is important to determine the cause/effect relationship between the changes to the atmospheric CO2 concentration and the pH of the ocean surface layer: i.e. which of these changes is causing the other to change.
The upwelling regions having lowest pH suggests that the ocean pH is changing to alter the atmospheric CO2 concentration. And the Vostock ice core data suggests a reason why this is likely.ā€
You again cite Zeng (2005) that assumes the rise in atmospheric CO2 concentration is anthropogenic. So, I again cite our paper that shows the available data can be used to demonstrate that several natural causes for the rise and an anthropogenic cause are all consistent with the rise. Hence, it cannot be known whether or not the rise is anthropogenic or natural in part or in whole.
Ref, Rorsch A, Courtney RS & Thoenes D, ‘The Interaction of Climate Change and the Carbon Dioxide Cycle’, E&E v16no2 (2005)
Please make a comment after you have read it.
Richard

Steven Goddard
February 3, 2009 6:50 am

One of the arguments being propagated is that low mixing rates between shallow and deep water prevents pH buffering. However, we know that under normal Pacific Ocean conditions, cold deep water is continuously dragged to the east up the thermocline along the South American Coast, and is replaced by warm water sinking in the mid-Pacific. Under La Nina conditions this becomes even more exaggerated.
http://en.wikipedia.org/wiki/El_Ni%C3%B1o-Southern_Oscillation
We also know that during the Cretaceous, the Carbonate Compensation Depth was much shallower than at present.
http://en.wikipedia.org/wiki/Carbonate_Compensation_Depth
I am still waiting for someone to produce raw data showing that global ocean pH has been dropping.

Pamela Gray
February 3, 2009 7:07 am

Mauna Loa is not the measure of average CO2 *and all its isotopes* after the equation of sources minus sinks is completed. It is part of the equation but is not the number that comes after the “equal” sign. Some people post about it as if it is exactly that.

Steven Goddard
February 3, 2009 7:48 am

John Philips,
What you describe as “abrupt changes” in CO2 over the last 100 years are in fact less than 3% of the difference between Ordovician and modern concentrations. Given that the corals are not directly exposed to the atmosphere and that the only recent pH data anyone here has produced does not show acidification, you have not yet demonstrated any reason to believe that recent changes in atmospheric CO2 have had or should have any direct impact on the corals.

Graeme Rodaughan
February 3, 2009 7:49 am

Garacka (07:28:48) :
5. Since I am the 1st to reveal this truth, I claim name ownership. Henceforth it will be known as ā€œGarackaā€™s Ruleā€.

Garacka – Truly – I bathe in the sunlight of your wisdom.
(great post-comment).

February 3, 2009 7:49 am

pkatt (02:34:40) :
Bill D (10:29:28) :
pretty obvious you didnā€™t read the link:)
another quote:The tube worms, limpets and lobsters were scarce, the shrimp, crab and scale worms the most commonly seen animals. Also, two types of starfish (red and another white) and anemones (white) plus 4 or 5 types of fish were noted as were some shells of a possible snail ~1-2 cm in length, near the end of the dive. :End quote
I seem to remember crab, and shrimp being qualified as shell fish. I did not attack Steven G. I was simply pointing out that definitively saying corals and shellfish cannot survive in acidic conditions was inaccurate.

Crab and shrimp are crustaceans with chitin based exoskeletons not shellfish (molluscs) which form aragonite shells (which are described as ‘scarce’ in the quotation).

Graeme Rodaughan
February 3, 2009 7:53 am

Alan Millar (05:34:24) :
So which of the alarmists are right?

Both – this subtle argument is very similar to the advanced theory that man made emissions of CO2 will in fact cause both Catastrophic Warming or Catastrophic Cooling…
With luck and much hard work chasing funding, you may become as wise as the wisest climate scientist and be able to fathom such mysterious ambiguities.

Graeme Rodaughan
February 3, 2009 7:58 am

In this forum – I also raise my hand and second Alan Millar’s request.
Could some one please explain how warming oceans can absorb more CO2 such that they can become acidified, given that warming oceans have a well known property of outgassing CO2.
I look forward to a real attempt to address this question.

foinavon
February 3, 2009 8:20 am

Richard S Courtney (05:59:06)

But, as I have repeatedly explained to you on the other thread,
ā€œthere are two components to the recent rise in atmospheric CO2 concentration: viz. the variation that is directly related to mean global temperature (i.e. Calderā€™s ā€˜CO2 thermometerā€™) and the steady rise of 0.4 per cent per year. As you say, Calderā€™s CO2 thermometer seems to be ENSO-related. Hence, it is the steady rise that we need to understand.ā€
And, as I have also repeatedly explained to you on the other thread, that steady rise does not relate to the anthropogenic emission. It is an empirical fact that is does not relate to the anthropogenic emission. Indeed, how could it when that rise is steady and the anthropogenic emission is very variable?

I’m not sure what’s to be gained by calling a scientifically well-characterized phenomenon (the ENSO-related contribution to interannual variability in the change in atmospheric CO2 concentration) someone’s “CO2-thermometer”. It isn’t a “thermometer” at all! The steady rise in atmospheric CO2 concentration relates rather well to our greenhouse gas emissions. It’s very obvious that during the early part of the Mauna Loa record when emissions were lowish, the rate of CO2 rise was smallish (0.7-0.9 ppm/yr). Now when our emissions are much larger, so the accumulation rate of CO2 in the atmosphre is larger (around 2 ppm/yr on average). One can go back to the high resolution Law Dome ice core data and see that one can follow this correlation back in time to the start of the industrial age. When our rate of emissions are low, so is the rate of accumulation of CO2 in the atmosphere; when emissions are high, so is the rate of accumulation of CO2 in the atmosphere. It could hardly be simpler!
So our emissions result in a progressive rise in the accumulation of CO2 in the atmosphere. Averaged over the short term the annual incremental increase correlates rather well with independent analysis of our emissions. Obviously there’s some interannual variability, so that occasionally the annual increment is higher than the trend would indicate, and sometimes its low. But we know why that is and don’t have to make a song and dance about it!

Rubbish! The ā€œreal world evidenceā€ is that the oceans release an order of magnitude more CO2 than the anthropogenic emission each year and they take back almost all of it each year. At issue is why they donā€™t take back all of it.

Really? Evidence please!
Richard, are you getting mixed up with the massive sinusoidal pattern of release and reuptake of CO2 due to the huge amount of seasonal plant growth and decay that is dominated by Northern Hemisphere growing cycles? Otherwise, the evidence indicates that there is a pretty progressive forcing of CO2 into the oceans, and that there isn’t that much of a variability in the interannual CO2 uptake. Not nearly as much as the variability that results from effects in the terrestrial environment.
e.g.:
Lee, K., et al. (1998), Low interannual variability in recent oceanic uptake of atmospheric carbon dioxide, Nature, 396, 155ā€“159.
Feely, R. A., et al. (2002), Seasonal and interannual variability of CO2 in the equatorial Pacific, Deep Sea Res., Part II, 49, 2443ā€“2469
Le QuĆ©rĆ©, C., et al. (2003), Two decades of ocean CO2 sink and variability, Tellus, B55(2), 649ā€“656.

You again cite Zeng (2005) that assumes the rise in atmospheric CO2 concentration is anthropogenic.

Not really Richard. Zeng et al (just one of many papers we could consider on this subject; citation below) addresses the origin of the interannual variation in the rise in atmospheric CO2 concentrations. The origin of the underlying rise in atmospheric CO2 is secondary to the study, although the authors note that interannual variations in the ocean uptake makes only a small contribution to interannual variation in atmspheric CO2, and it’s very well characterized that the oceans provide a strong sink for a significant proportion of our emissions (around 40% of our CO2 emissions go into the oceans so far, although this is likely to decrease in the future). This is directly and rather straightforwardly measurable in the real world. In relation to sinks and sources, the oceans cannot at the same time be a nett sink and a source!
N. Zeng (2005) Terrestrial mechanisms of interannual CO2 variability. Global Biogeochemical Cycles 19, GB1016

Simon Evans
February 3, 2009 8:28 am

Steven Goddard (07:48:41) :
the only recent pH data anyone here has produced does not show acidification
Santana-Casiano et al 2007, for example –
“Our series of experimental pHT data confirm the acidification of surface waters in the east Atlantic Ocean, with an interannual decrease of 0.0017 Ā± 0.0004 pH units yr-1”
http://cat.inist.fr/?aModele=afficheN&cpsidt=18717426

Simon Evans
February 3, 2009 8:41 am

Graeme Rodaughan (07:58:45) :
In this forum – I also raise my hand and second Alan Millarā€™s request.
Alan Millar’s question was addressed as follows:
Perhaps some of our alarmist friends would like to explain.
I’m not an alarmist, so I wont be responding to that.

Chris J
February 3, 2009 8:41 am

@ Steven Goddard,
“I am still waiting for someone to produce raw data showing that global ocean pH has been dropping.”
“Given that the corals are not directly exposed to the atmosphere and that the only recent pH data anyone here has produced does not show acidification,”
Once again, the HOTS (Hawaiin Ocean Time Series) and BATS (Bermuda Atlantic Time Series) demonstrate falling oceanic pH. These data are widely cited, readily available and cited in my post above. Additional datasets are available from NOAA for the tropical Western Atlantic, as well as several others. The data are right there and are unambiguous: oceanic pH and CO3= concentrations are dropping while TCO2, pCO2, and HCO3- concentrations are climbing. Further, the change in oceanic DIC (stable isotopes) matches that of fossil fuel derived CO2. The ocean is being acidified by fossil fuel CO2–it’s plain as day, if you bother to look at the data, of course.
“…you have not yet demonstrated any reason to believe that recent changes in atmospheric CO2 have had or should have any direct impact on the corals.”
Have you examined any of the experimental data wherein corals were exposed to various pCO2 concentrations???
Steven, your ignorance is not evidence. Simply ignoring the data doesn’t mean they don’t exist.
Chris

Bill DeMott
February 3, 2009 8:42 am

pkatt (02:34:40) :
Bill D (10:29:28) :
pretty obvious you didnā€™t read the link:)
Pk att:
Your are correct that I did not read the whole link and I should have, so I stand corrected.
I was concerned about the term “shellfish” when I wrote my original comment. This term may be ok for cook books and restaurant menus, but it refers to a disparate group of animals, none of which are fish. My understanding is that the term “shellfish” includes both crustaceans (which are arthropods) and bivalves (which are mollusks). These groups are quite far apart in terms of physiology, genetics, and phylogeny. The term “shellfish” is confusing and should not be used in scientific discussions. The term probably dates back to the middle ages and reflects something about “”seafood””.
Some posts have already established that the corals that during the ancient times of higher temperatures and atmospheric CO2 were quite different. However, at least these belong to a reasonable monophyletic group.

Richard S Courtney
February 3, 2009 8:47 am

Foinavon:
You assert:
ā€œSince there are very basic errors in the information that you seemed to have provided to the journalist [see foinavon (04:14:55)], the articles premises seem, in fact, not to be so ā€œquestionableā€.ā€
I know of none and you have cited none.
And I still await the apology for your unfounded and gratuitous insult.
John Philip:
You ignored all my points and used smear and inuendo of Jaworowski to deflect attention from my points. When I objected to that you said you ā€œbeg to differā€ and cited a blog article by Hans Oeschger in support of your smear and innuendo. And you challenged me to comment on that blog item saying you look forward to hearing from me. Yu are now hearing from me about it.
The blog is a typical pro-AGW web site called ā€œSome Are Boojumsā€, and it seems to have some of the characteristics of the laughable RealClimate.org. Its article by Oeschger begins saying:
ā€œJaworowskiā€™s article in ESPR is so hard to locate, it wouldnā€™t be too unreasonable to suspect that the journal is not eager now for people to take much notice of it. But it did get noticed by one giant in climate science ā€” Hans Oeschger.ā€
Now, what is that supposed to mean?
Was Jaworowskiā€™s paper hidden so it would not be noticed? Clearly not because they and Oeschger both noticed it. Anyway, Jawarowskiā€™s presentation for the US Senate was not hidden and can be seen at
http://www.warwickhughes.com/icecore/
Or was Jaworowskiā€™s paper so insignificant that it dioes not warrant attention? But Oschger clearly thought it was sufficiently important for him to dispute it.
And Oeschgerā€™s so-called critique on ā€œSome Are Boojumsā€ begins;
ā€œIt is with great hesitation that I write in reply to the paper by JAWOROWSKI, this paper deserves little attention.ā€
This beginning establishes the standard of his critique.
Oeschger second paragraph begins:
ā€œI have been personally involved in the development of this field since its inception.ā€
But he has not studied ice cores as long as Jawarowski who is the ā€˜grandaddyā€™ of scientists who have studied ice cores. Jawarowski has been doing it for over 4 decades. He mounted ten expeditions to glaciers and polar regions to extract ice cores and he developed the basic methods for their recovery, preservation and analysis.
Oeschger continues with a page of pro-AGW propoganda that makes assertions such as;
ā€œAlthough we knew since the nineteen fifties that human activities might change the climate of the Earth, it was not until the mid seventies we realised that mankind was faced with a serious problem.ā€
Really? In the ā€œmid seventies we realised that mankind was faced with serious problemā€? At that time the consensus was fear that anthropogenic aerosol emissions were likely to cause an ice age: ā€œconcerned scientistsā€ petitioned the US President about it. But he clearly states that the ā€œserious problemā€ was (is?) anthropogenic emissions of CO2 and, therefore, AGW. But, to date there is no empirical evidence for AGW; none, zilch, nada, nil. Decades of research have failed to find any. So, his propoganda is nothing more than twaddle.
Oeschger then mentions some of the many faults in ice core analyses that Jaworowski explains but Oeschger does not refute any of them. He merely denies the problems exist with such cogent scientific arguments as:
ā€œFor years he (i.e. Jaworowski) emphasizes only the difficulties of these studies, formulates the underlying assumptions which sometimes are only partly fulfilled and criticizes the work performed hitherto in an unscrupulous manner. He does this without any appreciation for the development of expertise in this field over several decades.ā€
And Oeschger concludes saying:
ā€œThe study of the history of Earth system parameters is an on-going process; an increasing number of laboratories have become involved and interact with each other. As it is the case in any field of science, the state of art is continuously critically assessed and attempts are made to improve the quality of the research. Ice-core information is fundamental for the assessment of one of the most urgent problems of our time. Based on my experience during decades of involvement in this field, I consider the chances as very small that the major findings from greenhouse gas studies on ice cores are fundamentally wrong; and I find the publications of JAWOROWSKI not only to be incorrect, but irresponsible.ā€
Irresponsible? It is ā€œirresponsibleā€ to point out methodological errors in a supposedly scientific analysis? And this accusation is not based on any evidence, information and/or argument but on his ā€œexperienceā€: i.e. his personal opinion.
If you had bothered to watch the video I cited (i.e. I wrote http://www.heartland.org/NewYork08/newyork2008-video.html
At that URL,scroll down to
Monday, March 3, 2008
4:00 – 5:30 p.m.
Track 1: Paleolimatology
and click on my name
then scrollback to the top where the video will appear.)
then you would have known my familiarity with Jaworowkiā€™s work and my decades of association with him.
Clearly, I know more of Jaworoskiā€™s work – and I understand it better – than Oschger. But Oschgerā€™s article suggests that he and I share the same opinion that Jaworowskiā€™s work is important and has important implications. Otherwise, why would Oschger have bothered to write the article, and why does his article fail to provide any evidence that refutes Jaworowskiā€™s main points?
Richard

paminator
February 3, 2009 8:57 am

Steven Goddard- you say “I am still waiting for someone to produce raw data showing that global ocean pH has been dropping.”
Absolutely agreed.
I am also looking for this dataset that would involve measuring ocean pH (measured with an accuracy of 0.01 pH or better to allow reliable measurements of annual or decadal trends in global pH) on an hourly or daily schedule at ten’s of thousands of points evenly distributed (not just near shorelines or along shipping lanes) across the globe’s oceans. Unfortunately, I am pretty sure that this dataset does not exist. It does not exist for a measurement of today’s ocean pH, let alone trends in ocean pH over the last decades or centuries.
The few data sets that exist show remarkably large (up to 1 pH!) daily, seasonal and annual variations in pH compared with the tiny trends people are claiming to know with robust precision. We are back to the same problem that plagues temperature trends, looking for tiny slopes amongst huge short-term variations.

Richard S Courtney
February 3, 2009 9:06 am

Foinavon:
I regret that I am getting tired with your obfuscations so I will address only one of your iterated assertions.
In response to my correctly disputing your assertion that CO2 is being ā€œforced into the oceansā€ I correctly said:
ā€œRubbish! The ā€œreal world evidenceā€ is that the oceans release an order of magnitude more CO2 than the anthropogenic emission each year and they take back almost all of it each year. At issue is why they donā€™t take back all of it.ā€
You replied:
ā€œReally? Evidence please!ā€
I answer that there is far, far too much evidence for me to cite it all here. As summer temperture rises the oceans warm and emit CO2, and they take it back each winter. This is demonstrated, for example, by the Mauna Loa data which you cite. The seasonal variability of CO2 measured at Mauna Loa is an order of magnitude greater than either the anthropogenic emission each year and the net increase in atmospheic CO2 each year.
Of course you could argue that this seasonal variation is a result of volcanology but then you would have to explain why the entire data set is not rubbish. Or you could try to argue that it is a result of land-based flora but then you would have to argue that the decision to measure at Mauna Loa to avoid such biogenic effects was mistaken.
Richard

Bill DeMott
February 3, 2009 9:07 am

foinavon (08:20:22) :
Richard S Courtney (05:59:06)
Foinavon: I am not an expert on the earth’s carbon budget, but everything that I”ve read over the last 20 years agrees with your comment that the oceans are the major carbon sink for the earth. Without losses to the oceans, it’s easy to calculate that the concentration of CO2 in the atmosphere would be rising much more quickly that it currently is.
I have not read or heard any disagreement with this conclusion (oceans are a net sink) before coming to this blog. So, when I read comments like those of Richard on this blog I get confused and wonder whether I am misunderstanding his terminology.
I know more about lakes than atmospherics and do know that the warming of tundra in Canada, Alaska and Siberia has resulted in substantial release of CO2 and methane from lakes and the numerous small ponds that dot the landscape. This is because of the thawing of permafrost soils that have been frozen for millenia. As we all know, when organic matter thaws, the rate of bacterial decomposition increases (for example, if your freezer breaks down and the food thaws; I once was away from home for two months and came home to a broken freezer). These northern soils represent a tremendous store of carbon, one that could cause carbon releases to the atmosphere to get out of human control (if the melting of the permafrost continues). This is not controversial, because it is easy to measure the organic carbon content of these peat rich soils and there is a lot of data. If the climate gets colder and the permafrost stays frozen during summer, this problem will subside. If the melting of the permafrost expands in extent, this problem will accelerate the increase in atmospheric CO2.

SteveSadlov
February 3, 2009 9:13 am

Forget about 200 years. Let’s look at 40 years.
Show me one study, which employed Gage R&R / MSA principles, which is an apples to apples comparison of a significant volume of ocean, across the depth profile, seasons, diurnal variations, which factors in measurement error and innate variations and bias, etc, that demonstrates, at Six Sigma or better, that there has been a general en masse decline in oceanic pH over the past 40 years.
I await such a study. It has yet to be revealed, assuming it exists at all.

foinavon
February 3, 2009 9:14 am

Graeme Rodaughan (07:58:45) :

In this forum – I also raise my hand and second Alan Millarā€™s request.
Could some one please explain how warming oceans can absorb more CO2 such that they can become acidified, given that warming oceans have a well known property of outgassing CO2.
I look forward to a real attempt to address this question.

Much like any solution of CO2, the dissolved concentration is a property of the ocean temperature and the atmospheric pressure of CO2 in the air above the solution. So as the atmospheric concentration of CO2 rises, so does the concentration of CO2 in the oceans. This is simply a mass-action effect defined by a simple partition equilibrium.
On the other hand solutions of CO2 have an inverse temperature-dependence in relation to their ability to absorb CO2. As a solution gets warmer it absorbs CO2 less efficiently.
So the nett effect is very much circumstance-dependent. Atmospheric CO2 concentrations have risen very dramatically since the start of the industrial age, and especially since the early-mid ’60s. The temperature rise has been rather significant (around 0.5-0.6 oC in the ocean). This is rather small in relation to the temperature-dependence of CO2 partitioning, so that the “force” driving CO2 into the oceans (greatly enhanced atmospheric concentrations) strongly dominates over the temperature effect. One can probably state that the warming of the oceans has slightly suppressed the ability of the oceans to take up CO2 from the atmosphere, and no doubt these contributions can be more precisely calculated. However it’s easy to establish that despite some warming, the oceans have done an excellent job of absorbing around 35-40% of our emissions (so far!).
Under the circumastance where temperature changes occur at least initially without changes in atmospheric CO2 concentration the situation is different. In this case the ocean temperature effect dominates, and in a warming world without an initially raised atmospheric CO2 concentration, the atmospheric CO2 concentration will rise in response to enhanced ocean warming (terrestrial contributions are also significant). This is likely the case during the glacial-interglacial transitions of the ice age cycles.
We can gain a pretty good estimate of this effect by observing that during ice age cycles the glacial-interglacial transitions rather uniformly produced a temperature rise of around 5-6 oC globally, associated with an increase in atmospheric CO2 concentration of around 90 ppm (around 180 ppm glacial to around 270 ppm interglacial). These transitions occurred slowly, such that the ocean-atmosphere system was probably pretty close to equilibrium.
So we can estimate that by and large, a 5-6 oC of global warming (initial forcings and resulting feedbacks and all!) results in an atmospheric CO2 rise near 90 ppm, or not far off 15 ppm of CO2 per oC of temperature rise…..

Chris J
February 3, 2009 9:21 am

@ Graeme Rodaughan
“In this forum – I also raise my hand and second Alan Millarā€™s request.
Could some one please explain how warming oceans can absorb more CO2 such that they can become acidified, given that warming oceans have a well known property of outgassing CO2.
I look forward to a real attempt to address this question”
Ha, that’s an incredibly easy question to answer. Gas solubility in water is governed by Henry’s law:
[X] = Kh*pX
where [X] is the concentration of the dissolved gas in umol/kg, Kh is a Henry’s law constant for that gas at a given temperature, pressure, and in sea water, salinity, and pX is the partial pressure of that gas in the overlying atmosphere. Kh for CO2 (and essentially any other common gas) has been well characterized in sea water over a wide range of temps, pressures, and salinities. Of course, these calculations can be easily verified, and re-verified, and re-re-verified ad nauseum by experimentally determing the DIC, k1 and k2 for carbonic acid.
CO2 has risen ~100 uatm to date: from ~285 uatm to ~385 atm. During that same time period mean oceanic temperature has risen ~0.5 C.
We can calculate dissolved CO2 for whatever set of conditions we like. For this example, let’s just set salinity at 35 ppt (mean oceanic value), total alkalinity at 2300 ueq/kg (mean), pressure at 1 atm (mean). We’ll calculate what happens to dissolved CO2 when we go from pCO2 = 285 uatm to 385 atm with and without 0.5 C of warming. We can do this at whatever (realistic) temp we choose, but letā€™s just use a standard temp of 25 C for ease of calculation.
[CO2] @ 25.0 C
pCO2 = 285 uatm, [CO2] = 8.07 umol/kg (pHsws = 8.15, seawater scale pH)
pCO2 = 385 uatm, [CO2] = 10.90 umol/kg (pHsws = 8.05)
Thatā€™s a (10.90-8.07)/8.07 = 35.1% increase in dissolved CO2, the same as the increase in pCO2
If we have the same increase in pCO2 but temperature rises to 25.5 C we get
[CO2] = 10.76 umol/kg (pHsws = 8.05)
Thatā€™s a (10.76-8.07)/8.07 = 33.3% increase in dissolved CO2 for a 35.1% increase in pCO2.
Of course, we can compensate for the increase in pCO2 by raising temperature a lot, to reduce CO2 solubility. In order to obtain the same amount of dissolved CO2 as we had with pCO2 = 285 uatm (= 8.07 umol/kg) all we have to do is raise temperature by 13.6 C up to 38.6 C, hotter than human body temperature! However, this increase in temperature itself results in an even larger reduction of pH than the increase in dissolved CO2 (from 8.15 to 8.03 instead of 8.15 to 8.05). The reduced pH results from a shift in K1 and K2 for carbonic acid, as well as a small influence of K2 for HSO4- and K for HF.
So sir, thereā€™s your answer. The increase in temperature has had a small effect on CO2 solubility. The slight reduction of [CO2] caused by the temp increase is an order of magnitude smaller than the increase in [CO2] caused by the increase in pCO2. See, itā€™s quite simple, and not at all difficult to answer (provided one understands the chemistry, of course).
Chris

foinavon
February 3, 2009 9:22 am

Richard S Courtney (09:06:35)

I answer that there is far, far too much evidence for me to cite it all here. As summer temperture rises the oceans warm and emit CO2, and they take it back each winter. This is demonstrated, for example, by the Mauna Loa data which you cite. The seasonal variability of CO2 measured at Mauna Loa is an order of magnitude greater than either the anthropogenic emission each year and the net increase in atmospheic CO2 each year.

Come on Richard. We all know that the marked sinusoidal variation in atmospheric CO2 that “piggy-backs” on the rising atmospheric CO2 trend, is dominated by the N. hemisphere seasonal plant growth/decay cycles. We surely don’t need to readdress such extraordinarily basic and well-characterised phenomena…
…and in response to my request for evidence, your response is that there is “far too much evidence for me to cite it all here”. I wonder who’s actually “obfuscating” here! I’m attempting to be as clear and careful as I can, and to provide evidence in suport of my points from the scientific literature.
P.S…. if there’s “far too much evidence” to cite, why not just cite a wee bit of it?!

foinavon
February 3, 2009 9:30 am

Bill DeMott (09:07:47)
Yes I agree with you Bill.
Incidentally, since you invited us to look at your publications in an early post, I did so. I have to say you have an impressive set of very beautiful and highly cited papers. I don’t think I’ve ever seen a publication record that is so uniformly well-cited and lacking in inconsequential “bits and pieces”….

E.M.Smith
Editor
February 3, 2009 9:33 am

J Lo (20:58:59) :
So what is this H+ doing? If it is just in solution, then pH lowers, right? ([H+] increasing). If it is reacting, what can it react with?

#DEFINE actually acid “pH 7.0”
#DEFINE neutralizing “pH ==> 0.0”
And here it comes together…
Have you considered that in a solution that is actually alkaline there is an excess of OH- (as opposed to one that is actually acid which has H3O+) and that your H+ is going to instantly react with the OH- to produce H2O ?
(And that is why it matters that something which is actually alkaline be described as ‘neutralizing’ when it’s pH number is becoming smaller as opposed to calling it ‘acidifying’; because to call it acidifying misleads as to the species of ion that are laying about and that leads to bad chemistry predictions.>

Steven Goddard
February 3, 2009 9:37 am

Chris J,
I plugged the first two HOTS pH data sets into a spreadsheet (Kahe and Aloha) and both showed a positive trend in pH over their length of record. I will look at the other two records later.
http://spreadsheets.google.com/pub?key=pj0h2MODqj3i9dc6DdtQDPw
http://spreadsheets.google.com/pub?key=pj0h2MODqj3h1BPd_ggZfSQ
You make bold claims that the data supports your contention of increased acidity, when in fact it does not.

E.M.Smith
Editor
February 3, 2009 9:38 am

Dang it. HTML stole my less than sign…
J Lo (20:58:59) :
So what is this H+ doing? If it is just in solution, then pH lowers, right? ([H+] increasing). If it is reacting, what can it react with?

#DEFINE actually acid “pH less than 7.0”
#DEFINE actually alkaline “pH greater than 7.0”
#DEFINE neutralizing “pH moving toward 0.0”
And here it comes together…
Have you considered that in a solution that is actually alkaline there is an excess of OH- (as opposed to one that is actually acid which has H3O+) and that your H+ is going to instantly react with the OH- to produce H2O ?
(And that is why it matters that something which is actually alkaline be described as ‘neutralizing’ when it’s pH number is becoming smaller as opposed to calling it ‘acidifying’; because to call it acidifying misleads as to the species of ion that are laying about and that leads to bad chemistry predictions.)

E.M.Smith
Editor
February 3, 2009 9:56 am

D (23:16:39) :
The claimant had said ‘super saturated’. I have no dispute that there must be suitable conditions, only over the degree. Freshwater lakes are not typically saturated with carbonate and calcium… though some good water for whiskey comes from the Karst areas šŸ˜Ž BTW, the freshwater clams I referred to were gathered from the Sacramento River basin. Not exactly limestone country (but not zebra’s either)

February 3, 2009 9:57 am

Graeme Rodaughan (07:58:45) :
In this forum – I also raise my hand and second Alan Millarā€™s request.
Could some one please explain how warming oceans can absorb more CO2 such that they can become acidified, given that warming oceans have a well known property of outgassing CO2.
I look forward to a real attempt to address this question.

The absorption of CO2 depends on the Revelle factor of the sea water. The concentration of CO2 is independently increasing, under those circumstances outgassing of CO2 will only occur if the sea surface temperature increases sufficiently to result in a greater mixing layer CO2 concentration than would be in equilibrium with the atmosphere (Revelle factor). If that isn’t the case the ocean will continue to uptake more CO2 from the atmosphere.

Patrick Henry
February 3, 2009 10:04 am

I looked at the other two HOTS data sets, and they don’t have pH data. So far we have seen three pH time series – Monterey Bay, Aloha and Kahe, and they all show a trend towards increased pH (decreasing acidity) over the last 10-15 years.

Richard S Courtney
February 3, 2009 10:11 am

Foinavon:
You say:
“Come on Richard. We all know that the marked sinusoidal variation in atmospheric CO2 that ā€œpiggy-backsā€ on the rising atmospheric CO2 trend, is dominated by the N. hemisphere seasonal plant growth/decay cycles. We surely donā€™t need to readdress such extraordinarily basic and well-characterised phenomenaā€¦”
Well, I am aware of another group who say, “We all know Father Christmas exists”.
Sorry, but the N. hemisphere variation cannot explain the seasonal variation at Mauna Loa except as being an oceanic release and sequestration of CO2 relatively local to Hawaii. If you fail to understand this then look at a map and check the literature to determine how long it takes for CO2 released from the land in the N. Hemisphere to reach Hawaii.
Please do this check for yourself because everything I tell you seems to flow off you like water from a duck.
Richard

alf
February 3, 2009 10:19 am

After millions of years of evolving adaptive genes, is it possible that coral has the ability to adapt to changes of co2 in it’s environment?

J Lo
February 3, 2009 10:21 am

foinavon:
That is an excellent explanation of how buffering works with the real world numbers. I think they fail to realized that there is ALREADY an “excess” of CO3(2-) in the ocean due to CaCO3 CO3(2-) + Ca(2+).
So while they pound the table that “OMG MORE CO2 IN H2O MEANS MORE H2CO3 MEANS MORE CO3(2-)” in a water only solution they are right.
But the ocean has high [CO3(2-)] from the tons of CaCO3 added to it. Think about it, the pH is ~8.1. Not HCO3(-1)
3. Le Chatelierā€™s principle states that if you add H(+) to a system, youā€™ll push the equilibria in a manner that depletes initial [CO3(-2)]
4. So the question is, what is more important to the higher [CO3(-2)] ALREADY in the ocean at pH 8.1, HCO3(-1) or H+?
5. [CO3(-2)] is already present in the ocean probably from all the CaCO3 added to it.
Alan Wilkinson review your PhD.
I’m off to work on mine.

foinavon
February 3, 2009 10:23 am

Richard S Courtney (10:11:52)

Sorry, but the N. hemisphere variation cannot explain the seasonal variation at Mauna Loa except as being an oceanic release and sequestration of CO2 relatively local to Hawaii.

Not really Richard. Go to the Mauna Loa observatory site, look at the Mauna Loa data, and scroll down to the Global Monthly Mean data (averaged over all the ocean surface sites). You’ll see that they’re rather similar. On the mothly/seasonal timescale the equilibration of CO2 across the globe is reasonably efficient. Clearly the Mauna Loa data is not measuring a “relatively local” effect.
Here’s the data:
http://www.esrl.noaa.gov/gmd/ccgg/trends/

Mary Hinge
February 3, 2009 10:29 am

Steven Goddard (07:48:41) :
What you describe as ā€œabrupt changesā€ in CO2 over the last 100 years are in fact less than 3% of the difference between Ordovician and modern concentrations. Given that the corals are not directly exposed to the atmosphere and that the only recent pH data anyone here has produced does not show acidification, you have not yet demonstrated any reason to believe that recent changes in atmospheric CO2 have had or should have any direct impact on the corals.

Directly comparing the qualities of modern corals to the Paleazoic corals in this context is laughable and plainly ridiculous. You do undertand the basic process of evolution do you? You do understand that a lot of changes happen to organisms over geological time (in this case over 400,000,000 years)?
We need to know, do you really understand evolution?

gary gulrud
February 3, 2009 10:34 am

“the seasonal variation at Mauna Loa except as being an oceanic release and sequestration of CO2 relatively local to Hawaii.”
Makes sense to me.

John Philip
February 3, 2009 10:41 am

What you describe as ā€œabrupt changesā€ in CO2 over the last 100 years are in fact less than 3% of the difference between Ordovician and modern concentrations.
For the third time corals species that were extant in the Ordovician are (a) calcite-forming and (b) now extinct anyway, so I don’t really see where you’re going with the comparison. But let’s follow this through … you are equating a change in CO2 concentrations from 6000 to 385ppm over 460,000,000 years [assuming your figures are correct] with a rise of circa 100ppm over 100 years? Do you really expect corals to adapt in a few generations to such a historically steep rise.
Others have now pointed out where to find the evidence of falling ocean pH, I could have added that there were copious references in the Royal Society report on Ocean Acidification (damn, there it is again, In fact the term even has its own domain name and an NOAA web page) I linked to above.
No answer to my request for a marine biologist who agrees with your ‘no big deal’ stance yet. OTOH, Ove Hoegh-Guldberg has over 100 publications in this area and you can read his blog here.

J Lo
February 3, 2009 10:42 am

Wow html WRECKED my last post.
E.M.Smith:
Actually, there are [H+] ions (or H3O+ if you like), in solution at pH greater than 7. They don’t ALL react with OH- at pH above 7. All pH above 7 means is that OH- molecules outnumbers H+ ions in solution.
Water has a dissociation constant of 10^(-14) [which is why a pH scale generally ranges from 0-14. Water spontaneous dissociates H2O -> H+ & OH-.
foinavon:
That is an excellent explanation of how buffering works with the real world numbers. I think they fail to realized that there is ALREADY an ā€œexcessā€ of CO3(2-) in the ocean due to CaCO3 == CO3(2-) + Ca(2+).
So while they pound the table that ā€œOMG MORE CO2 IN H2O MEANS MORE H2CO3 MEANS MORE CO3(2-)ā€ in a water only solution they are right.
But the ocean has high [CO3(2-)] from the tons of CaCO3 added to it. Think about it, the pH is ~8.1.
Wilkinson, you said:
J Lo, if you add some other acid (not CO2) to the ocean, yes, you will reduce carbonate ion levels. But if you add CO2 you wonā€™t because you are adding carbonate ion with the acid.

1. CO2 adds H+ to the ocean
2. H(+) & CO3(-2) -> HCO3(-1),
3. [CO3(-2)] is already present in the ocean, probably from all the CaCO3 == Ca(2+) & CO3 (2-)
4. Le Chatelierā€™s principle states that if you add H(+) to a system, youā€™ll push the equilibria in a manner that depletes initial [CO3(-2)].
5. So the question is, what is more important to the higher [CO3(-2)] ALREADY in the ocean at pH 8.1 starting, dissociation of HCO3(-1) or the addition of H+?
Alan Wilkinson review your PhD.
Iā€™m off to work on mine.

E.M.Smith
Editor
February 3, 2009 10:44 am

pkatt (02:34:40) : Can I say EEEK? Anyone wanna know what happens to corals when you get a plankton bloom??
http://www.int-res.com/articles/meps/60/m060p299.pdf
so I guess its ok to destroy it to save it huh?

Sigh. And we had the link upthread about NO3 causing coral death due to their nitrate sensitivity. So let me get this straight… We’re going to dump a load of nitrogen fertilizer into the ocean to save the coral from the evil CO2? And we’re adding iron to stimulate the growth of plankton as though the bloom is not going to be a problem? OK…
Well, look on the good side, it’s only about 3 Buicks worth of iron…
Hopefully they learn something other than how to create a bloom. (We already know how to do that…)
You know, I have to wonder what the bottom dwelling organisms will think about all this food rich planktonic rain falling on them. Gotta be good, right? It’s not like we don’t know much about the deep oceans. Heck, we’ve been to the moon, we must know more about the ocean bottom. /sarcoff>

Chris J
February 3, 2009 10:47 am

@ Steven Goddard,
“Chris J,
I plugged the first two HOTS pH data sets into a spreadsheet (Kahe and Aloha) and both showed a positive trend in pH over their length of record. I will look at the other two records later.
http://spreadsheets.google.com/pub?key=pj0h2MODqj3i9dc6DdtQDPw
http://spreadsheets.google.com/pub?key=pj0h2MODqj3h1BPd_ggZfSQ
You make bold claims that the data supports your contention of increased acidity, when in fact it does not.”
I don’t know what you’re doing wrong, but there issomething seriously wrong with your data query. The data you present above are not the data you think you have.
You can see the pH time series here (select pH comparison):
http://hahana.soest.hawaii.edu/hot/trends/trends.html
pH was assessed using both spectophotometric methods with m-cresol purple (= ‘measured’) and in accordance with equilibria given measured values of TCO2 and TA (= ‘calculated’).
As you can clearly see, pH is taking a nose dive. The BATS data show the same trend, as do other data sets.
How you ever got it in your head that oceanic pH is rising, or that these data sets show an increase in pH is beyond my comprehension. It requires nothing more complicated than looking at the time-series…perhaps that’s too much to ask. I forget who it was that said it, but it rings ever true: you are entitled to your own opinion, but you are not entitled to your own facts.
You say my claims are bold: no sir, far from it. I am simply familiar with this issue and with the pertinent data, while you clearly do not have even a rudimentary understanding of the chemistry or the available data. As you can see very clearly oceanic pH is dropping, precisely as I said, and opposite your claims to the contrary.
Chris

J. Peden
February 3, 2009 10:59 am

J Lo:
I think they fail to realized that there is ALREADY an ā€œexcessā€ of CO3(2-) in the ocean due to CaCO3 CO3(2-) + Ca(2+).
J Lo, “they” – the equations involved – don’t “fail to realize” anything. And I would assume that your obsession with anthropocentrizing inorganic chemistry also extends to your whole thought process.

Steven Goddard
February 3, 2009 11:04 am

John Philip,
The NOAA web page shows a graph with decreasing pH from HOTS over the last 20 years. However, if you go to the HOTS web site and extract the data for yourself (as I did and linked above and below) there is no such trend.
http://hahana.soest.hawaii.edu/hot/hot-dogs/bextraction.html
http://spreadsheets.google.com/pub?key=pj0h2MODqj3i9dc6DdtQDPw
That is why I asked for raw data.
Mary Hinge,
Your rude post really isn’t worth responded to, but if you believe that the chemical properties of CaCO3 have changed since the Ordovician, please share that theory with us.

E.M.Smith
Editor
February 3, 2009 11:07 am

JamesG (04:18:42) : To me the Cuba conundrum eliminates CO2 as a stress on coral because it is pristine while surrounded by Caribbean coral which is highly ā€œstressedā€. You donā€™t need to be a chemist or biologist to reach that conclusion but anyway, marine biologists say this pristine Cuban coral is due to other human factors and not due to a lack of acidification. If there is actually a particularly alkaline sea found around Cuba then again please point this out to me
Fascinating …
Hmmm. What’s different about Cuba?
1) Embargo.
2) No herds of beached northern white whales on vacation (I are one…)
3) Generally brown / dark skins.
4) Less intensive agriculture.
So I see 2 possible things to investigate (plus whatever I didn’t see šŸ˜‰
1) It’s the sunscreen (as mentioned upthread).
2) It’s the ag runoff (or lack thereof).
I tend to doubt #2 just from a bias that they might not have the best sewage systems, but that’s a preconceived bias on my part. Any statistics on sunscreen sales in Cuba?
Are there any other tropical paradise settings with pristine coral not being flooded with sunscreen laden tourists? It would make an interesting thing to map…

Steven Goddard
February 3, 2009 11:25 am

Just to clear some of the FUD from the water, the chemical composition of aragonite and calcite (CaCO3) is identical, and there are many forms of shellfish in the oceans now that are quite similar to ones that lived in the Ordovician.
And yes we all know that there are lots of scientists who are worried about CO2. That is the point of examining the unfiltered data directly in these articles, to see if their underlying assumptions are correct.

E.M.Smith
Editor
February 3, 2009 11:30 am

Graeme Rodaughan (07:53:57) :

Alan Millar (05:34:24) :
So which of the alarmists are right?

With luck and much hard work chasing funding, you may become as wise as the wisest climate scientist and be able to fathom such mysterious ambiguities.
Ahhh… Enlightenment is coming to me now…
I propose that we skeptics form the “CO2 is Evil Working Group to Save the Corals” and that we get a grant to study the pristine corals response to sunscreen when in an enhanced CO2 regime. This will involve jetting off to pristine tropical locations, slathering on lots of sunscreen, sucking down as much carbonated beverages as we can hold, then swimming out to examine the Corals. Repeatedly. We will also need a specific area set aside for the ‘nitrogen enrichment’ control group that results some time after large amounts of carbonation …

SteveSadlov
February 3, 2009 11:34 am

No one has taken my 6 Sigma offer. OK, price reduction.
4 Sigma.

gary gulrud
February 3, 2009 11:45 am

RE: Moving seamlessly from aragonite to calcite skeletons with pH ~7.7.
I forget the organism but I remember reading, in the last year, of this as accomplished fact. Before you lash back, I’m an aquarist and have a Bio major focussed on evolution(yeah, I’m pro).

gary gulrud
February 3, 2009 11:57 am

“Alan Wilkinson review your PhD.”
Hold up a sec.
The crustal abudance of both Ca and Mg are an order of magnitude greater than C. In the ocean at low pressure and high temperatures CO2 precipitates out of solution in combination with either metal.
In the high pressures of the abyss, CO2 re-enters solution. There are 50,000 Gtons of dissolved CO2 in the oceans, perhaps twice that in precipitates.

Bill D
February 3, 2009 12:00 pm

Some of the postings on this blog start with the false premise that the oceans are releasing more CO2 than they take up and this process is sometimes referred to as “out gassing.” What is the basis for this idea? It is completely false.
Every basic text book on the environment notes that the oceans are the major sink for the earth’s C02. This means, on a net basic, that much carbon is absorbed into the oceans and is eventually deposited on the bottom. This is not just about inorganic carbon chemistry. Most of the carbon that ends up on the bottom of the ocean enters food chains through algal photosynthesis. This is why some people are talking about fertilizing the southern oceans with iron (Fe) to increase the uptake of CO2 by the oceans. My readings on this suggest that even a massive effort would not work, because much of the organic carbon will decompose before it gets deep enough and exchange of surface and deep water is too slow. Some of the carbon that sinks to bottom is in the form of calcareous protists, such as the ones forming the “Cliffs of Dover.” However, my understanding is that most of the sedimenting carbon was fixed by photosynthetic algae (if anyone can come up with data on the relative contributions of these sources (calcareous heterotrophs vs phytoplankton), I would like to see the data.
Please give up on the notion that the oceans are releasing more CO2 than they take up. The number posted above by foinavan says that the oceans are helping us by removing 40% of human-released carbon dioxide. I don’t have the numbers on my fingertips, but this seems about right. This is a massive amount of carbon moving from the atmosphere to the ocean sediment. This makes the increase in atmospheric CO2 slower than it would have been without this sink.
There has been some discussion of how pH changes with depth. This also has a biological explanation, rather than an explanation in inorganic chemistry. Photosynthesis exceeds respiration in well lit surface waters, leading to slightly more basic pH in the upper layers. (remember that photosynthesis takes up CO2 and this reduces acidity). As you go deeper in the water column of a (deep) lake or an ocean, there is not enough light for photosynthesis, so respiration of algae, bacteria and animals leads to a net release of CO2 and a lowering of pH. Corals are fairly shallow, so they response to near surface pH, temperature and light. Any number of lab experiments show that corals are negatively impacted by increases in temperature, decreases in pH and high levels of UV light. Corals require light for their symbiotic algae, but too much light, especially in the ultra violet wave lengths, is destructive.

Bill Junga
February 3, 2009 12:03 pm

So tell me now, just how much CO2 is bubbling up from the floors of the oceans? When a submarine volcano forms a new island does the ph in the surround waters change and how much?
Does this CO2 bubbling up from the floors of the oceans dissolve into the ocean water more readily than does CO2 from the atmosphere? If I have some time I will check these things out. But blaming an “man’s CO2 emissions for a lowering ocean ph when there are many, many things we don’t know about the oceans seems questionable.
A surface ocean Ph of 8.179 or 8.104 seems to be as much of a fiction number as the annual global mean temperature.

George E. Smith
February 3, 2009 12:07 pm

“” Richard S Courtney (10:11:52) :
Foinavon:
You say:
ā€œCome on Richard. We all know that the marked sinusoidal variation in atmospheric CO2 that ā€œpiggy-backsā€ on the rising atmospheric CO2 trend, is dominated by the N. hemisphere seasonal plant growth/decay cycles. We surely donā€™t need to readdress such extraordinarily basic and well-characterised phenomenaā€¦ā€
Well, I am aware of another group who say, ā€œWe all know Father Christmas existsā€.
Sorry, but the N. hemisphere variation cannot explain the seasonal variation at Mauna Loa except as being an oceanic release and sequestration of CO2 relatively local to Hawaii. If you fail to understand this then look at a map and check the literature to determine how long it takes for CO2 released from the land in the N. Hemisphere to reach Hawaii.
Please do this check for yourself because everything I tell you seems to flow off you like water from a duck.
Richard “”
I must be getting senile; I downloaded the NOAA graph of the Mauna Loa Data, so I could see the “marked sinusoidal variation” that Foinavon mentioned; and I can’t find hide nor hair of a sinusoidal variation.
I do see about a 6 ppm peak to peak sawtooth looking variation which has an upside taking 8 months of the year, and a downside for the next 4 months, with very sharp turnaround at the extrema; but I maybe don’t have enough resolution to see the sinusoid he mentioned.
If I had to bet, I would say that the sawtooth is actually the exponential decay of an integrated rectangular waveform, with a 2:1 duty cycle. With a 6ppm drop in four months, that starting rate would eliminate 100 ppm in about 5 1/2 years. But assuming it is an exponential decay of the form:-
1-e^-(t/T), then it would take three time constants to eliminate 95% of the excess, or 99% in five time constants; and the time constant is that 5.5 year number.
So 95% could be removed in 16.5 years by whatever process is causing the ML saw tooth. At the North pole the amplitude of the saw tooth is 18 ppm, so it only takes 5.5 years at that location.
But tell me more about the sinusoidal component ?

J. Peden
February 3, 2009 12:12 pm

foinavon:
What happens to the protons? They mostly protonate carbonate because carbonate has a higher affinity for protons than bicarbonate.
“Mostly”, really?
foinavon, your reasoning is obviously circular/wishful* and qualitative, not quantitative. Adding CO2 on the left must increase CO3 on the right, of course, along with increased H, as per usual. “Chemical intuition” has nothing to do with it. From a chemical bonding perspective, H doesn’t “like” CO3 any more than it used to. There are indeed more H’s, but there are also more CO3’s, and in the exact same proportions as there were before.
Again, there is more CO3!
So there is no new distorting perturbation from adding CO2 which magically causes CO3 to disappear at a net rate greater than it did before, as compared to the reactions which form it, and which are producing more CO3: the ratio of CO3/HCO3 is the same, but there is indeed more CO3.
*It appears that you are now using the increased H twice, once to do what it does as a result of the basic inorganic chemistry involved, then once more to form an excess of HCO3 beyond the basic chemistry, almost as if it “decided” to do it because you want it to. That doesn’t work.
Otherwise, foinavon, simply write the equations which actually show a net loss of CO3 resulting from the addition of CO2.

L Nettles
February 3, 2009 12:13 pm

I guess it wouldn’t suit their purposes to describe the process of changing the pH from 8.179 to 8.104 as a neutralization of the ocean’s pH which is accurate as opposed to acidification which is inaccurate

Bill D
February 3, 2009 12:14 pm

alf (10:19:14) :
After millions of years of evolving adaptive genes, is it possible that coral has the ability to adapt to changes of co2 in itā€™s environment?
Alf: Over the last few million years, coral has adapted to lower than current pH and CO2 in the environment. My understanding is, however, that increased temperature (rather than pollution or acidification) is reponsible for most of the coral losses in the last 20 years (pollution is a problem near populated areas). However, given projected use of fossil fuels, the atmospheric CO2 and ocean pH are easily predicted and the CO2 problem will become more serious over the next few decades, even if the climate does not continue to warm.

Bill D
February 3, 2009 12:23 pm

alf (10:19:14) :
After millions of years of evolving adaptive genes, is it possible that coral has the ability to adapt to changes of co2 in itā€™s environment?
Alf: The corals have adapted to lower than current CO2 and pH for millions of years. Evolution can not predict that a change will occur, in this case human burning of fossil fuels accumulated over the last 500 million years within several hundred years. My understanding is that loss of corals over the last 20 years has been mostly due to heating events. I am not an expert on this, but many coral experts expect that effects of higher CO2 will be serious over the next few decades. Given scenarios for human fuel consumption, calculation of atmospheric CO2 is fairely straight forward.

HasItBeen4YearsYet?
February 3, 2009 12:50 pm

D (12:00:09) :
Time to look at some other text books, or read the ones you have more carefully.
Too bad there are so many “completely false” results as those presented in this abstract, where they “flasely” claim “On a daily basis, the oxbow lake was a net source to the atmosphere of both CO2 (147.1 Ā± 10.8 mmol māˆ’2 dāˆ’1) and CH4 (116.3 Ā± 8.0 mmol māˆ’2 dāˆ’1).”
I suggest you complain to the editor of that publication.

Bill D
February 3, 2009 1:02 pm

One more point—the seasonal variations in the CO2 measured at Mauna Loa are due to increased photosynthesis (mostly terrestrial) during the northern hemisphere spring and summer and low photosynthesis relative to respiration during our fall and winter. This means that plants grow mainly in the spring and summer and respiration and decomposition predominate in the fall and winter. The northern hemisphere predominates over the southern hemisphere because its land mass (North America, Europe, and Asia) is much greater than the land mass of South America, southern Africa and Australia. The oceans don’t have much net effect. I guess that this means that ocean photosynthesis is similar in the northern and southern hemispheres.
Remember that plants take up CO2. On an annual basis, the CO2 is mostly released as plants are eaten by animals or leaves decompose. Photosynthesis and respiration balance almost completely (not decrease or increase over an annual cycle) unless there is a significant increase or decrease in plant (especially forest) acreage. Burning of fossil fuels is far more important than the increases or decreases in plant tissue.
Sometimes I teach a general undergraduate biology class that includes a chapter on the environment. This explanation is what I read in the text and also in scientific papers and what I tell my students. Although some of you may believe that this makes it false, this is also what Al Gore said in his movie. Since I try to give my students the most accurate and up to date scientific explanations, anyone who has a credible source of information should post the source of their opposing view. I would like to read and evaluate it.
Based on my reading and knowledge (which are not always correct) anyone who thinks that the seasonal variation in atmospheric CO2 is due to a local or global ocean exchange is misinformed. Iā€™d like to learn about a mechanism and data that would support the hypothesis that the ocean causes regular seasonal changes in the earthā€™s CO2 atmosphere. ā€œHey it sounds possibleā€ or If itā€™s opposite Al Goreā€™s opinion it must be trueā€ would not be convincing for me. (I am getting a little sarcastic as bed time approaches).

foinavon
February 3, 2009 1:02 pm

George E. Smith (12:07:00)
George, we’ve already had the dismal non-“argument” about the meaning of “acidification”. Are you really going to proceed down a pedantic diversion over the meaning of “sinusoidal”?
Remember that words are only labels for the things that we are choosing to describe.
“Sinusoidal” is actually not a bad description of the very well-characterised cyclic variation in the atmospheric CO2 concentration that follows the seasonal growth/decay cycle in the N. hemisphere which is where most of the earth’s flora “resides”. Since the sinusoidal variation lies on a rising trend of growing atmospheric CO2 it does look a bit “sawtooth”.
So let’s call it “sawtooth” if you like. We both know what we’re looking at.

Glenn
February 3, 2009 1:14 pm

Steven Goddard (11:25:19) :
“Just to clear some of the FUD from the water, the chemical composition of aragonite and calcite (CaCO3) is identical, and there are many forms of shellfish in the oceans now that are quite similar to ones that lived in the Ordovician.”
How about the Dover cliffs of chalk? From the Cretaceous (meaning “chalk bearing”) period, a time of warm temperatures, no icecaps or glaciers, high sea levels, 3 to 7 times the atmospheric CO2 of today, we see massive amounts of chalk made up of shelled fossil creatures that died contributing to the Cliffs we see now, apparently survived. Whatsupwithat? Timing, perhaps.

Bill D
February 3, 2009 1:17 pm

gary gulrud (11:45:46) :
RE: Moving seamlessly from aragonite to calcite skeletons with pH ~7.7.
I forget the organism but I remember reading, in the last year, of this as accomplished fact. Before you lash back, Iā€™m an aquarist and have a Bio major focussed on evolution(yeah, Iā€™m pro).
Gary, you say that the idea that the ocean seems like a plausible explantion for the seasonal (saw tooth, sinusoidal oscillations) in the CO2 data. As a bio major, I hope that you consider the explantion that I gave above. If you still have you old bio text book, you should find a convincing reason before considering its explanation false. signed–an interested bio/ecology/evolution prof.

Glenn
February 3, 2009 1:22 pm

An interesting article, concerning whether coral can survive high CO2:
http://www.bioedonline.org/news/news.cfm?art=3235
“He subjected specimens in the lab to increasingly acidic conditions. It didn’t take long for the colonies in the most acidic environments ā€” those with pH levels as low as 7.3 ā€” to show remarkable changes; within a few weeks, their calcium carbonate skeletons had started to dissolve and the polyps became entirely exposed, he and a colleague report in Science.
Surprisingly, the polyps seemed to fare well under these conditions, growing up to three times their original size and reproducing unhindered. “No one expected that corals could survive such low pH,” says Fine.”
[…]
“Daphne Fautin, a marine zoologist at the University of Kansas, suggests that the calcium carbonate skeleton, which we see as a defining characteristic of stony corals, may in fact be an ephemeral trait that waxes and wanes in response to environmental changes. “

Mary Hinge
February 3, 2009 1:28 pm

Steven Goddard (11:04:19) :
Your rude post really isnā€™t worth responded to, but if you believe that the chemical properties of CaCO3 have changed since the Ordovician, please share that theory with us.

Of course the chemical properties haven’t changed, that’s an absurd statement. What has changed in over 450,000,000 years is the variety and forms of corals.
Corals formed and started evolving into different forms during the ordovician. Many of these became extinct at the end of the Ordovician (the 2nd largest mass extinction event after the Permian). Surviving groups flourished and today there are thousands of different species including the soft corals.
This species have their individual way of dealing with different temperatures, salinity, pH, light levels, tides, seasonal changes etc. There are over 800 known species of reef building corals. This diversity is the important thing and a third of these species are shown to be at risk. A recent study, the Global Marine Species Assessment (2008) by the leading scientists in this field showed that one third of the species study were threatened with extinction.
[snip] (unless of course you know better than the 39 marine biologists that participated).
[snip]
Reply: Mary Hinge, you are stepping over the line here. It is time to enforce civil discourse again…I’mmmmm baaaack ~ charles the moderator

HasItBeen4YearsYet?
February 3, 2009 1:31 pm

Junga (12:03:18) :
1 – see first link in my last post, at (12:50:41)
2 – actual photo of co2 venting from sea floor.
3 – Bubbles of carbon dioxide also are streaming upwards as gases escape from the lava.” HREF=”http://www.noaanews.noaa.gov/stories2006/s2635.htm”>REFERENCE
IT’s a tad more complex than the simplistic Abbot Costello routines of some here, like J Lo, would have you believe. HREF=”http://www.iaea.or.at/programmes/ripc/ih/volumes/vol_one/cht_i_09.pdf”>REFERENCE
MORE ON EXCHANGE OF CO2 AT WATER SURFACES…
A recent estimate of CO2 outgassing from Amazonian wetlands suggests that an order of magnitude more CO2 leaves rivers through gas exchange than is exported to the ocean as organic or inorganic carbon. REFERENCE
“strong vertical mixing of CO2 rich waters during autumn and winter resulted in the area to act as an annual net CO2 source to the atmosphere”[while it was a sink in the spring.] HREF=”http://www.cosis.net/abstracts/EGU04/07322/EGU04-A-07322.pdf”>REFERENCE
And, J Peden, please, I beg of you, DO NOT ASK THEM TO WRITE OUT ANY MORE EQUATIONS, …..PLEEEEEZE. It’s too painful to watch.

Mary Hinge
February 3, 2009 1:41 pm

Iā€™mmmmm baaaack ~ charles the moderator

Hi Charles! Welcome back, missed you! I’m assuming by the snips I was correct in my assumption!
Reply: All that I saw was you being inappropriately rude. I have censored posters being rude to you (multiple times). I will censor you when you are being rude to others. There is nothing else for you to conclude from my actions. I have no personal extra knowledge that you think I may be aware and I have had no contact with Steven Goddard. I read this website less than you do. I generally just scan for tone. ~ charles the moderator.

Bill D
February 3, 2009 1:47 pm

HasItBeen4YearsYet? (12:50:41) :
D (12:00:09) :
Time to look at some other text books, or read the ones you have more carefully.
Too bad there are so many ā€œcompletely falseā€ results as those presented in this abstract, where they ā€œflaselyā€ claim ā€œOn a daily basis, the oxbow lake was a net source to the atmosphere of both CO2 (147.1 Ā± 10.8 mmol māˆ’2 dāˆ’1) and CH4 (116.3 Ā± 8.0 mmol māˆ’2 dāˆ’1).ā€
I suggest you complain to the editor of that publication.
Four years:
I agree with the mechanism and arrows shown in the online text that you cite. These diagrams don’t put any numbers of the rates and amounts, so they don’t disagree with what I have said about which rate dominate.
As for the abstract, I assume that these are measured rates, something that is not difficult to do in a small lake. Without seeing the larger data set or reading the researcher’s methods, no one can evaluate the validity of their (his or her) abstract. Many small lakes, especially those with high inputs of DOC (dissoved inorganic carbon) from their water sheds are net heterotrophic (release rather than store carbon). This is not the case for the world’s oceans, however.

John F. Pittman
February 3, 2009 1:49 pm

MAry The abstract reads “”The conservation status of 845 zooxanthellate reef-building coral species was assessed by using International Union for Conservation of Nature Red List Criteria. Of the 704 species that could be assigned conservation status, 32.8% are in categories with elevated risk of extinction. Declines in abundance are associated with bleaching and diseases driven by elevated sea surface temperatures, with extinction risk further exacerbated by local-scale anthropogenic disturbances. The proportion of corals threatened with extinction has increased dramatically in recent decades and exceeds that of most terrestrial groups. The Caribbean has the largest proportion of corals in high extinction risk categories, whereas the Coral Triangle (western Pacific) has the highest proportion of species in all categories of elevated extinction risk. Our results emphasize the widespread plight of coral reefs and the urgent need to enact conservation measures. “”
Do not see that CO2 induced pH changes are the source, but rather many anthropogenic sources, and the natural source of temperature increase. Even IPCC agrees that natural increased temperature has occurred since the LIA.

Chris J
February 3, 2009 2:00 pm

@ Steven Goddard,
“John Philip,
The NOAA web page shows a graph with decreasing pH from HOTS over the last 20 years. However, if you go to the HOTS web site and extract the data for yourself (as I did and linked above and below) there is no such trend.
http://hahana.soest.hawaii.edu/hot/hot-dogs/bextraction.html
http://spreadsheets.google.com/pub?key=pj0h2MODqj3i9dc6DdtQDPw
That is why I asked for raw data.”
Sir, you are flat-out lying. Go to the link (HOT data), select pH comparison–notice the trend line is sharply down: http://hahana.soest.hawaii.edu/hot/trends/trends.html
“Just to clear some of the FUD from the water, the chemical composition of aragonite and calcite (CaCO3) is identical,”
No, they are not. Calcite can range from hi-Mg calcite (~12-20 mol % MgCO3 in today’s sea water) to low-Mg calcite (< 4 mol % MgCO3). Aragonite is very poor in MgCO3, but comparatively enriched with SrCO3. It is not remotely true to say that calcite and aragonite are chemically identical.
Further, physical differences among hi- and low-Mg calcite and aragonite are profound. Aragonite is ~1.5x as soluble as low-Mg calcite while hi-Mg calcite is ~1.5-1.7x as soluble as aragonite. Not appreciating the differences among these polymorphs is like not appreciating differences among diamond, graphite, and buckeyballs.
“and there are many forms of shellfish in the oceans now that are quite similar to ones that lived in the Ordovician.”
Similar how? Similar in general body plan? Tridacna spp. (giant clams) and hydrothermal vent clams (Calyptogena magnifica) have similar body plans, but they could not be more different. By that same token, people and salamanders have similar body plans. Suggesting that two organisms are physiologically and ecologically equivalent because of similar body plans is, frankly, incredibly nieve.
“And yes we all know that there are lots of scientists who are worried about CO2. That is the point of examining the unfiltered data directly in these articles, to see if their underlying assumptions are correct.”
I couldn’t agree more. Why then are you misrepresenting or flat-out lying about the data??? We SHOULD be discussing the data and the implications thereof. Why are you inventing it as you go?
Chris
Reply: Let’s tone down the accusations of lying please. Back it down gently. We are trying to stay civil around here. First warning.~ charles the moderator.

J Lo
February 3, 2009 2:09 pm

HasItBeen4YearsYet?:
~snip~
J. Peden and Alan Wilkinson:
http://www.publicaffairs.noaa.gov/releases2002/mar02/noaa02r305.html
“Our results are important in understanding the ocean’s role in the global carbon cycle,” Anderson said. “Prior to this study, large changes in ocean carbonate chemistry had been proposed to explain the changes in atmospheric carbon dioxide. Over thousands of years, calcium carbonate compensation appears to be the dominant variable controlling the ocean carbonate (and carbon dioxide) inventory. When carbon dioxide from the atmosphere is added to the oceans, the calcium carbonate on the seafloor dissolves to minimize the carbon dioxide change in the ocean.
If [CO2] increases [CO3(-2)] in the ocean, shouldn’t it be easier to form CaCO3 due to this equilibria: CaCO3 == Ca(++) & CO3(-2) according to Le Chatlierā€™s principal?
You guys are too focused on the generation of CO3(-2) by CO2 in pure water. CaCO3 is the much greater buffer (which is why oceans are alkaline and not acidic).
I rest my case.

gary gulrud
February 3, 2009 2:25 pm

“Gary, you say that the idea that the ocean seems like a plausible explantion for the seasonal (saw tooth, sinusoidal oscillations) in the CO2 data. As a bio major, I hope that you consider the explantion that I gave above.”
I’m more of a low IQ polymath, lately eating as a garden-variety computer engineer.
Obviously any, seasonal fluence can contribute to the seasonal signal. The oceanic biogenic leg I take as not well-understood, and likely larger than currently thought reasonable. Just as most oil now seems of bacterial origin in meteor-schocked sedimentary formations.
The October minimum in the signal, of course, is reached when the contributing fluences have virtually all terminated carbon lay up. NH terrestrial biogenic leg would have done so in July/August so is probably not a big player. The 800 pound gorilla is the SO.
You may, of course, emphasize cyanobacteria, I have to beat drum of the partial-pressure of dissolved CO2, it’s rather inclusive.

Chris J
February 3, 2009 2:25 pm

@ J Peden
“foinavon, your reasoning is obviously circular/wishful* and qualitative, not quantitative. Adding CO2 on the left must increase CO3 on the right, of course, along with increased H, as per usual. ā€œChemical intuitionā€ has nothing to do with it. From a chemical bonding perspective, H doesnā€™t ā€œlikeā€ CO3 any more than it used to. There are indeed more Hā€™s, but there are also more CO3ā€™s, and in the exact same proportions as there were before.”
Oh my sir. Oh my, my, my, your lack of understanding of basic carbonate chemistry is astounding.
You complain about qualitative and not quantitaive reasoning–I couldn’t agree more!
Your claim is that CO3= concentration in sea water increases (as does H+) upon the addition of CO2(g). Great, perform the calculation for us.
Go ahead and use standard seawater conditions (S = 35 ppt, TA = 2300 ueq/kg, P = 1 atm, T = 25 C), to keep things easy. Also, in the interest of ease I’ll even give you the references you need for K1 and K2 for carbonic acid (Mehrbach et al. as refit by Dickson and Millero, 1987) and K2 for HSO4- (Dickson, 1990).
Go ahead and calculate all the carbonate system parameters for us (pHsws, pCO2 in uatm, TCO2, [CO2], [HCO3-], [CO3=], all in umol/kg) at 3 levels of pCO2: 280 uatm, 380 uatm, 840 uatm.
Oh, and show your work. These calculations should be a breeze for you, afterall, and it should be easy to demonstrate that upon the addition of CO2(g) [CO3=] increases, as does [H+].
Of course, in reality you’re completely wrong. I doubt very much you have any idea how to perform these calculations (yes I do, can, and have no problem doing so) so as to determine precisely all components of the carbonate system from the two given components: total alkalinity and pCO2.
If you’re convinced you’re correct and [CO3=] increases upon CO2 addition, please demonstrate mathematically. If you can’t, please listen more and talk less.
Chris

Chris J
February 3, 2009 2:28 pm

“Reply: Letā€™s tone down the accusations of lying please. Back it down gently. We are trying to stay civil around here. First warning.~ charles the moderator.”
Charles,
Should I not call a spade a spade??? However, I will stive to be more cordial.
Best,
Chris

Glenn
February 3, 2009 2:37 pm

ā€œJust to clear some of the FUD from the water, the chemical composition of aragonite and calcite (CaCO3) is identical,ā€
“No, they are not. Calcite can range from hi-Mg calcite (~12-20 mol % MgCO3 in todayā€™s sea water) to low-Mg calcite (< 4 mol % MgCO3). Aragonite is very poor in MgCO3, but comparatively enriched with SrCO3. It is not remotely true to say that calcite and aragonite are chemically identical.”
Get a grip. Aragonite and calcite have identical chemical composition.
Neither are magnesium carbonate or strontium carbonate.
Perhaps you are trying to address the chemical makeup of certain corals, shells, fossils or minerals.

Chris J
February 3, 2009 2:48 pm

@ Glenn,
“Glenn (14:37:30) :
ā€œJust to clear some of the FUD from the water, the chemical composition of aragonite and calcite (CaCO3) is identical,ā€
ā€œNo, they are not. Calcite can range from hi-Mg calcite (~12-20 mol % MgCO3 in todayā€™s sea water) to low-Mg calcite (< 4 mol % MgCO3). Aragonite is very poor in MgCO3, but comparatively enriched with SrCO3. It is not remotely true to say that calcite and aragonite are chemically identical.ā€
Get a grip. Aragonite and calcite have identical chemical composition.
Neither are magnesium carbonate or strontium carbonate.
Perhaps you are trying to address the chemical makeup of certain corals, shells, fossils or minerals.”
Typical aragonite might be on the order of ~0.1 mol % MgCO3, some SrCO3, other impurities, and the rest as CaCO3. Typical hi-Mg calcite might be 20 mol % MgCO3 and less than 80 mol % CaCO3 with very little SrCO3. These are chemically identical???? Are you serious???
Also, hi-Mg calcite, low-Mg calcite, and aragonite ARE three different minerals….
Chris

Mary Hinge
February 3, 2009 2:48 pm

Reply: All that I saw was you being inappropriately rude. I have censored posters being rude to you (multiple times). I will censor you when you are being rude to others. There is nothing else for you to conclude from my actions. I have no personal extra knowledge that you think I may be aware and I have had no contact with Steven Goddard. I read this website less than you do. I generally just scan for tone. ~ charles the moderator.

Point taken, it is just frustrating when a guest poster cannot graps the processes he writes about.

HasItBeen4YearsYet?
February 3, 2009 2:56 pm

D (13:47:23)
“….they donā€™t disagree with what I have said about which rate dominate.”
A “net outgassing” means that the rate out is greater than the rate in, so yes they do.
_______________________________________________________________________
THE NORMAL pH RANGE OF SEAWATER IS ABOUT 7.2 – 8.2, WITH THE AVERAGE AT ABOUT 7.6
_____________________________________________________________________
“Piss off. Adults are talking.” — J Lo
Sorry, Mr. Gumby, I didn’t realize you were in the middle of brain surgery.

Glenn
February 3, 2009 2:57 pm

Seems the chimneys of hot CO2 pumpering underwater hydrothermal vents are partially made of – calcite, which has the unusual character of being less soluble in water at higher temperatures. There’s a situation to consider.
Picture of a soft coral growing on a black smoker chimney (page 7, fig 5):
http://www.cshe.unimelb.edu.au/downloads/SLiMEs_and_black_smokers-Microbes.pdf

Glenn
February 3, 2009 3:08 pm

“Sir, you are flat-out lying. Go to the link (HOT data), select pH comparisonā€“notice the trend line is sharply down:” http://hahana.soest.hawaii.edu/hot/trends/trends.html
I did. What trend line? You mean the “calculated” line mean? I don’t know what “calculated” means, but I suspect it is a prediction, like “acidification”.
But look at the “measured” ph. 1992 – 1998 shows no downward trend, if anything an upward trend. 2003 – 2008, except for the last gasp in 2008, shows no downward trend. The two series together show no downward trend, or very little, starting in 1992 around 8.085 and ending in 2008 at around 8.085. Perhaps you are relying on that little red line going straight down on the right hand border of the graph?

Glenn
February 3, 2009 3:10 pm

Piss off. Adults are talking.ā€ ā€” J Lo
“Sorry, Mr. Gumby, I didnā€™t realize you were in the middle of brain surgery.”
He thinks he’s acting like an adult.

Steven Goddard
February 3, 2009 3:21 pm

Chris J, Mary H,
The hysterics round here are getting very annoying.
The HOTS graph which you pointed to has “calculated” and “measured” data smeared together. If you look at their actual measured data of seawater pH, there is no trend.
You can do this by going to to the HOTS data – http://hahana.soest.hawaii.edu/hot/hot-dogs/bextraction.html select pH and hit the “Sumbit Query” Button. Repeat, but this time select Station Kahe Pt. Again no trend. This is the second or third time I have explained this here, and if you had of taken the 20 seconds of effort required you would know this for yourself.
Before you start calling people liars or stupid, you might want to check your thought process.
Biologists are being told that global temperatures are rising rapidly and that the ocean is becoming acidic. Of course they are concerned. What I am trying to uncover is if the base information they are being given is correct. So far, the prognosis is the same old story for CO2. Lots of hysterics and very little actual data to support them.

Glenn
February 3, 2009 3:32 pm

Chris J,
“Typical aragonite might be on the order of ~0.1 mol % MgCO3, some SrCO3, other impurities, and the rest as CaCO3. Typical hi-Mg calcite might be 20 mol % MgCO3 and less than 80 mol % CaCO3 with very little SrCO3. These are chemically identical???? Are you serious???”
My bad, I didn’t realize you were referring to the completely different mineral called “typical aragonite”. Try adding a couple more question marks and see if you don’t attain enlightenment. I’ll help a little more:
“Typical” aragonite and calcite is CaCO3, which is called “calcium carbonate”.

Alan Millar
February 3, 2009 3:43 pm

Chris
“So sir, thereā€™s your answer. The increase in temperature has had a small effect on CO2 solubility. The slight reduction of [CO2] caused by the temp increase is an order of magnitude smaller than the increase in [CO2] caused by the increase in pCO2. See, itā€™s quite simple, and not at all difficult to answer (provided one understands the chemistry, of course).”
So you agree, that these alarmists who constantly bang on about how the AGW warmed planet will cause the oceans to outgass CO2 and therefore add a significant positive feedback to atmospheric CO2 levels, are talking rubbish as the oceans will actually absorb more CO2 as concentrations increase and therefore the oceans need to be factored in as a negative feedback to increasing levels of CO2?
Please confirm that that is your position.
I need confirmation as I am fed up of alarmists trying to stir up panic on both sides of the issue, often in the same post!
Do the GCMs have the oceans as a negative parameter?
Alan

jarhead
February 3, 2009 4:04 pm

Chris J
I am a slow student and I am trying to follow the argument about the raw ph data.
The Aloha records show a starting ph of 7.575 on 4/16/92 and a ph of 7.972 on 12/21/7. The Kahe Pt shows 8.092 on 6/8/92 and 8.097 on 12/20/7. Both these locations show a HIGHER ph over 15 years. What is wrong with the data?

Glenn
February 3, 2009 4:19 pm

“You can do this by going to to the HOTS data – http://hahana.soest.hawaii.edu/hot/hot-dogs/bextraction.html select pH and hit the ā€œSumbit Queryā€ Button. Repeat, but this time select Station Kahe Pt. Again no trend. This is the second or third time I have explained this here, and if you had of taken the 20 seconds of effort required you would know this for yourself.”
Don’t be too hard on Chris. He might be color blind, and didn’t see all the red ink on the left below his blue “trend line” and all the red ink above that line on the right of the chart.
Steven, have you considered that Hawaii seeps fresh water all over the place, under and around and over the ocean (not to mention the stuff that is in the runoff etc), and that ocean currents are complex and vary considerably? I wouldn’t be surprised that this data represents as much or more variability from these sources as does carbonic acid, if that varies much at all. Of course, there is the local condition of the volcano spewing out CO2 into unpredictable and unobservable wind patterns mixed with warmth and frequent rainfall. I’d be interested in data gathering methods and locations, among other things, to attempt to find out how and what data is actually collected and the quality of that data.
But my bigger question is whether seawater is or can be tested specifically for carbonic acid and other chemicals and gases. So far I’ve become frustrated trying to find the answer. There are many things that can affect water ph. I think this would be the acid test, so to speak. But perhaps the specific makeup of seawater is just too difficult or not possible to directly isolate and quantify.

HasItBeen4YearsYet?
February 3, 2009 4:26 pm

@Glenn (15:08:36) :
“What trend line? You mean the ā€œcalculatedā€ line mean?”
Talk about “massaging the data!” (depending on what they mean by “calculated”)
“Whaddya mean this square peg doesn’t fit? I’ll show ya. Where’s my data-hammer? ”
Hold on. This is odd. Have you looked at “pCO2 Comparison” at that link? I wonder how they get an inverse relationship between atmospheric [CO2] and it’s partial pressure at sea level?
Let’s see, higher conc., of CO2 gives lower pressure, and lower conc., give higher pressure….? You don’t suppose Maxwell’s demon is real, do you?!

HasItBeen4YearsYet?
February 3, 2009 4:30 pm

@ Steven Goddard (15:21:32)
btw, the 2nd half of my last comment was directed your way

HasItBeen4YearsYet?
February 3, 2009 5:21 pm

Finally, here’s about as clear an overview of CO2 atmosphere/ocean interaction as you’re going to find.

HasItBeen4YearsYet?
February 3, 2009 5:33 pm

Sorry, but after I entered that comment (16:26:15) I went back to the links above about that topic and realized some didn’t take you where I wanted, so… in order to (hopefully) minimize confusion, http://hahana.soest.hawaii.edu/hot/trends/trends.html“>this is the site to go to, from which to select “pCO2 Comparison”.

February 3, 2009 5:48 pm

Glenn (15:32:47) :
Chris J,
ā€œTypical aragonite might be on the order of ~0.1 mol % MgCO3, some SrCO3, other impurities, and the rest as CaCO3. Typical hi-Mg calcite might be 20 mol % MgCO3 and less than 80 mol % CaCO3 with very little SrCO3. These are chemically identical???? Are you serious???ā€
My bad, I didnā€™t realize you were referring to the completely different mineral called ā€œtypical aragoniteā€. Try adding a couple more question marks and see if you donā€™t attain enlightenment. Iā€™ll help a little more:
ā€œTypicalā€ aragonite and calcite is CaCO3, which is called ā€œcalcium carbonateā€.

And they have different crystal structures which causes the two minerals to have different properties, such as solubility, density etc. Calcite is the more stable form at atmospheric temperature and pressure.
In the context of this discussion different organisms produced different structures in their shells depending on the chemical environment, see below for example:
http://gsa.confex.com/gsa/2008AM/finalprogram/abstract_150348.htm
http://findarticles.com/p/articles/mi_qa4067/is_200507/ai_n15348256

February 3, 2009 6:00 pm

HasItBeen4YearsYet? (17:21:15) :
Finally, hereā€™s about as clear an overview of CO2 atmosphere/ocean interaction as youā€™re going to find.

From a string theorist who has a limited knowledge of the subject!
Henry’s law only applies for solutions where the solvent does not react chemically with the gas being dissolved. A gas that does react with the solvent is carbon dioxide which reacts with water. He should have used Revelle factors.

J. Peden
February 3, 2009 6:59 pm

foinavon:

pH = pKa + log[base/acid]
so if the pKa for the bicarbonate – carbonate equilibrium is 9.1 in seawater (canā€™t remember the exact value) then at pH 8.1 the carbonate concentration is around 10% of the bicarbonate concentration. If the ocean pH drops by 0.3 pH units (say), the carbonate concentration drops to 5% of the bicarbonate concentrationā€¦and so onā€¦

[Yes, log 2 = .3. I’ve had this memorized for about 40 years, only because 20 is about the average/”normal” ratio of HCO3 to dissolved CO2 in blood.]
Certainly that’s what the Henderson Hasselbach equation might say in a vacuum: CO3 could be lower, given an unspecified drop in pH – that is, due to an unspecified addition of H.
But what happens when CO2 in particular is added to the solution is different. Given a resulting measured pH – from the addition of CO2 – all [base/acid] = [CO3/HCO3] has to do is to be in the right ratio to get the measured pH. So CO3 can indeed be increased. This is pretty obvious, right?
pH can also be calculated using [base/acid] = [HCO3/dissolved CO2].
Now, I personally saw HCO3 increase, virtually always – probably at least hundreds of times – in cases where increased amounts of CO2 were added to Human blood – while pH went down, as expected.
In cases of “CO2 retention” involving respiratory insufficiency where excess CO2 could not be “blown off”, measured pH decreased and measured HCO3 increased, just as the equations say it should.
Again, with the addition of CO2 to plasma/blood, measured HCO3 virtually always increased over “average” depending upon how much CO2 increased. It never decreased.
This increase makes more HCO3 available to then dissociate to H and CO3, resulting in at least some increase in CO3, just as in the Oceans.
The problem with the initial example is that in the Oceans all of the reactions are going on in a dynamic equilibrium, so they can’t simply be isolated into a theoretical H.H. equation where individual constituents are manipulated in isolation, to “prove”, for example, that if pH drops, CO3 must have dropped.

Chris J
February 3, 2009 7:17 pm

@ Steven Goddard,
ā€œChris J, Mary H,
The hysterics round here are getting very annoying.
The HOTS graph which you pointed to has ā€œcalculatedā€ and ā€œmeasuredā€ data smeared together. If you look at their actual measured data of seawater pH, there is no trend.ā€
Steven, I already explained the where these two different data sources come from. They are using different methodologies to measure different things. The graphic I linked to is for the Aloha station. They have a long-term dataset for a huge number of parameters, including DIC, TA, S, T, P, DIP, total silicate, etc. pH can be calculated from these data more accurately than it can be measured with the tools that were available when they started taking this data (namely electrodes). As above, the ā€˜calculatedā€™ pH values are for the mixed depth using these data. This method remains at least tied for the most accurate way to determine seawater pH, and the data continue to the present. These data are available for the Aloha and Kahe stations.
After they had already started taking these data a new spectrophotometic method for seawater pH determination became available (Clayton and Byrne, 1992) using m-cresol purple, which proved to be highly accurate (much better than electrodes). Soon after that method became available they began taking another data set using this method at both stations. These two data sets measure slightly different water masses, but show the same trends (see below).
ā€œYou can do this by going to to the HOTS data – http://hahana.soest.hawaii.edu/hot/hot-dogs/bextraction.html select pH and hit the ā€œSumbit Queryā€ Button. Repeat, but this time select Station Kahe Pt. Again no trend. This is the second or third time I have explained this here, and if you had of taken the 20 seconds of effort required you would know this for yourself.ā€
Steven, honestly I wish I could help, but I donā€™t know what is giving you trouble. I copied and plotted the pH data for both the Aloha and Kahe stations and surely enough, the trend in pH is down for both.
ā€œBefore you start calling people liars or stupid, you might want to check your thought process.ā€
To be fair, I never called anyone stupid. Perhaps I did jump the gun above and for that I apologize. It does seem youā€™re genuinely confused/having trouble.
ā€œBiologists are being told that global temperatures are rising rapidly and that the ocean is becoming acidic. Of course they are concerned.ā€
Believe me, I know. Iā€™m one of them: biominerlization and, secondarily, the effects of ocean acidification are my area of research. Ocean acidification is a difficult issue, and there is much left to learn, no question about it. However, spending time trying to undermine issues that were resolved long ago (i.e., dissolve CO2 into seawater and the pH and CO3= concentration drop like a rock) is simply unproductive. There are real issues that need to be tackled here, there are real questions remaining. Iā€™d love to discuss those. Itā€™s unfortunate no one else seems to care to.
ā€œWhat I am trying to uncover is if the base information they are being given is correct. So far, the prognosis is the same old story for CO2. Lots of hysterics and very little actual data to support them.ā€
Steven, the data are right there for you. Iā€™d be happy to try to help you trouble-shoot, and Iā€™ve done my best to explain how those data were derived. There are areas where we do lack data, and more work needs to be done. Unfortunately weā€™re quibbling here over things that are old hat instead of discussing the actual unanswered questions in this field.
Best,
Chris

Chris J
February 3, 2009 7:23 pm

@ Glenn,
“Chris J,
ā€œTypical aragonite might be on the order of ~0.1 mol % MgCO3, some SrCO3, other impurities, and the rest as CaCO3. Typical hi-Mg calcite might be 20 mol % MgCO3 and less than 80 mol % CaCO3 with very little SrCO3. These are chemically identical???? Are you serious???ā€
My bad, I didnā€™t realize you were referring to the completely different mineral called ā€œtypical aragoniteā€. Try adding a couple more question marks and see if you donā€™t attain enlightenment. Iā€™ll help a little more:
ā€œTypicalā€ aragonite and calcite is CaCO3, which is called ā€œcalcium carbonateā€.”
The point I was making evidently did not come across. Calcite and aragonite are chemically different. Aragonite is mostly CaCO3, though there are impurities, while most calcite, especially hi-Mg calcite is significantly composed of MgCO3. Yes, they are both principally CaCO3, but a basketball court and a treehouse are both principally wood. There are very, very important differences related to the different chemical composition, as well as fundamental phyisical differences (due to distinct lattice structure) that imparts substantially different solubilites, stabilities, etc.
Chris

Chris J
February 3, 2009 7:50 pm

@ Alan Millar,
“Chris
ā€œSo sir, thereā€™s your answer. The increase in temperature has had a small effect on CO2 solubility. The slight reduction of [CO2] caused by the temp increase is an order of magnitude smaller than the increase in [CO2] caused by the increase in pCO2. See, itā€™s quite simple, and not at all difficult to answer (provided one understands the chemistry, of course).ā€
So you agree, that these alarmists who constantly bang on about how the AGW warmed planet will cause the oceans to outgass CO2 and therefore add a significant positive feedback to atmospheric CO2 levels, are talking rubbish as the oceans will actually absorb more CO2 as concentrations increase and therefore the oceans need to be factored in as a negative feedback to increasing levels of CO2?
Please confirm that that is your position.
I need confirmation as I am fed up of alarmists trying to stir up panic on both sides of the issue, often in the same post!
Do the GCMs have the oceans as a negative parameter?
Alan”
The oceans have absorbed much (a bit over 1/3) of the CO2 produced from burning fossil fuels. The oceanic mixed layer (~50 m) takes about a year or so to come to equilibrium with respect to DIC, and hence with [CO2]. Given measured fluxes of CO2 (depends heavily on wind, mixing) to the ocean from the atmosphere and the relatively fast equilibration of the mixed layer, the surface ocean (outside of areas of upwelling, of course) is usually pretty close to equilibrium with atmospheric CO2. Right now (can be seen in the HOT, BATS, etc. data) [CO2] in the surface mixed layers is usually only a few years ‘behind’ the rise in atmospheric CO2. Of course that’s expected since the CO2 is added to the atmosphere and has to diffuse to the ocean.
That surface water is eventually mixed down through the ocean though. The time needed to turn the ocean over is ~600 years, at present. Hence, some of the CO2 gets slowly buried in the deep ocean while most of it remains partitioned among the shallow ocean and atmosphere on short timescales.
Hence, the oceans definitely are absorbing and will continue to asorb CO2. The real problem, and I would guess the one that you allude to above (though I would be at all surprised the clueless going off half-cocked and declaring the ocean will become a CO2 source while we’re still emitting CO2), is that as the ocean warms it can hold less CO2. That means more CO2 stays in the atmosphere. The ocean won’t stop absorbing CO2, but it can slow down the rate of absorption (and in fact it has in the past couple of decades, relative to what it used to take up–it’s not 100% clear why though, to the best of my knowledge).
As long as we are emitting fossil fueld CO2 to the atmosphere the ocean will absorb at least some of it. However, once we stop emitting CO2 to that atmosphere (even if it is simply when we burn every bit of fossil fuel on the planet) the atmospheric concentration will begin to drop as CO2 is taken up by terrestrial plants, and through chemical weathering. Now we’ll see the reverse process playing out, where the ocean is a source of CO2 and terrestrial environments become the sink. Effectively what that shapes out to is that a quantity of CO2 equivalent to a portion of our CO2 emissions will be in the atmosphere/shallow ocean for a long, long time (hundreds of thousands of years+).
The ocean and the atmosphere are neigther sources nor sinks all the time, only in context.
As for GCMs, I’m a somewhere between a biologist, chemist and geologist in terms of my work, but a climatologist or computer programmer I am not. Yes, feedback loops between ocean and atmosphere like this are amongst the most fundamental parts of GCMs, from what I know, but you’d need to talk with someone that works with them for specifics.
Hope that helps,
Chris

February 3, 2009 7:51 pm

Glenn (15:08:36) :
ā€œSir, you are flat-out lying. Go to the link (HOT data), select pH comparisonā€“notice the trend line is sharply down:ā€ http://hahana.soest.hawaii.edu/hot/trends/trends.html
I did. What trend line? You mean the ā€œcalculatedā€ line mean? I donā€™t know what ā€œcalculatedā€ means, but I suspect it is a prediction, like ā€œacidificationā€.

Then I suggest you educate yourself about the measurement of the properties of sea water. The ‘calculated’ pH is determined from the measurement of total CO2 and total alkalinity of the sample, it’s a standard routine chemical method for determining the pH of sea water.
pH, alkalinity and total CO2 are inter-related so measure any two and you can calculate the third. This method is used to calculate in situ pH. Direct measurement of sample pH depends on the temperature and pressure at which the measurement is made. Measuring alkalinity and TCO2 allows the in situ pH to be calculated without that complication. (See for example: “Methods of Seawater Analysis”, Klaus Grasshoff, Manfred Ehrhardt, Klaus Kremling, Lief G. Anderson)
http://cdiac.ornl.gov/ftp/cdiac74/sop03.pdf

Steven Goddard
February 3, 2009 7:58 pm

Chris J,
I have no idea why you are continuing to propagate this story. I explained the methodology, generated the raw HOTS data from their web site, and provided links to spreadsheets with the HOTS data for both Aloha and Kahe. I have calculated linear regressions for both trends as well as the standard deviations, and I have repeated this exercise several times using narrower depth profiles for both sites – and always see the same thing. There is no statistically significant downward trend in pH at either site. Certainly nothing within an order of magnitude of the 150% increase in acidity which the IPCC claims by the end of the century. And as Glenn pointed out, the Hawaii data is possibly influenced by freshwater flowing into the ocean.
The Monterey Bay data actually shows a minor trend towards higher pH.
Nobody so far has presented any raw data which corroborates the idea that the oceans are rapidly increasing in acidity.

jarhead
February 3, 2009 8:02 pm

To Chris J
You did not answer my question. The raw data source shows no real change in two locations over a 15 year time span.
You wrote “Steven, honestly I wish I could help, but I donā€™t know what is giving you trouble. I copied and plotted the pH data for both the Aloha and Kahe stations and surely enough, the trend in pH is down for both.” The site you used shows this data…
The Aloha records show a starting ph of 7.575 on 4/16/92 and a ph of 7.972 on 12/21/7. The Kahe Pt shows 8.092 on 6/8/92 and 8.097 on 12/20/7. Both these locations show a HIGHER ph over 15 years.
Why do you claim the data shows a downward trend?? Can you please post the data you used? Thanks in advance.

Chris J
February 3, 2009 8:05 pm

@ J. Peden,
What’s the problem, I thought you were going to calculate the full carbonate parameters for standard sea water for us at different levels of pCO2, showing how to perform the calculations, no? You know, that calculation that, according to you, will produce an increase in CO3= concentration and a reduction in pH… Where are the calculations? Above you discuss an increase in HCO3- concentration upon the addition of CO2 (which absolutely does occur, as I said), now show us that CO3= increase you keep promising us. Give us the numbers–the concentrations.
Or, if you’d prefer, we could see how the calculation is performed, and you can see that in fact pH and CO3= drop like a rock with the addition of CO2.
Chris

Glenn
February 3, 2009 8:13 pm

Chris J,
Ok, although you messed up big time with claims about the chemical composition of aragonite and calcite, you have offered what apparently
looks like some knowledge of the ph graph, and I found this from prior posts of yours:
“pH was assessed using both spectophotometric methods with m-cresol purple (= ā€˜measuredā€™) and in accordance with equilibria given measured values of TCO2 and TA (= ā€˜calculatedā€™).”
“They have a long-term dataset for a huge number of parameters, including DIC, TA, S, T, P, DIP, total silicate, etc. pH can be calculated from these data more accurately than it can be measured with the tools that were available when they started taking this data (namely electrodes). As above, the ā€˜calculatedā€™ pH values are for the mixed depth using these data.”
TCO2 is the total concentration of all forms of carbon dioxide including bicarbonate and carbonate as well as dissolved CO2? And TA is titration alkalinity, a quantity of hydrogen ions in moles?
And that a calculation using only these two measures results in the ph of a water sample?
Can you provide some evidence that what you say is true concerning “measured” and “calculated”?
http://hahana.soest.hawaii.edu/hot/protocols/chap23.html
“pH is measured electrochemically using a combination
electrode.”
“The pH of seawater samples is calculated using the
electrode slope and isoelectric point and sample temperature.”

February 3, 2009 8:30 pm

Richard S Courtney (09:06:35) :
Foinavon:
I regret that I am getting tired with your obfuscations so I will address only one of your iterated assertions.
In response to my correctly disputing your assertion that CO2 is being ā€œforced into the oceansā€ I correctly said:
ā€œRubbish! The ā€œreal world evidenceā€ is that the oceans release an order of magnitude more CO2 than the anthropogenic emission each year and they take back almost all of it each year. At issue is why they donā€™t take back all of it.ā€

Nonsense! The mass of the atmosphere is ~5×10^18kg, the annual fluctuation of CO2 is ~4ppm so that gives an annual fluctuation of ~20 Gtonne. The annual emission of fossil fuel worldwide in 2004 was ~27 Gtonne, so for your ‘order of magnitude’ greater release of CO2 should result in an annual fluctuation of ~50ppm!
You replied:
ā€œReally? Evidence please!ā€
I answer that there is far, far too much evidence for me to cite it all here. As summer temperture rises the oceans warm and emit CO2, and they take it back each winter. This is demonstrated, for example, by the Mauna Loa data which you cite. The seasonal variability of CO2 measured at Mauna Loa is an order of magnitude greater than either the anthropogenic emission each year and the net increase in atmospheic CO2 each year.

As demonstrated above this is wrong, your apology for misleading posts is awaited.

Glenn
February 3, 2009 8:50 pm

Phil,
“Then I suggest you educate yourself about the measurement of the properties of sea water. The ā€˜calculatedā€™ pH is determined from the measurement of total CO2 and total alkalinity of the sample, itā€™s a standard routine chemical method for determining the pH of sea water.
pH, alkalinity and total CO2 are inter-related so measure any two and you can calculate the third.”
Thank you for the reference. I must study and cross reference this and your claims before coming to any conclusions. As I said before, I don’t remember much chemistry. This method though appears to be possibly close to what I have been searching for, a direct and dependable way of determing amounts of acid in seawater produced by CO2.
But I have other concerns about these graphs. It seems clear that the “measured” shows no downward trend. Yet these measured values are not plotted for the complete time series. The measured and calculated values are not even close to being the same. Some data points of each measurement at certain times are off by more than the total variation of either in the chart. See where I am having a problem? Without the full range of measured, no comparison at all can be made, only the calculated values show a trend. And it seems that measurements would be a lot easier and more likely to have been done and recorded than the “comparison” process of finding ph. If one took out the comparison data, and “filled in” or “adjusted” the missing measurement data, there would be no downward trend. One or the other isn’t reliable, and collection or data integrity is suspect.
http://hahana.soest.hawaii.edu/hot/trends/trends.html (ph comparison)

Bill Junga
February 3, 2009 8:50 pm

So then, just how much CO2 is necessary to drop seawater pH from 8.1 to say 7.1 and if an addition of CO2 supposedly causes pH to drop like a rock and just how long would this take?And this CO2 comes from the combustion of fossil fuels.

Glenn
February 3, 2009 8:55 pm

Chris J,
“The oceans have absorbed much (a bit over 1/3) of the CO2 produced from burning fossil fuels.”
Sorry, that quantification is somewhat speculative, since we are spending millions of dollars to find that out right now.
http://www.theregister.co.uk/2008/11/14/nasa_oco_launch_site/

J. Peden
February 3, 2009 8:55 pm

Chris J (20:05:08) :
@ J. Peden,
Whatā€™s the problem, I thought you were going to calculate the full carbonate parameters for standard sea water for us at different levels of pCO2, showing how to perform the calculations, no?

No, Chris, that’s what you demanded, in somewhat of a desperate fury, I might add. Not a good sign.
No, it’s not up to me to disprove the equations of basic inorganic chemistry, it’s up to those who claim the disproof. I’m willing to be corrected, just not by wish, “intuition”, or “counter-intuition”. Not to mention not by a phobic “fear of acid”.
Btw, where do you think CO3 comes from to begin with?

February 3, 2009 9:00 pm

Steven Goddard (19:58:05) :
I have no idea why you are continuing to propagate this story. I explained the methodology, generated the raw HOTS data from their web site, and provided links to spreadsheets with the HOTS data for both Aloha and Kahe. I have calculated linear regressions for both trends as well as the standard deviations, and I have repeated this exercise several times using narrower depth profiles for both sites – and always see the same thing. There is no statistically significant downward trend in pH at either site. Certainly nothing within an order of magnitude of the 150% increase in acidity which the IPCC claims by the end of the century.

The trend shown here is ~0.03 pH units in 20 years so over the next century we might expect ~0.15 pH units which gives ~150% increase in H+
http://hahana.soest.hawaii.edu/hot/trends/trends.html

Glenn
February 3, 2009 9:11 pm

Chris J,
“The point I was making evidently did not come across. Calcite and aragonite are chemically different.”
No, Chris, they are not. Pure calcite has the same chemical composition as pure aragonite. When mixed with impurities, they are not pure. But when you say “calcite”, you shouldn’t mean magnesium calcite. It isn’t hard to understand, or convey.

Bill D
February 3, 2009 10:25 pm

One of the problems I see for this discussion is that some bloggers think that the demonstration that a process occurs tells us something about its importance. For example, none of us who have documented the roles of terrestrial photosynthsis and respiration in the seasonal dynamics of atmopheric CO2 disagree that deep sea vents can release CO2. The question is how great is this flux relative to othere fluxes.
All sorts of scientists calculate “budgets” which are directly analogous to economic budgets. For example, if I pay $500 per month for my family’s food and $2.00 for chewing gum, I can probably ignore the chewing gum expense if I need to bring my budget into balance. Scientists need to know which fluxes (expenses and incomes) are important and also which are changing.
I published a

Bill D
February 3, 2009 11:21 pm

One important issue for bloggers here is that the fact that a process occurs does not say anything about its importance. Scientists of all kinds address this issue by developing budgets. Those of us who have documented that seasonal cycles in atmospheric CO2 are caused by seasonal changes in terrestrial photosynthesis and respiration do not dispute that deep sea vents release CO2. I am very aware of CO2 and methane release by wetlands, lakes and ponds ( There was an international conference on this topic last week at my institute in The Netherlands but not in my department). Conclusions about the importance of terrestrial photosynthesis, fossil fuel burning, burial in the oceans etc are based on measurements and calculations of these rates in comparison to other rates.
A scientific budget is directly analogous to a monetary budget. For example, if I spend $500 per month for my familyā€™s food and an additional $1 on chewing gum, I do not need to be concerned about chewing gum if my budget needs to be balanced. I published a study on the phosphorus and carbon balance of Daphnia using radioactive C14 (carbon) and P32 (phosphorus) to help calculate the fluxes (DeMott et al. 1998, Limnology and Oceanography). If you want to criticize this example, you should be able to find a PDF by Googling. This study included some important and somewhat surprizing findings that have incorporated into models over the last 5 years or so. Thus, the citation record of my article shows that my study had a strong positive effect on the field. This study was not related to climate or to pollution (at least not directly) and is mainly applicable in basic understanding of seasonal and between-lake comparisons.
In making budgets, scientists are very concerned to evaluate the uncertainty in various estimates and measurements. Itā€™s very easy for someone to say ā€œthese are only estimatesā€ or ā€œI donā€™t believe the numbers or statisticsā€. If you feel this way, you really need to go back and carefully analyze the original papers and their data sources and assumptions.
In general, if a paper published in a good journal states that estimates have a high certainty or probability , most scientists will assume that the authors, reviewers and editors have done their due diligence (and are not conspiring to mislead other scientists). This is why I place more credibility on the published scientific literature than on internet postings that have not been peer reviewed. This is also why using unpublished, unreviewed internet postings to attack the scientific literature does not have credibility. If something in one of my publications is mistaken or inaccurate, I expect to read about it in new scientific articles. Scientists are always eager to publish and finding a significant error in an earlier publication is a great reason for a new publication and further data collection to verify the error. Since scientists are also concerned about their reputations and credibility with other scientists, they are very cautious about what they publish. The idea more than a very small number of scientific publications are blatantly false or based on misunderstandings of basic principals has no credibility. The idea that new studies will clarify and modify the conclusions of earlier studies IS very true.

Richard
February 4, 2009 12:12 am

Chris J. has completely owned this thread. Thank you for trying to educate those (Mr. Goddard for example) who wish to deceive, manipulate, and generally misrepresent these processes and their associated evidence.

Bill DeMott
February 4, 2009 1:22 am

HasItBeen4YearsYet? (14:56:37) :
D (13:47:23)
ā€œā€¦.they donā€™t disagree with what I have said about which rate dominate.ā€
A ā€œnet outgassingā€ means that the rate out is greater than the rate in, so yes they do.
4 years:
Perhaps this “net outgassing” only refers to the outgassing and not the global CO2 budget. That would be my interpredation to your quote.
The Oceans take up far more CO2 than they release. The contention is whether that uptake will be slowed as pH declines.
One important paper (Sabine et al. 2004 Science 305:367-371 estimates that the oceans have absorped almost 50% of the anthropogenic CO2 released since the beginning of the industrial revolution. The title is “The oceanic sink for antrhopogenic CO2.”
When talking about net changes, we need to be careful to understand whether the net is for a single process or the whole budget.

MartinGAtkins
February 4, 2009 1:30 am

“There is uncertainty over whether the Chicxulub impact made much of an impact on the end-Cretaceous extinction/global warming/ocean anoxia/acidification. The evidence indicates that it predates the K/T boundary event by around 300,000 years.”
The Cretaceousā€“Tertiary boundary contain a concentration of iridium many times greater than normal (30 times and 130 times the usual background) have been found in sedimentary rocks all over the world. The event was catastrophic and more than enough to destroy the life cycle of the Dinosaurs.
Far from CO2 warming the planet, the event sent temperatures plummeting. Geological speaking the situation didn’t last long but it destroyed much of the flora and fauna, initially by fire but also by smothering and blocking the sun. This was confirmed by layers of ash at same at time of impact.
“In general many of the major extinction events in the deep past are associated with massive and prelonged tectonic events resulting in enhanced greenhouse warming, ocean anoxia (reduced pHā€¦reduced oxygen).”
This is patently untrue. During the warmer periods of the earths history, life abounded when CO2 was at much higher levels than now. While it is probable that tectonics have played a part in some extinctions, sudden cooling and the rapid change in the ocean currents indicate that that was the cause of ocean anoxia. During these times coral still survived.
From the paper.
“Our record shows stable Late Cretaceous/ Early Tertiary background pCO(2) levels of 350-500 ppm by volume, but with a marked increase to at least 2,300 ppm by volume within 10,000 years.”
Funny how their records show this. The late Cretaceous/ Early Tertiary studies show the exact opposite. They were steady at just under 3000 ppm during Late Cretaceous/ Early Tertiary and only fell to 350-500 ppm in the late Tertiary.
http://tinyurl.com/d3uul3

E.M.Smith
Editor
February 4, 2009 1:40 am

Aragonite is a carbonate mineral, one of the two common, naturally occurring polymorphs of calcium carbonate, CaCO3. The other polymorph is the mineral calcite. Aragonite’s crystal lattice differs from that of calcite, resulting in a different crystal shape, an orthorhombic system with acicular crystals. Repeated twinning results in pseudo-hexagonal forms.
Looks like the trace inclusions do not determine the mineral definition, but the crystalline structure does. While I’ll grant there may be trivial differences in reactivity between the two structures; it sure looks like the bulk character is going to be pretty much the same; both being calcium carbonate…
I’m noticing a trend here. “Warmers” like to change definitions on the fly and make up new rules of how things work. They get cranky when folks want them to use the established ‘shared’ understandings. “Skeptics” like to adhere to established rules of operation, shared definitions, and get cranky when folks go changing definitions on the fly. Hmmm Not sure what to make of it…

Mary Hinge
February 4, 2009 2:19 am

Steven Goddard (15:21:32) :
Chris J, Mary H,
The hysterics round here are getting very annoying.
Before you start calling people liars or stupid, you might want to check your thought process.

I never called you a liar, stupid, or any combination of these two. You are however ignorant (in the nicest and most correct sense of the word) on the biology of corals and of evolutionary processes. This is alarming as it is the main premise in your argument. You cannot compare primive palaezoic corals from the complex and divergent corals of today. To say that because corals have survived higher CO2 levels in the distant geological past does not mean that symbiotic reef building corals will do so now. Remember that whilst increased temperatures and reduced pH may not kill them, the loss of fitness due to having to grow in sub-optimum conditions will result in increases in disease events ( Willis, B., Page, C and E. Dinsdale., 2004, Coral disease on the Great Barrier Reef, Coral Health and Disease, E. Rosenber and Y.
Loya, 69-104, Springer-Verlag Berlin Heidelberg), (Weil, E., 2004, Coral reef diseases in the wider Caribbean, Coral Health and Diseases, E. Rosenberg and Y. Loya, 35-68, Springer
Verlag, NY) ,(Sutherland, K.P., Porter, J.W., and Torres, C., 2004, Disease and immunity in Caribbean and Indo-Pacific zooxanthellate corals,
Marine ecology progress series, 273-302),( Jacobson, D.M., 2006, Fine Scale Temporal and Spatial Dynamics of a Marshall Islands Coral Disease Outbreak: Evidence for
Temperature Forcing, EOS, Transactions, American Geophysical Union36, suppl.)(,Bruno, J.F., Selig, E.R., Casey, K.S., Page, C.A., Willis, B.L., Harvell, C.D.,, 2007, Thermal Stress and Coral Cover as Drivers of
Coral Disease Outbreaks
Sweatman, H., and Melendy, A.M., PLoS Biol6, e124, )and the increase in growth of more adaptable species. This will reduce biodivirsity which is essential for global fish stocks as coral reefs are important natural hatcheries for many fish species .
The experts in this field agree that one third of reef building coral species are threatened with extinction. I am very sure they know a lot more about this subject than you do.

Richard S Courtney
February 4, 2009 3:34 am

Phil:
I have made no ā€œmisleading postsā€. I have only made factually accurate ones as anybody can check for themselves. If an apology is needed then it is from you for saying otherwise.
You say:
ā€œNonsense! The mass of the atmosphere is ~5Ɨ10^18kg, the annual fluctuation of CO2 is ~4ppm so that gives an annual fluctuation of ~20 Gtonne. The annual emission of fossil fuel worldwide in 2004 was ~27 Gtonne, so for your ā€˜order of magnitudeā€™ greater release of CO2 should result in an annual fluctuation of ~50ppm!ā€
Sorry, but No!
The Mauna Loa seasonal fluctuation is about 10 ppmv per year (not 4 ppm) see
http://www.esrl.noaa.gov/gmd/ccgg/trends/
And Mauna Loa is chosen as a sample site because its seasonal fluctuation is exceptionally low being less than half that elsewhere: e.g. the seasonal fluctuation is more than double that where measured in the Northern Hemisphere, e.g. at Alert, Estavan (both in Canada) and in the Shetland Islands (ref Keeling and Worf, ā€˜On Line Trendsā€™ CDIAC.ORNL).
Your statement that ā€œThe annual emission of fossil fuel worldwide in 2004 was ~27 Gtonneā€ emphasises my repeated (above) statement that the anthropogenic emissions vary greatly from year-to-year.
As I said, ā€œin some years almost all the anthropogenic emission seems to be sequestered and in other years almost noneā€ (according to data from CDIAC.ORNL). And I have repeatedly pointed out that there are justifiable reasons for smoothing the annual emissions data with at most 3-year averageing but the IPCC uses 5-year averages because 2-yeaqr, 3-year and 4-year smoothings do not work.
Typically, according to the NASA estimate, the human emission is about 6.5 GtC/year: see
http://science.hq.nasa.gov/oceans/system/carbon.html
The accumulation rate of CO2 in the atmosphere is equal to almost half the human emission. The human emission is about 6.5 GtC/year but the accumulation rate is about 3 GtC/year. However, this does not mean that half the human emission accumulates in the atmosphere, as is often stated. The system does not ā€˜knowā€™ where an emitted CO2 molecule originated and there are several CO2 flows in and out of the atmosphere that are much larger than the human emission. The total CO2 flow into the atmosphere is at least 156.5 GtC/year with 150 Gt of this being from natural origin and 6.5 Gt from human origin. So, on the average, about 2% of all emissions accumulate.
And the NASA estimate is that about 100 Gt of carbon are released to the air from the oceans and is sequestered by the oceans each year. This alone is a seasonal fluctuation that justifies my statement that the seasonal variation is an order of magnitude greater than the anthropogenic emission.
Furthermore, according to the NASA estimate, the carbon in the air is less than 2% of the carbon flowing between parts of the carbon cycle. And the recent increase to the carbon in the atmosphere is less than a third of that less than 2%.
The flows between deep ocean and ocean surface layers are completely unknown and it is not possible even to estimate them. All we know is that the air contains aboout 760 GtC, the ocean surface layer about 800 GtC, and the deep oceans about 38,000 GtC. The thermohaline circulation conveys the major flows between deep ocean and ocean surface layers.
NASA also provides an estimate that the carbon in the ground as fossil fuels is 5,000 GtC, and humans are transferring it to the carbon cycle at a rate of 6.5 GtC per year.
In other words, the annual flow of carbon into the atmosphere from the burning of fossil fuels is less than 0.02% of the carbon flowing around the carbon cycle.
It is not obvious that so small an addition to the carbon cycle is certain to disrupt the system because no other activity in nature is so constant that it only varies by less than +/- 0.02% per year.
Richard

foinavon
February 4, 2009 3:54 am

J. Peden (18:59:16) :
I don’t really see what you think is to be gained by attempting to extemporize away the laws of physics and physical inorganic chemistry!

Certainly thatā€™s what the Henderson Hasselbach equation might say in a vacuum: CO3 could be lower, given an unspecified drop in pH – that is, due to an unspecified addition of H.

Since chemical acid/base equilibria are solution phenomena, the notion of what might happen in a vacuum is meaningless.

But what happens when CO2 in particular is added to the solution is different. Given a resulting measured pH – from the addition of CO2 – all [base/acid] = [CO3/HCO3] has to do is to be in the right ratio to get the measured pH. So CO3 can indeed be increased. This is pretty obvious, right?

Since the dissolution of CO2 results in the release of protons, and the pH drops, the ratio of CO3– to HCO3- decreases as we can establish easily both from theory and from experiment as described above [foinavon (02:43:33)].

Now, I personally saw HCO3 increase, virtually always – probably at least hundreds of times – in cases where increased amounts of CO2 were added to Human blood – while pH went down, as expected.

Yes. That’s exactly what the analysis of the chemical equilibria and proton affinities of the species leads one to expect. It’s exactly what I described above [foinavon (02:43:33)]. If you add CO2 to blood the pH drops since hydrated CO2 is an acid (H2CO3 or carbonic acid). Since the pH of blood is higher than the pKa for dissociation of H2CO3 to HCO3- + H+, the concentration of bicarbonate will increase. Since the pH of blood is lower than the pKa for dissociation of HCO3- to CO3– + H+, and the dissociation of carbonic acid to bicarbonate releases a proton, the concentration of carbonate (CO3–) will decrease.
Surely by your own reasoning (add CO2 to blood…the pH goes down), it’s completely obvious that the carbonate concentration of blood will also decrease.

This increase makes more HCO3 available to then dissociate to H and CO3, resulting in at least some increase in CO3, just as in the Oceans.

No. see [foinavon (02:43:33)]. Since the pH decreases, the equilbrium dissociation of bicarbonate (HCO3-) to carbonate (CO3–) is shifted in the direction of bicarbonate. The concentration of carbonate decreases. This can be calculated explicitly using the Henderson-Hasselbalch equation. The concentration of carbonate is already very low (especially in blood where the pKa of the bicarbonate-carbonate equilibrium is higher than in seawater), and the decrease in carbonate by the acid-induced shift towards bicarbonate considerably outweighs the tiny increase in carbonate that one might presume from application of mass-action notions without considering the effects of the protons on the position of the equilibria (see [foinavon (02:43:33)]).

The problem with the initial example is that in the Oceans all of the reactions are going on in a dynamic equilibrium, so they canā€™t simply be isolated into a theoretical H.H. equation where individual constituents are manipulated in isolation, to ā€œproveā€, for example, that if pH drops, CO3 must have dropped.

Not true. The positions of each of the equilbria can be determined using the Henderson Hasselbalch equation just as can be done in blood. Knowing the total carbon content of the oceans or blood, the absolute concentrations of the species linked by the dissociation equilibria can be calculated knowing the pH and the various pKa’s.

JamesG
February 4, 2009 4:13 am

Mary Hinge
“The experts in this field agree that one third of reef building coral species are threatened with extinction. I am very sure they know a lot more about this subject than you do.”
You miss the point! I’m sure the experts are correct to worry about that. It’s also fair to assume that it’s likely to be entirely man’s fault. I bet the majority of the people on this site are also worried about the coral too. However, just imagine that we thought it was one specific chemical that caused it, despite a multitude of other manmade chemicals being dumped in the sea, as well as raw sewage and physical damage from fishing vessels. Now assume we put all our efforts towards limiting the release of that particular chemical and did nothing about all the others. Now suppose we were wrong and the coral disappeared because we were just too dogmatic. Do you see now the real issue and why it’s important to be continue to investigate and get it right, regardless of our respective ideologies?
Not one of these experts has tied CO2 to coral extinction. If it’s not actually to blame then that will never be possible. Most experts say there are multiple factors involved. It’s simply fashionable to focus exclusively on blaming CO2 for everything nowadays – probably because it brings in funding rather more easily when you do so. But is it correct?
Despite the numerous derailing attempts here about carbonate chemistry, ancient history or cherry-picked papers using an assumption as a conclusion, there is still no definite link to CO2. Yet to suspect CO2 is entirely justified. The next step in the process though is to eliminate all other possibilities. I’ve mentioned twice now that Cuba’s pristine coral puts a great big hole in the CO2 “stress” theory and nobody has yet challenged that. Since you are good at citing papers, can you point me to one which has mentioned this conundrum? Or am I the first to do so?

foinavon
February 4, 2009 4:20 am

Richard S Courtney (03:34:56)

And Mauna Loa is chosen as a sample site because its seasonal fluctuation is exceptionally low being less than half that elsewhere

That’s simply not true as simple inspection of the Mauna Loa data shows. Go to the NOAA Mauna Loa site (link just below) and inspect the seasonal fluctuation at Mauna Loa. Now scroll down a bit to view the seasonal fluctuation averaged over all of the sea surface sites. It’s very obvious that the amplitude of the seasonal fluctuation is is perhaps 20% higher than the fluctuation averaged over the sea surface sites:
http://www.esrl.noaa.gov/gmd/ccgg/trends/
Why is the amplitude at Mauna Loa a bit larger? It’s because Mauna Loa is in the Northern hemisphere. The Northern hemisphere contains far more biomass than the Southern hemisphere since there is far more Northern hemisphere land mass than in the S hemisphere. The seasonal fluctuation in atmospheric CO2 concentration is the result of the seasonal plant growth cycles. As the carbon dioxide diffuses through the atmosphere, the seasonal fluctuations remain “sharpest” in the N. hemisphere atmosphere, and are “smoothed” somewhat as one moves to the S. hemisphere (and high latitudes of both hemispheres). Since many of the sea surface measuring stattions for CO2 are in the S. hemisphere, the global average is somewhat “smoothed” relative to Mauna Loa.
This is all very basic and well-characterized stuff Richard. Why the persistent attempt to convey notions that simply aren’t true?

Graeme Rodaughan
February 4, 2009 4:43 am

Simon Evans (08:41:06) :
Graeme Rodaughan (07:58:45) :
In this forum – I also raise my hand and second Alan Millarā€™s request.
Alan Millarā€™s question was addressed as follows:
Perhaps some of our alarmist friends would like to explain.
Iā€™m not an alarmist, so I wont be responding to that.

Fair enough – I’ll re-ask politely.
Is anyone able to explain how a warming ocean could absorb CO2 and become more acidic – given that warming oceans have a well known property of outgassing CO2? – Or is this simply a non-starter?
Thanks.

Graeme Rodaughan
February 4, 2009 4:47 am

Whoops – Thanks Phil at Phil. (09:57:57) : For an answer.
(Will need to look up Revelle)

Graeme Rodaughan
February 4, 2009 4:49 am

Whoops (take 2) and Foinavon, and Chris J.
Thanks for the effort guys… Much Appreciated.
Cheers G

foinavon
February 4, 2009 5:17 am

MartinGAtkins (01:30:09)

foinavon (10:53:07) : ā€œThere is uncertainty over whether the Chicxulub impact made much of an impact on the end-Cretaceous extinction/global warming/ocean anoxia/acidification. The evidence indicates that it predates the K/T boundary event by around 300,000 years.ā€
The Cretaceousā€“Tertiary boundary contain a concentration of iridium many times greater than normal (30 times and 130 times the usual background) have been found in sedimentary rocks all over the world. The event was catastrophic and more than enough to destroy the life cycle of the Dinosaurs.

Well yes, but the K/T boundary doesn’t correspond temporally with the Chicxulub impact crater (the latter is dated around 300,000 years too early). It’s not a big deal. However it’s considered that the K/T boundary is associated with another impact whose crater hasn’t been found.
see for example:
Keller G (2005) Impacts, volcanism and mass extinction: random coincidence or cause and effect? Austral. J. Earth Sci 52 725-757.
(I’ve reproduced the abstract below [***] )

foinavon: ā€œIn general many of the major extinction events in the deep past are associated with massive and prelonged tectonic events resulting in enhanced greenhouse warming, ocean anoxia (reduced pHā€¦reduced oxygen).ā€
This is patently untrue. During the warmer periods of the earths history, life abounded when CO2 was at much higher levels than now. While it is probable that tectonics have played a part in some extinctions, sudden cooling and the rapid change in the ocean currents indicate that that was the cause of ocean anoxia.

The evidence indicates otherwise. The evidence supports major tectonic processes as underlying many of the major extinctions in earth’s history. These have been reviewed recently by Wignall and by Twitchett who both resent copious evidence for an association between major tectonic events and extinctions in the deep past:
Wignall P (2005) The link between large igneous province eruptions and mass extinctions Elements 1, 293-297
Abstract: “In the past 300 million years, there has been a near-perfect association between extinction events and the eruption of large igneous provinces, but proving the nature of the causal links is far from resolved. The associated environmental changes often include global warming and the development of widespread oxygen-poor conditions in the oceans. This implicates a role for volcanic CO2 emissions, but other perturbations of the global carbon cycle, such as release of methane from gas hydrate reservoirs or shut-down of photosynthesis in the oceans, are probably required to achieve severe green-house warming. The best links between extinction and eruption are seen in the interval from 300 to 150 Ma. With the exception of the Deccan Trap eruptions (65 Ma), the emplacement of younger volcanic provinces has been generally associated with significant environmental changes but little or no increase in extinction rates above background levels.”
R. J. Twitchett (2006) The palaeoclimatology, palaeoecology and palaeoenvironmental analysis of mass extinction events
Palaeogeog., Palaeoclimatol., Palaeoecol. 232, 190-213

Notice also that the “common-sense” notion of warm being “good” for the abundance and diversity of life is debatable to say the least!. See for example:
PJ Mayhew et al. (2007) A long-term association between global temperature and biodiversity, origination and extinction in the fossil record Proceedings of The Royal Society B 275, 47ā€“53.
Abstract: “The past relationship between global temperature and levels of biological diversity is of increasing concern due to anthropogenic climate warming. However, no consistent link between these variables has yet been demonstrated. We analysed the fossil record for the last 520Myr against estimates of low latitude sea surface temperature for the same period. We found that global biodiversity (the richness of families and genera) is related to temperature and has been relatively low during warm ‘greenhouse’ phases, while during the same phases extinction and origination rates of taxonomic lineages have been relatively high. These findings are consistent for terrestrial and marine environments and are robust to a number of alternative assumptions and potential biases. Our results provide the first clear evidence that global climate may explain substantial variation in the fossil record in a simple and consistent manner. Our findings may have implications for extinction and biodiversity change under future climate warming.”

I’ll address the graph in your link in another post, since that very misleading sketch (which appears in the top “article” of this thread), is patently wrong…
—————————————-
[***]Abstract: “Large impacts are credited with the most devastating mass extinctions in Earth’s history and the Cretaceous – Tertiary (K/T) boundary impact is the strongest and sole direct support for this view. A review of the five largest Phanerozoic mass extinctions provides no support that impacts with craters up to 180 km in diameter caused significant species extinctions. This includes the 170 km-diameter Chicxulub impact crater regarded as 0.3 million years older than the K/T mass extinction. A second, larger impact event may have been the ultimate cause of this mass extinction, as suggested by a global iridium anomaly at the K/T boundary, but no crater has been found to date. The current crater database suggests that multiple impacts, for example comet showers, were the norm, rather than the exception, during the Late Eocene, K/T transition, latest Triassic and the Devonian-Carboniferous transition, but did not cause significant species extinctions. Whether multiple impacts substantially contributed to greenhouse worming and associated environmental stresses is yet to be demonstrated. From the current database, it must be concluded that no known Phanerozoic impacts, including the Chicxulub impact (but excluding the K/T impact) caused mass extinctions or even significant. species extinctions. The K/T mass extinction may have been caused by the coincidence of a very large impact ( > 250 km) upon a highly stressed biotic environment as a result of volcanism. The consistent association of large magmatic provinces (large igneous provinces and continental flood-basalt provinces) with all but one (end-Ordovician) of the five major Phanerozoic mass extinctions suggests that volcanism played a major role. Faunal and geochemical evidence from the end-Permian, end-Devonian, end-Cretaceous and Triassic/Jurassic transition suggests that the biotic stress was due to a lethal combination of tectonically induced hydrothermal and volcanic processes, leading to eutrophication in the oceans, global warming, sea-level transgression and ocean anoxia. It must be concluded that major magmatic events and their long-term environmental consequences are major contributors, though not the sole causes of mass extinctions. Sudden mass extinctions, such as at the K/T boundary, may require the coincidence of major volcanism and a very large Impact.”

Steven Goddard
February 4, 2009 5:21 am

Mary Hinge,
No one disagrees that coral reefs are under stress. Here is an excellent GIS site which I have already discussed, and maps out the threats for every reef in the world.
http://reefgis.reefbase.org/default.aspx?wms=RGWRR&bbox=-30,-193.324022346369,330,193.324022346369&layers=Coral%20Reefs,Countries,Mangroves,Country%20Borders,Coastlines,ThreatExploitation,
with the primary threats being exploitation, coastal development, overfishing and inland pollution.
The claim that I am disputing is that increasing atmospheric CO2 will lead to lower pH and thus undersaturated carbonate, which will make it impossible for CaCO3 shells to be excreted. The same mechanism which has been present in shellfish and corals for at least 500 million years – when CO2 levels were an order of magnitude higher than now.
It is wonderful that you are concerned about the corals. I am too.

Mike Bryant
February 4, 2009 6:01 am

E M Smith,
You are correct, the proponents of AGW believe we live on an unstable earth, on which any change, no matter how small, inevitably becomes a cascade event with a catastrophic outcome. I like to read the science/environment articles at physorg, and it seems that every study or paper cited contains the word “alarming” uttered by either the researchers or the publishers.
This crying of “WOLF, WOLF” increasingly and incessantly over every issue that has research money attached to it, has become painfully obvious even to the non-scientist.
Mike Bryant

JamesG
February 4, 2009 6:03 am

Now i know that bleaching is nothing to do with acidification and bleaching is the wrong term anyway because coral is naturally white – the colors are from parasites. But here’s something quite interesting:
http://news.nationalgeographic.com/news/2001/07/0725_coralbleaching.html
/quote
Is Bleaching Coral’s Way of Making the Best of a Bad Situation?
For an organism that can’t move, coral turns out to be pretty nimble.
Coral has a critical partnership with certain algae that absorb sunlight and convert it to energy needed to feed the complex array of life found in a reef ecosystem. The loss of these algae, a common consequence of pollution or climate change, leaves a reef “bleached” and unable to produce energy from sunlight.
Coral bleaching has increased widely in recent decades. Because it often precedes coral death and the loss of the reef itself, conservationists are naturally concerned that many of the world’s reefs are in trouble.
But new findings suggest that when coral is threatened, bleaching may be part of the solution.
It now appears that coral colonies, when confronted with dramatic environmental changes, may purge themselves of existing algae to make room for other algae more capable of thriving in the challenging conditions. Bleaching, then, may not signify coral’s imminent demise, but its ability to tough out new conditions.
In one set of experiments, marine scientist Andrew C. Baker of the New York Aquarium found that corals that undergo bleaching after being exposed to sudden environmental change are moreā€”not lessā€”likely to survive in the long run.
“This counters conventional wisdom that bleaching is detrimental from all perspectives,” Baker said. ”
Many Threats
Although many corals look bony and durable, reefs are highly fragile ecosystems, sensitive to human disturbance and environmental stress. Coral reefs all around the world are threatened by water pollution, soil erosion, fertilizers, fishing with explosives, careless diving, and other assaults.
Rising global air and water temperatures are another threat. Although warm tropical waters are ideal for reef development, excessively high sea temperatures can harm or kill algae.
Global warming may accelerate the melting of polar ice caps, causing sea levels to rise. Sunlight doesn’t penetrate deep water, so reefsā€”and their algaeā€”may be deprived of a critical source of energy.
“The frequency of coral bleaching will increase dramatically during this century as a result of increased global warming,” said Malcolm McCulloch, a geochemist at Australian National University in Canberra.
Recent studies by McCulloch and Baker offer hope that imperiled corals are flexible enough to survive.
In Edinburgh, McCulloch drew on geological records to demonstrate the resilience of coral during periods of significant climate change over the past 500,000 years. According to his data, eras of warm global temperaturesā€”when sea levels rose by as much as 18 feet (6 meters) above today’s levelā€”were periods in which reefs flourished rather than suffered.
Explaining the results, McCulloch said rising sea levels provide “space for corals to grow, and warmer ocean temperatures allow expansion of reefs to sub-tropical regions.”
Future warming won’t necessarily spell the end of reefs, but “it’s all a matter of timing,” he said. “[Reefs] could do well in a warmer worldā€”as long as the rate of warming is no faster than they can cope with, and assuming that our pollution doesn’t kill them off first.”
The experiments by Baker, reported in the June 14 issue of the journal Nature, also suggest that coral is remarkably adaptable, thanks in part to its cunning use of algae.
Baker transplanted dozens of coral colonies in the San Blas archipelago of Panama to depths that were shallower or deeper than those in which the corals had naturally developed. The study was designed to simulate the environmental change that stationary reefs would be exposed to as a result of rising or falling sea levels.
Coral colonies at different depths host different types of algae. So Baker monitored the transplanted corals to see whether their algae would survive at the new depths, and whether the coral colonies themselves would ultimately live or die.
The colonies that shed their original algae, he found, were able to attract different species of algae that were more suited to living at the new depths. Of the 11 coral colonies that experienced significant bleaching, none died during a 12-month follow-up period. In comparison, seven colonies that had kept their original algae species after being transplanted eventually died.
Artificially changing the depth at which a coral colony lives is one thing. But it remains unclear whether the adaptive process of bleaching will be enough to save coral reefs bombarded with pollution or slowly roasting in ever-warming waters.
At an international conference last month in Edinburgh, Scotland, McCulloch noted that the total area of Earth’s coral reefs has shrunk by 30 percent in the past three decades. The Caribbean, for example, has lost as much as 90 percent of its reefs.
McCulloch said: “We should be refocusing our efforts to reduce the effects of direct human-caused stresses on reefs, rather than be too sidetracked by coral bleaching.”
/endquote
Now when I ignore the boilerplate global warming hysteria inserted by the editor, I take home these messages:
1. Warmth in the past actually led to more growth of coral. Warmer sub-tropical oceans encourage coral growth where it didn’t exist previously. This should counteract any “stress” caused by rising temperatures elsewhere.
2. Coral bleaching is not a trigger of a die-off, it is self-protection against another problem.
3. The main reason for die-offs is therefore most likely to be other, more direct, human pollution.
4. While the rate of sea temperature growth affects the speed of adaptability of the coral, sudden natural warmings, eg in el niƱo years, demonstrably cause more bleaching than any underlying warming.
So the figures say that It is incredibly obvious that coral die-offs are directly related to human settlements, tourism and pollution. The science says warmer temperatures just redistribute coral, that bleaching is a self-protection and ENSO causes more temperature stress than any anthropogenic warming. Why then do we focus so much on an assumed CO2-related stress that doesn’t seem to have any foundation whatsoever?

Steven Goddard
February 4, 2009 6:30 am

Phil,
Several things are wrong with your last post. The link you posted, which has already been discussed at length – http://hahana.soest.hawaii.edu/hot/trends/trends.html – is a mixture of measured and calculated data. They provide no explanation of how they calculated data during years when there was no measurement. If you look just at their actual measured data in red (which is all that I am willing to work with,) there is no statistically significant trend. You can download all of their measured data for both of their measurement locations as I have explained and have provided spreadsheets of here.
Secondly, your calculation of what a 150% increase in H+ would comprise of is incorrect. A 150% increase is a ratio of 2.5/1 and log10(2.5) = 0.4 – not 0.15 as you stated.

Richard S Courtney
February 4, 2009 7:08 am

Bill D:
You say:
ā€œA scientific budget is directly analogous to a monetary budget. For example, if I spend $500 per month for my familyā€™s food and an additional $1 on chewing gum, I do not need to be concerned about chewing gum if my budget needs to be balanced.ā€
Oh yes you do if you want the balance to be accurate to $1 per month.
And the balance achieved by a budget of flows of CO2 in and out of the air needs to be accurate to better than 3 GtC of carbon per year if it is to determine the cause of the annual increase of about 3 GtC in the air per year.
Also, if your bank account is being depleted (or added to) by fraud (i.e. an unknown sink or source) then your budget may balance but your accountancy would be wrong unless the fraud were detected and accounted. The balance could be achieved by assuming an incorrect magnitude of an inadequately quantified input or output.
So, the estimation of your budget requires quantitative knowledge of each and all incomes and expenditures for it to be right. Unfortunately, most of the CO2 emissions to the air and sequestrations of CO2 from the air are not quantified to a degree that permits a budget with sufficient accuracy to calculate the effect of the (relatively small) anthropogenic emission.
Simply, the variations in the total natural emission each year and the total natural sequestration each year are not known. And it is a mathematical fact that the resultant variation of two added variables tells nothing about how either is varying. So, any achieved balance when they are accounted is ā€“ and can only be ā€“ a function of the assumptions concerning magnitudes of the components of the total natural emission and the total natural sequestration. Furthermore, this problem is not resolved by averaging over a number of years because the variation may be persistent (e.g. a change to ocean surface layer pH induced by upwelling from deep ocean that results in altered equilbrium concentrations between air and ocean).
Of course, some of the individual components of an atmospheric carbon budget may be measured but most are merely guesstimates.
The known facts of the matter are:
1.
The increase in atmospheric CO2 concentration each year is much less than the natural variations in atmospheric CO2 concentration within each year.
2.
The increase in atmospheric CO2 concentration over each year is the residual of the natural variations in atmospheric CO2 concentration within each year.
3.
The anthropogenic emission of CO2 each year is much less than the natural variation within each year.
4.
The change to the 12C:13C isotope ratio of atmospheric CO2 is in the direction expected if the recent increase in atmospheric CO2 concentration were caused by the anthropogenic emission of CO2.
But if the ratio changes then there is a 50:50 chance that it will change in that direction or the other.
5.
The magnitude of the change to the 12C:13C isotope ratio of atmospheric CO2 is much smaller than expected if the recent increase in atmospheric CO2 concentration were caused by the anthropogenic emission of CO2.
6.
The fact in point (5) indicates that most of the change to the 12C:13C isotope ratio of atmospheric CO2 and most of the recent increase in atmospheric CO2 concentration was caused by some unknown, natural (i.e. non-anthropogenic) effect.
7.
The fact in point (6) indicates that all of the change to the 12C:13C isotope ratio of atmospheric CO2 and all of the recent increase in atmospheric CO2 concentration may have been caused by the same unknown, natural (i.e. non-anthropogenic) effect.
Simply,
it is possible that none of the rise in atmospheric CO2 concentration and none of the change to the 13C:12C atmospheric isotope change were caused by anthropogenic emission
but were due to the unknown, natural (i.e. non-anthropogenic) effect that caused most of the change to the 12C:13C isotope ratio of atmospheric CO2.
8.
But the anthropogenic emission may have disturbed the carbon cycle such that the equilibrium state(s) of some parts of the carbon cycle have altered.
Therefore,
it is possible that all of the rise in atmospheric CO2 concentration and all of the change to the 13C:12C atmospheric isotope change were caused by the anthropogenic emission
that induced the unknown, natural (i.e. non-anthropogenic) effect that caused the observed change to the 12C:13C isotope ratio of atmospheric CO2.
9.
It is possible that both the effects noted in points 7 and 8 contributed to the change to the 12C:13C isotope ratio of atmospheric CO2 and to the recent increase in atmospheric CO2 concentration.
Therefore,
it is possible that some of the rise in atmospheric CO2 concentration and some of the change to the 13C:12C atmospheric isotope change were due to the anthropogenic emission.
10.
The change in atmospheric oxygen concentration in recent years is consistent with the amount of fossil fuel that was burned in those years.
In summation, the known facts (listed as points 1 to 10 above) demonstrate that
there is no conclusive evidence that any of the 20th century increase in atmospheric CO2 concentration is or is not due to the burning of fossil fuels.
Richard

Richard Sharpe
February 4, 2009 7:14 am

Phil. says:

The trend shown here is ~0.03 pH units in 20 years so over the next century we might expect ~0.15 pH units which gives ~150% increase in H+
http://hahana.soest.hawaii.edu/hot/trends/trends.html

Does it matter? That suggests that over 1,000 years at that rate, if it should continue, pH would fall to around 7.1. Is there any evidenced that coral species cannot adapt to that change and have never adapted to such change in the past. There seems to be evidence that they have quite a bit of selectable variation.
Mary Hinge says of Stephen Goddard:

You are however ignorant (in the nicest and most correct sense of the word) on the biology of corals and of evolutionary processes.

Since you are such an expert, pray tell, how many generations will corals need to adapt to the changes in pH and why is the variation obviously present in the various existing species insufficient?
You might like to know that recent papers provide evidence that in 100 generations humans have adapted to different sunlight conditions by completely changing their skin color (in both directions) and similarly have completely changed in other ways (The 10,000 Year Explosion contains a lot of accessible details).

gary gulrud
February 4, 2009 7:22 am

“colors are from parasites”
Symbionts.

Steven Goddard
February 4, 2009 7:23 am

Richard,
It is OK that you are not able to follow the technical discussion, but it is simply not acceptable for you to make claims like “I wish to deceive” or other ad hominem attacks. You have no idea what you are talking about.

February 4, 2009 7:55 am

Steven Goddard (06:30:43) :
Phil,
Several things are wrong with your last post. The link you posted, which has already been discussed at length – http://hahana.soest.hawaii.edu/hot/trends/trends.html – is a mixture of measured and calculated data. They provide no explanation of how they calculated data during years when there was no measurement.

As has been explained to you above the data labelled ‘calculated’ is obtained from measurements, there is no justification for not using it.
If you look just at their actual measured data in red (which is all that I am willing to work with,) there is no statistically significant trend. You can download all of their measured data for both of their measurement locations as I have explained and have provided spreadsheets of here.
See above
Secondly, your calculation of what a 150% increase in H+ would comprise of is incorrect. A 150% increase is a ratio of 2.5/1 and log10(2.5) = 0.4 – not 0.15 as you stated.
Agreed, your use of % misled me into thinking you meant a ratio, in any case a 0.15 decrease in pH is within the range of the IPCC SRES scenarios, the largest decrease is 0.35 so I’m not sure where the ‘150% prediction’ comes from? The A1FI scenario which gives the decrease of 0.35 is the ‘Fossil Fuel Intensive’ one with rapid economic growth.
Perhaps a more honest representation of the IPCC result would be to say that the range of values of pH in 2100 is from 7.75-7.95 down from the 2000 value of just under 8.1? Rather than take the worst case scenario, convert it to a % change (confusing to the average reader in any case since they might think that it referred to a change in pH), and then round up to the nearest 50%.

foinavon
February 4, 2009 8:50 am

Richard S Courtney (07:08:15)
You continue to make assertions that are not only unsupported by evidence, but are demonstrably untrue. Let’s look at your comments on CO2 levels, and particularly carbon isotopes, in the light of the data that is accessible to policymakers and their scientific advisors:
The 13C data can be obtained by direct measurement (Mauna Loa since 1959; numerous other measuring stations) and from high resolution ice cores (especially the Law Dome cores). Some of the data and the methodologies are described here, for example:
Francey RJ, Allison CE, Etheridge DM, et al. (1999)
A 1000-year high precision record of delta C-13 in atmospheric CO2 TELLUS B-Chem Phys. Meteor 51, 170-193.
Meure CM et al. (2006) Law Dome CO2, CH4 and N2O ice core records extended to 2000 years BP Geophys. Res. Lett. 33, art # L14810
D. M. Etheridge et al (1996) “Natural and anthropogenic changes in atmospheric CO2 over the last 1000 years from air in Antarctic ice and firn. J. Geophys Res. 101, 4115 -4128

Here are some of your assertions:

4. The change to the 12C:13C isotope ratio of atmospheric CO2 is in the direction expected if the recent increase in atmospheric CO2 concentration were caused by the anthropogenic emission of CO2.
But if the ratio changes then there is a 50:50 chance that it will change in that direction or the other.

That doesn’t work. The 12C:13C ratio isn’t just “in the direction expected” due to “a 50:50 chance that it will change in that direction or the other”. Inspection of the data demonstrates that the change in 12C:13C ratio has been in the “expected direction” continuously throughout the last 300 years or more. When our emissions were very low, the change in 12C:13C was very low (but in the “expected direction”). When our emissions were middling, so was the change in 12C:13C (still in the “expected direction”!), when our emissions were large, the change in the 12C:13C ratio was/is large (still in the “right direction”).
So for example we can inspect the record (see data in Francey cited above, for example) and find that the annual changes in delta 13C are negative (as carbon is returned to the atmosphere from burning fossil fuels the 13C content of atmospheric CO2 <reduces since fossil fuels are 13C-depleted). Here’s some of the data grouped into periods. The change in 13C:12C (- delta, delta 13C per year) was not much above zero in the period 1700-1800, started to rise through the 19th century, was rather substantial during the first half of the 20th century, and rose very quickly in the 2nd half of the 20th century as our emissions similarly rocketed upwards during this period. Now the -delta,delta-13C values are changing by around 25e-2 per year.
year range…………..(-)delta-delta-13c
1700-1800………….<0.3e-3 per year
1800-1850………….1.5-2.1e-3 per year
1850-1900………….3.3e-3 per year
1900-1950………….6.2e-3 per year
1950-2000………….~18e-2 per year

5. The magnitude of the change to the 12C:13C isotope ratio of atmospheric CO2 is much smaller than expected if the recent increase in atmospheric CO2 concentration were caused by the anthropogenic emission of CO2.

That’s not true. If anything the rate of change in 13C:12C is a bit faster than expected in recent decades since the rate of increase of atmospheric CO2 is faster than the 13C-replenished atmospheric CO2 is able to equilibrate with CO2 in the surface layers of the oceans. See Figure 11 of Francey et al cited above.

6. The fact in point (5) indicates that …..

Since the premises are false [your point (5) doesn’t contain a fact], your conclusions from here on are erroneous…

Richard S Courtney
February 4, 2009 8:57 am

Foinavon:
I have said nothing here that is not true and everything I have said here is capable of checking by anybody with little effort. Your repeated claims to the contrary do not alter that.
And I am frustrated by your knit-picking and changing of the subject so whatever comments you now make to me – however silly and/or offensive they may be – wil go unanswered by me.
Steven Goddard:
I wish to ensure that you and all others are clear that I am not – repeat not -the “Richard” who made the grossly offensive remark to you. And, yes, whomever that anonymous person is, he/she should apologise to you.
Richard

Steven Goddard
February 4, 2009 9:39 am

Phil,
Given that there are quite a few years in the graph with “calculated data” that had no “measured data,” it is clear that the “calculated data” is not derived from any reported measured data.
If you download their measured data set, you can see that there are many years with no data and that the data set corresponds with the red (measured) data in the graph.
So far people have reported three raw measured pH data sets. Monterey, Aloha and Kahe. None of them show a statistically significant trend towards lower pH.

J. Peden
February 4, 2009 9:51 am

foinavon (03:54:11):
Surely by your own reasoning (add CO2 to bloodā€¦the pH goes down), itā€™s completely obvious that the carbonate concentration of blood will also decrease.
Au contraire, foinavon: by my “own reasoning” CO3 increases, as per my explanation, which you have not refuted in any way.
All you’ve done is to simply re-state over and over that CO3 must decrease when pH decreases from the addition of CO2 to solution, because, lo and behold, “H + CO3 = HCO3” if isolated from everything else – that is, when you have not shown this to be the case anywhere else – except in your in vacuo H.H. example, which, as I noted, simply postulated a ratio, quite apart from what actually happens when CO2 is added to water, both in the basic equations of inorganic chemistry and in real solutions.

J. Peden
February 4, 2009 10:04 am

J. Peden (09:51:57)
n.b. in order to be crystal clear regarding the meaning of “this” as per the statement below from the above-referenced post:
that is, when you have not shown this to be the case anywhere else
“this” refers to “that CO3 must decrease when pH decreases from the addition of CO2 to solution”

foinavon
February 4, 2009 10:10 am

Richard S Courtney (08:57:13) :

Foinavon:
I have said nothing here that is not true and everything I have said here is capable of checking by anybody with little effort. Your repeated claims to the contrary do not alter that.

That’s the point ‘though isn’t it Richard? We have “checked” and found that quite a bit of what you have said is demonstrably untrue. Isn’t that concerning to you?
It seems to me that we should be attempting to address the science in much the same way that scientists, policymakers and their advisors do. Otherwise we’re going to be increasingly at odds with well-informed policymaking in these important areas. It’s all very well to pursue notions that don’t accord with the straightforward evidence, but if we want to understand policymaking that relates to scientific analysis we should be more like King Canute, and less like his misguided courtiers!

February 4, 2009 11:07 am

Richard S Courtney (03:34:56) :
Phil:
I have made no ā€œmisleading postsā€. I have only made factually accurate ones as anybody can check for themselves. If an apology is needed then it is from you for saying otherwise.

No you constantly make misleading posts, this one included!
You say:
ā€œNonsense! The mass of the atmosphere is ~5Ɨ10^18kg, the annual fluctuation of CO2 is ~4ppm so that gives an annual fluctuation of ~20 Gtonne. The annual emission of fossil fuel worldwide in 2004 was ~27 Gtonne, so for your ā€˜order of magnitudeā€™ greater release of CO2 should result in an annual fluctuation of ~50ppm!ā€
Sorry, but No!

Actually, yes, as anyone who cares to do the simple calculation can verify.
The Mauna Loa seasonal fluctuation is about 10 ppmv per year (not 4 ppm) see
http://www.esrl.noaa.gov/gmd/ccgg/trends/

Which part of ‘global’ didn’t you understand? In any case reference to that site reveals that the seasonal fluctuation at Mauna Loa is ~6ppm not the 10ppm that you claim. Misleading again!
And Mauna Loa is chosen as a sample site because its seasonal fluctuation is exceptionally low being less than half that elsewhere: e.g. the seasonal fluctuation is more than double that where measured in the Northern Hemisphere, e.g. at Alert, Estavan (both in Canada) and in the Shetland Islands (ref Keeling and Worf, ā€˜On Line Trendsā€™ CDIAC.ORNL).
That was not the reason Mauna Loa was chosen, you conveniently chose ‘elsewhere’ to be restricted to the N hemisphere. Of course the sites in the S hemisphere show much lower fluctuations: Cape Grim, Baring Head, Samoa, Christmas Island etc. Here’s Bering Head for example:http://cdiac.ornl.gov/trends/co2/graphics/Baring_Head_NZ_CO2.jpg
More misleading information!
Your statement that ā€œThe annual emission of fossil fuel worldwide in 2004 was ~27 Gtonneā€ emphasises my repeated (above) statement that the anthropogenic emissions vary greatly from year-to-year.
How?
As I said, ā€œin some years almost all the anthropogenic emission seems to be sequestered and in other years almost noneā€ (according to data from CDIAC.ORNL). And I have repeatedly pointed out that there are justifiable reasons for smoothing the annual emissions data with at most 3-year averageing but the IPCC uses 5-year averages because 2-yeaqr, 3-year and 4-year smoothings do not work.
Yes you did say that, care to justify it with data?
Typically, according to the NASA estimate, the human emission is about 6.5 GtC/year: see
http://science.hq.nasa.gov/oceans/system/carbon.html

Why the switch in units to GtC, you wouldn’t be trying to mislead would you?
6.5 GtC= 24 Gtonne CO2.
The accumulation rate of CO2 in the atmosphere is equal to almost half the human emission. The human emission is about 6.5 GtC/year but the accumulation rate is about 3 GtC/year. However, this does not mean that half the human emission accumulates in the atmosphere, as is often stated.
No it means that the total non-anthropogenic sources-sinks must be less than the ‘human emission’ by ~3 GtC/year (11 Gtonne CO2)
The system does not ā€˜knowā€™ where an emitted CO2 molecule originated and there are several CO2 flows in and out of the atmosphere that are much larger than the human emission. The total CO2 flow into the atmosphere is at least 156.5 GtC/year with 150 Gt of this being from natural origin and 6.5 Gt from human origin. So, on the average, about 2% of all emissions accumulate.
And these fluxes are ~balanced so they don’t show up in the measurements other than to modulate the CO2 uptake on a seasonal basis.
And the NASA estimate is that about 100 Gt of carbon are released to the air from the oceans and is sequestered by the oceans each year. This alone is a seasonal fluctuation that justifies my statement that the seasonal variation is an order of magnitude greater than the anthropogenic emission.
If it were a seasonal flux it would show up in the results but it doesn’t except in a small way as described above, it’s averaged out spatially and temporally (e.g. day/night). A bowl of water containing CO2 in equilibrium with a constant composition atmosphere above it doesn’t change [CO2] but fluxes of CO2 in both directions continue in both directions (as seen in by the atom test C-14 response, the spike took 15 yrs to half).
Furthermore, according to the NASA estimate, the carbon in the air is less than 2% of the carbon flowing between parts of the carbon cycle. And the recent increase to the carbon in the atmosphere is less than a third of that less than 2%.
The flows between deep ocean and ocean surface layers are completely unknown and it is not possible even to estimate them. All we know is that the air contains aboout 760 GtC, the ocean surface layer about 800 GtC, and the deep oceans about 38,000 GtC. The thermohaline circulation conveys the major flows between deep ocean and ocean surface layers.
NASA also provides an estimate that the carbon in the ground as fossil fuels is 5,000 GtC, and humans are transferring it to the carbon cycle at a rate of 6.5 GtC per year.
In other words, the annual flow of carbon into the atmosphere from the burning of fossil fuels is less than 0.02% of the carbon flowing around the carbon cycle.
It is not obvious that so small an addition to the carbon cycle is certain to disrupt the system because no other activity in nature is so constant that it only varies by less than +/- 0.02% per year.

Disingenuous, because the net contribution by anthropogenic CO2 must be 11 Gtonne/year.

gary gulrud
February 4, 2009 11:08 am

“The 13C data can be obtained by direct measurement (Mauna Loa since 1959; numerous other measuring stations)”
As I have taken pains to make clear on the prior CO2 Temperatures and Ice Ages thread, Spencer one year ago here at WUWT compared the 13C:12C fraction of the MLO seasonal signal with the long-term trend under F-Test. They were identical.
As the biogenic fluences are seasonal and the anthropogenic is given to be cause for the long term trend the 13C decrease cannot be assigned with any certainty whatever to the latter. The anthropogenic fluence, at least, has been scrubbed from view by the natural. Multiplying words does not add a jot to your argument.

Simon Evans
February 4, 2009 11:13 am

Graeme Rodaughan (04:43:05) :
Simon Evans (08:41:06) :
Graeme Rodaughan (07:58:45) :
In this forum – I also raise my hand and second Alan Millarā€™s request.
Alan Millarā€™s question was addressed as follows:
Perhaps some of our alarmist friends would like to explain.
Iā€™m not an alarmist, so I wont be responding to that.
Fair enough – Iā€™ll re-ask politely.
Is anyone able to explain how a warming ocean could absorb CO2 and become more acidic – given that warming oceans have a well known property of outgassing CO2? – Or is this simply a non-starter?
Thanks.

Thanks Graeme. My explanation would be that both occur at the same time – outgassing and absorption, that is – the net effect simply being a matter of whichever is the greater, according to the variables of temperature (and also pH, a lowering of which will itself reduce the sink capacity of the oceans) and atmospheric concentration. At the moment the oceans are absorbing more than they are emitting, but the projections are for the reverse. Therefore, the extent of acidification is limited and, eventually it would be undone. The concern for the corals is that they will be destroyed in the interim. I should stress, though, that this is not my field, so don’t take my word for it! šŸ™‚

Glenn
February 4, 2009 11:13 am

Steven Goddard (09:39:49) :
Phil,
“Given that there are quite a few years in the graph with ā€œcalculated dataā€ that had no ā€œmeasured data,ā€ it is clear that the ā€œcalculated dataā€ is not derived from any reported measured data.”
Yes, but the claim is that “calculated” data comes from a different methodology not reliant on “measured” data methods. These words “calculate” and “meaure” could be confused when using same in the course of debating the issue.
“If you download their measured data set, you can see that there are many years with no data and that the data set corresponds with the red (measured) data in the graph.”
Holy moly. Can you repost a link to this data set? I think you may have already posted this, but it’s hard for me to search WUWT (especially a long thread like this one), and MS “Find” crashes my browser.
If there is no saved data from the past that could have been used to reconstruct ph for those missing “calculated” times, then it becomes very clear that this graph is very misleading, and junk. Are you sure you are looking at all data sets, not just the ones for the “measured” data?
Even were this not the case though, and “calculated” data plotted did exist, there is still the problem of why no “measured” data exists on much of the graph, why the “measured” was even included if the “calculated” method was more reliable or one was not a calibration of another (which by the large variation in data between the two is clearly not the case).
And there is the question of why the “measured” data was not trendlined as was the “calculated”, if the “measured” data was reliable and an accurate source of ph values.

J Lo
February 4, 2009 11:24 am

J. Peden:
Btw, where do you think CO3 comes from to begin with?
CaCO3! We’ve been beating that drum for the last 100 posts!
You say that the Henderson Hasselbach equation is too simple to definitively show that CO2 levels reduce CO3(-2) equations. But this complicated science has ALREADY been done AND observed.
I’ll quote myself again:
http://www.publicaffairs.noaa.gov/releases2002/mar02/noaa02r305.html
ā€œOur results are important in understanding the oceanā€™s role in the global carbon cycle,ā€ Anderson said. ā€œPrior to this study, large changes in ocean carbonate chemistry had been proposed to explain the changes in atmospheric carbon dioxide. Over thousands of years, calcium carbonate compensation appears to be the dominant variable controlling the ocean carbonate (and carbon dioxide) inventory. When carbon dioxide from the atmosphere is added to the oceans, the calcium carbonate on the seafloor dissolves to minimize the carbon dioxide change in the ocean. ā€
If [CO2] increases [CO3(-2)] in the ocean, shouldnā€™t it be easier to form CaCO3 due to this equilibria: CaCO3 == Ca(++) & CO3(-2) according to Le Chatlierā€™s principal? In fact, the opposite is shown to be true. The addition of H+ ions is more important to [CO3(-2)] than the dissociation of HCO3(-1) by CO2.
You guys are too focused on the generation of CO3(-2) by CO2 in pure water. CaCO3 is the much greater buffer (which is why oceans are alkaline and not acidic).
I rest my case again.

February 4, 2009 11:37 am

Steven Goddard (09:39:49) :
Phil,
Given that there are quite a few years in the graph with ā€œcalculated dataā€ that had no ā€œmeasured data,ā€ it is clear that the ā€œcalculated dataā€ is not derived from any reported measured data.

No that’s not true the ‘measured data’ refers to direct measurement of pH, ‘calculated’ refers to calculated from other related titrametric methods. I cited a reference earlier.

February 4, 2009 11:44 am

gary gulrud (11:08:35) :
ā€œThe 13C data can be obtained by direct measurement (Mauna Loa since 1959; numerous other measuring stations)ā€
As I have taken pains to make clear on the prior CO2 Temperatures and Ice Ages thread, Spencer one year ago here at WUWT compared the 13C:12C fraction of the MLO seasonal signal with the long-term trend under F-Test. They were identical.

And as others here, including me have pointed out, that was the result of an elementary math error by Spencer. If you read his recent blog on the subject he makes a different argument about C12/C13 and studiously avoids reference to his post of a year ago! Clearly even he doesn’t believe what he wrote a year ago was reliable, but hasn’t posted a retraction.
http://www.drroyspencer.com/2009/01/increasing-atmospheric-co2-manmadeā€¦or-natural/

Pete D
February 4, 2009 11:45 am

J Peden, Foinavon:
If there is still debate on this, a little General Chem…
1) H2CO3 = H+ + HCO3- with Ka1 = [HCO3-][H+]/[H2CO3] = 4.2E-7
2) HCO3- = H+ + CO32- with Ka2 = [H+][CO32-]/[HCO3-] = 4.8E-11
overall equilibrium constant, K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-]
Increasing CO2 = increasing H2CO3 via CO2 + H2O = H2CO3. Since [H2CO3] is in the denominator of K, an increase in H2CO3 is compensated for by an increase in [HCO3-] and a decrease in [CO32-] governed by the equilibria above. The reason that 2) shifts to the left is due to the relatively large increase in the amount of H+ via 1) because Ka1 is 4 orders of magnitude higher that Ka2! Incidentally, this overall K is equivalent to the RC statement that CO2+H2O+CO32- = 2HCO3-
Chem iz fun…but Chem Eng iz funner

February 4, 2009 11:52 am

In Phil. (11:07:54) above :Why the switch in units to GtC, you wouldnā€™t be trying to mislead would you?
6.5 GtC= 24 Gtonne O2

O2 is a typo it should be CO2, moderator please adjust it if possible. Thanks.
Reply: Done ~ charles the moderator

Mary Hinge
February 4, 2009 12:32 pm

JamesG (04:13:29) :
Not one of these experts has tied CO2 to coral extinction. If itā€™s not actually to blame then that will never be possible. Most experts say there are multiple factors involved.

Your comment shows what is wrong with the sceptic view. You just don’t read the evidence,or ignore it if you do. Below is the report on one species Heliopora coerulea from the aforementioned assessment by the 39 scientists. You say that they do not mention CO2, well look closely (I’ve highlighted the relevant part to help you) and see for yourself.
This species is collected for the curio and jewelry trade (dried skeletons give blue color), and the aquarium trade. In 2005, 2,868
pieces of live and 5,787 pieces of raw Heliopora coerulea were exported for the aquarium and curio trade (E. Wood, pers
comm.).
The huge Heliopora stands that extend for almost 10 km in Banda Aceh, Indonesia were the most damaged species of all corals
due to the earthquake (Foster et al. 2006).
In general, the major threat to corals is global climate change, in particular, temperature extremes leading to bleaching and
increased susceptibility to disease, increased severity of ENSO events and storms, and ocean acidification.
In addition to global
climate change, corals are also threatened by disease, and a number of localized threats. The severity of these combined threats
to the global population of each individual species is not known.
Coral disease has emerged as a serious threat to coral reefs worldwide and is a major cause of reef deterioration (Weil et al.
2006). The numbers of diseases and coral species affected, as well as the distribution of diseases have all increased dramatically
within the last decade (Porter et al. 2001, Green and Bruckner 2000, Sutherland et al. 2004, Weil 2004). Coral disease epizootics
Conservation Measures
have resulted in significant losses of coral cover and were implicated in the dramatic decline of acroporids in the Florida Keys
(Aronson and Precht 2001, Porter et al. 2001, Patterson et al. 2002). In the Indo-Pacific, disease is also on the rise with disease
outbreaks recently reported from the Great Barrier Reef (Willis et al. 2004), Marshall Islands (Jacobson 2006) and the
Northwestern Hawaiian Islands (Aeby, 2006). Increased coral disease levels on the Great Barrier Reef were correlated with
increased ocean temperatures (Willis et al. 2007) supporting the prediction that disease levels will be increasing with higher sea
surface temperatures. Escalating anthropogenic stressors combined with the threats associated with global climate change of
increases in coral disease, frequency and duration of coral bleaching and ocean acidification place coral reefs in the Indo-Pacific
at high risk of collapse.

Here is a link to the reports on individual coral species in the assessment. http://www.sci.odu.edu/gmsa/about/corals.shtmlRead them and you will see repeated many times the main danger to coral species from climate change and ocean acidification.
I’m sure you mean well and are as concerned about the corals as I am, but you have to look at the evidence and take notice of what the experts in their firld are telling us. Only then can we take the steps necessary to protect a very important resource for future generations.

SteveSadlov
February 4, 2009 12:43 pm

Hmmmm … still no takers.
OK … 2 sigma.
(Meaning, show me, that the “signal” of lowering pH can be demonstrated, via a classical Gage R&Red set of runs, to be able to demonstrate a 2 sigma margin versus all errors and noise vis a vis repeatability and reliability, plus, bias factors, across a semi infinite half space of ocean mass).

George E. Smith
February 4, 2009 1:08 pm

“” This species is collected for the curio and jewelry trade (dried skeletons give blue color), and the aquarium trade. In 2005, 2,868
pieces of live and 5,787 pieces of raw Heliopora coerulea were exported for the aquarium and curio trade (E. Wood, pers
comm.).
The huge Heliopora stands that extend for almost 10 km in Banda Aceh, Indonesia were the most damaged species of all corals
due to the earthquake (Foster et al. 2006). “”
Yep ! unmistakable evidence of global warming and acidification !
George

George E. Smith
February 4, 2009 2:08 pm

“” foinavon (13:02:16) :
George E. Smith (12:07:00)
George, weā€™ve already had the dismal non-ā€argumentā€ about the meaning of ā€œacidificationā€. Are you really going to proceed down a pedantic diversion over the meaning of ā€œsinusoidalā€?
Remember that words are only labels for the things that we are choosing to describe.
ā€œSinusoidalā€ is actually not a bad description of the very well-characterised cyclic variation in the atmospheric CO2 concentration that follows the seasonal growth/decay cycle in the N. hemisphere which is where most of the earthā€™s flora ā€œresidesā€. Since the sinusoidal variation lies on a rising trend of growing atmospheric CO2 it does look a bit ā€œsawtoothā€.
So letā€™s call it ā€œsawtoothā€ if you like. We both know what weā€™re looking at. “”
Well Foinavon; contrary to what you appear to have assumed, my comment was not at all a “pedantic diversion”; and it was not intended to be dismissive of your comment. If you took it that way, then I apologise.
BUT; would you not agree that the distinction between “roughly sinusoidal” and “roughly sawtooth”, is very significant in the sense that each would be the result of quite different physical processes.
For example, when I look at the satelite graphs of the solar constant measured over sunspot cycles, the resulting variation I would call “roughly sinusoidal”, or even “sinusoidal” if trying to be brief; yet it clearly isn’t sinusoidal, because the peaks are sharper than the troughs, indicating the presence of a second harmonic component. That then begs the question of what physical processes going on in the sun lead to that second harmonic deviation from a sinusoid.
So back to the ML data. The peak and trough turnarounds are very sharp transitions from upslope to downslope and vice versa. Clearly this is not the result of a nearly linear feedback oscillator, which would produce a sinusoidal oscillation.
There is a definite on/off transition occurring, which cause the ML cyclic seasonal variation; and that leads to the question; what is that on/off mechanism.
Now for one thing, deciduous trees lie dormant through the fall/.winter, and then sprout leaves (very quickly) in the spring. I have a home in California’s central valley agricultural area where stone fruit orchards abound (and grapes). Those plants are sprouting leaves en masse, as I type this.
Those trees in the winter, are not taking up CO2 since they have no leaves. The leaves return in the spring in a matter of a week or two; and from there they start sucking up CO2. To a large extent, the mass of foliage doesn’t change after that two week leaf growth period, so you have a rather constant CO2 extraction rate once the leaves are there, and such a mechanism would in fact lead to a saw tooth cyclic variation in CO2. To me the leaf growth/shedding processes of spring and fall, amount to a rectangular pulsed waveform, with rise and fall times of the order of two weeks, but since the time constant of the excess CO2 uptake by that growth process is long comared to the season, the CO2 response is an integration of that rectangular drive signal.
NOW ! I am NOT claiming that this is the process which explains the ML cyclic waveform; but I am saying it is one operating process, which would create such a response.
If you find, and look at the NOAA three dimensional CO2 graph form pole to pole, you will notice that the southern hemisphere cycling is much suppressed from the northern, and to my eye, the very limited south pole cycling, is in fact much closer to a “roughly sinusoidal” variation (still with harmonic content) than it is to a saw tooth; and that suggests to me that the southern CO2 uptake, is likely more ocean related, than land plant growth.
So you see, I was not trying to be smart alecky; but hinting that the waveform isa clue to the mechanism.
But as I said, if you took it as frivolous comment on your post please accept my apology; it wasn’t intended that way at all.
George

Mary Hinge
February 4, 2009 2:32 pm

George E. Smith (13:08:48) :
ā€œā€ This species is collected for the curio and jewelry trade (dried skeletons give blue color), and the aquarium trade. In 2005, 2,868
pieces of live and 5,787 pieces of raw Heliopora coerulea were exported for the aquarium and curio trade (E. Wood, pers
comm.).
The huge Heliopora stands that extend for almost 10 km in Banda Aceh, Indonesia were the most damaged species of all corals
due to the earthquake (Foster et al. 2006). ā€œā€
Yep ! unmistakable evidence of global warming and acidification !
George

Well done George for doing what sceptics do best…picking that little bit that suits your point of view whilst ignoring the more important and relevant evidence and information. If you continue reading you see the main reasons, read the other reports and you may finally remove those sound bite blinkers.

Chris J
February 4, 2009 5:52 pm

@ Steven Goddard et al.,
There still seems to be a great deal of confusion over the meaning of ā€˜calculatedā€™ vs. ā€˜measuredā€™ for pH data from the HOT datasets, despite that fact that Iā€™ve explained the meanings at least twice now. In any event, let me try to communicate once and for all how these data were generated.
Seawater pH can be assessed using three methods:
1) With combination electrodes calibrated in appropriate buffers (NIST buffers donā€™t work wellā€”one needs to use Tris-based buffers made in an artificial seawater solution).
Of the three methods available, this is the LEAST ACCURATE method, and wasnā€™t used to obtain any of the HOT (or BATS, etc.) data. While this method can be precise to better than +/- 0.005 pH units, it is rarely accurate to +/- 0.005 pH units or better.
2) Spectrophotometrically using the indicator dye m-cresol purple (Clayton and Byrne, 1992). This method did not exist when people started taking the HOT data, therefore could not be used.
Accuracy, as has been assessed in the lab and on many NOAA cruises, is on the order of +/- 0.001 pH units or better. Precision (assessed likewise) is typically +/- 0.0004 pH units or better, and can be up to an order of magnitude better. This is a good method to determine pH when very high accuracy is needed, but unfortunately is somewhat labor intensive (I know, Iā€™ve used this method extensively). This method was used to determine pH in SOME of the Niskin water samples from these sites from 1992-1997, and 2003-present.
The ā€˜measuredā€™ pH data for the HOT datasets were assessed using this method.
3) Calculated given measured values of:
1) total CO2/DIC, 2) total alkalinity, 3) salinity, 4) total P, 5) total Si, 6) in situ pressure, 7) in situ temperature, 8) experimentally determined dissociation constants (e.g., K1, K2) for carbonic acid.
The accuracy and precision of this method are similar to the m-cresol purple spec. method (~accuracy +/- 0.0007 or better, precision +/- 0.0005 or better).
The ā€˜calculatedā€™ pH data for the HOT datasets were assessed using this method, and can be re-assessed ad nauseum. All of these data are freely available on the website, and we can produce our own analyses of these results all we want all day long everyday. These data (along with a great deal more) cover the entire period.
Something worth pointing out is that all of these methods, and indeed EVERY possible method of determining pH relies on calculations from measured values. All provide a ā€˜calculatedā€™ pH relative to experimentally determined calibration values.
The ā€˜measuredā€™ data in the graphic I presented are for a given subset of the Nisken bottle samples during the sampling period. Only a subset of the Nisken samples could be analyzed because these measurements are somewhat time sensitive, so have to be analyzed rather quickly after sampling.
The ā€˜calculatedā€™ data in the graphic include data from a much larger set of Nisken bottle samples.
Hence, these data were collected at the same general sites, but they represent measurements of different water masses. The ā€˜calculatedā€™ values are broader in scope while the ā€˜measuredā€™ values include only a subset of the same water masses.
If I may use an analogy, the ā€˜measuredā€™ values here are like measuring the rate of unemployment in all cities in Florida with a population greater than 70,000. The ā€˜calculatedā€™ values here are like measuring the rate of unemployment in all cities in Florida with a population greater than 5,000. They will inherently include some of the same values and express the same property, but not over precisely the same landscape.
If you still donā€™t understand where these data come from (and keep in mind, we can analyze and re-analyze, and re-re-analyze all we want since all of the data are freely available) Iā€™m not sure how much more I can help. If youā€™d like help in obtaining the pertinent data and in analysis Iā€™m happy to get you started.
Claiming that the data should be thrown out simply because you donā€™t understand where they came from (itā€™s all in the references/methodology), however, is ridiculous, and terribly nieve. Again, your ignorance is not evidence.
Best,
Chris
p.s. And beyond this point of contention, look at the big picture: if CO2 is added to the atmosphere, is it logically possible that some of it will not dissolved into the ocean? (no, of course not) Is it logically possible (notwithstanding J. Peden et al.,ā€™s severe misunderstanding of carbonate chemistry) to add CO2 to sea water and not reduce the pH of that water? (no, of course not)

maksimovich
February 4, 2009 6:25 pm

Phil (11:07:54) :
“Of course the sites in the S hemisphere show much lower fluctuations: Cape Grim, Baring Head, Samoa, Christmas Island etc. Hereā€™s Bering Head for example:http://cdiac.ornl.gov/trends/co2/graphics/Baring_Head_NZ_CO2.jpg
More misleading information!’
Indeed it is.Baring head station information you supplied has been “seasonally adjusted” This is not a continuous sample it is adjusted for the southern wind flows only ie southern ocean.This is good reasoning as the northern and prevailing aspect is dominated by a regenerating temperate rainforest .
Niwa comments as such
“CO2 concentrations in units of 10^ā€“6 mole/mole (ppm) are shown to the period 2007. Data points represent measurements during southerly wind events extracted from a near-continuous record which has much greater high frequency variability but displays the same long term trend. The red curve shows a time varying trend with the seasonal cycle removed.”
The seasonal ‘sawtooth” of the “unadjusted” co2 record is similar to the CH4 (albeit with different measurements)
http://www.niwa.co.nz/__data/assets/image/0020/43454/Bhd_ch4_800.jpg

Steven Goddard
February 4, 2009 7:28 pm

Chris J,
If you look at the “calculated” pH data, it has an extremely high standard deviation, does not correlate well with the measured pH data in coincident years, and shows a large inexplicable drop in pH from 1989-1994 (before the measured pH data set started.) That drop, plus inconsistent low calculated readings the last couple of years accounts for almost their entire claimed trend. The calculated data shows variations as high as 0.8 during time periods when the measured data has a peak variance of only 0.2.
I am surprised that they would include such an obviously flawed data set in their trend analysis.

J. Peden
February 4, 2009 7:42 pm

Pete D (11:45:37) :

J Peden, Foinavon:
If there is still debate on this, a little General Chemā€¦
1) H2CO3 = H+ + HCO3- with Ka1 = [HCO3-][H+]/[H2CO3] = 4.2E-7
2) HCO3- = H+ + CO32- with Ka2 = [H+][CO32-]/[HCO3-] = 4.8E-11
overall equilibrium constant, K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-]

Thanks for setting out the situation in that way. It makes a lot of sense. However, looking at Ka2, I’m still not totally convinced that, given the equally large increase in [HCO3] in equation 1 resulting from an addition of CO2, equation 2 will be driven to the left by the increase in [H] enough/net to necessitate a net decrease in CO3. K doesn’t necessarily say that, either.
I’ll conceed that you might be right, but I’m still not sure about the net decrease of CO3.

Glenn
February 4, 2009 8:27 pm

Steven Goddard (19:28:19) :
This is almost funny. I already provided the documentation of how ph is measured from the HOT site (below). Now I’m not betting the farm on that being correct, but it is more than Chris has done. But his latest reasoning has sent me into orbit. The earlier years weren’t measured because they didn’t have the instruments, the way he claims “calculated” comes from is superior to the “measured”, “measured” and “calculated” are taken from different and more depths, anyone could go back and recreate the same results… this all seems to be lipstick on the pig. And none of it makes sense when one looks at the graph.
Going back and recreating is trivial with the values recorded (if they are), but it is doubtful the actual samples are saved so that they could be retested. Doesn’t legitimize the graph. The only thing that could be tested is the math.
The “measured” has a gap in the middle, so they did have the means at that time, but it is absent. Chris doesn’t address that.
Including two sources of data which come from different depths and including both on one graph would be just downright unprofessional, worse than sloppy.
If the method he claims is used for “calculated” is superior to any other, there would be no reason to include the “measured” to the graph at all. Certainly the two do not support a single trend. They are at odds.
Chris hasn’t provided any reasoning for why the two measurement exist on the graph, and neither he nor Phil have responded to any of these concerns,
Chris hasn’t documented any of his claims, yet he accuses you of ignoring data.
the graph (select pH comparison):
http://hahana.soest.hawaii.edu/hot/trends/trends.html
http://hahana.soest.hawaii.edu/hot/protocols/chap23.html
ā€œpH is measured electrochemically using a combination
electrode.ā€
ā€œThe pH of seawater samples is calculated using the
electrode slope and isoelectric point and sample temperature.ā€

Chris J
February 4, 2009 9:01 pm

@ Steven Goddard,
ā€œChris J,
If you look at the ā€œcalculatedā€ pH data, it has an extremely high standard deviation,ā€
Sure, seasonal changes in primarily primary production and secondarily a few other factors (e.g., salinity, net community calcification, etc.) produce a fair amount of deviation around the trend, though in absolute terms itā€™s a relatively modest amount of variation.
ā€œā€¦does not correlate well with the measured pH data in coincident years,ā€
Do you still not understand that these data represent different water masses?
ā€œā€¦and shows a large inexplicable drop in pH from 1989-1994 (before the measured pH data set started.)ā€
Au contraire, the drop in pH is easily inexplicable: pCO2 for the seawater increased ~10 uatm. See the trend in pCO2 here (select pCO2 comparison): http://hahana.soest.hawaii.edu/hot/trends/trends.html
ā€œThat drop, plus inconsistent low calculated readings the last couple of years accounts for almost their entire claimed trend.ā€
Yes, the drop in pH from 1989-1994 plus the drop from 1994-2007 accounts for the drop in pH. I mean, is that somehow surprising?
ā€œThe calculated data shows variations as high as 0.8 during time periods when the measured data has a peak variance of only 0.2.ā€
Sure, the ā€˜measuredā€™ dataset is only a subset of the ā€˜calculatedā€™ dataset. The ā€˜calculatedā€™ dataset covers a larger spatial volumeā€”youā€™d expect it to have a higher variance.
ā€œI am surprised that they would include such an obviously flawed data set in their trend analysis.ā€
Ha, Steve, thereā€™s absolutely nothing wrong with the data. They are what they are, and theyā€™re freely available to you. Whether or not you like them doesnā€™t particularly matter.
The trendline for the pH data shows a mean 0.025 reduction in pH over the last 20 years at Aloha, with a s.d. almost as large. Clearly seasonal and interannual variation in rainfall (salinity, total alkalinity), primary production (dissolved CO2), calcification (total alkalinity, dissolved CO2), etc., all affect instantaneous chemistry parameters. This small reduction in pH is not something we much worry about, and if 0.025 units was the extent of the problem I would see no reason to worry much about this issue. However, this small reduction in pH ISNā€™T what weā€™re concerned about.
Since the preindustrial atmospheric pCO2 has risen form ~285 to 385 uatm. Standard seawater in equilibrium with those atmospheres (mean chemistry parameters in the shallow ocean are essentially in equilibrium with the atmosphere) would give seawater scale pH values of 8.15 and 8.05, respectively. This 0.10 unit reduction in pH, four times what can be seen in the HOT datasets, is more concerning, but even that is not enough that I think it a major problem.
The problem here is really the effects of a pH reduction (and changes in other chemistry parameters induced by it) in line with what weā€™re on track to see later this century. Given current rates of increase of atmospheric CO2 weā€™ll easily top 700 uatm by the end of the century, and could very well top 840 uatm for a value ~3x preindustrial. For standard seawater that gives a mean pHsws = 7.76.
The concern is not a 0.025 pH unit decrease, or even so much a 0.10 unit decrease, itā€™s the overall ~0.39 unit decrease (and related changes in chemistry) weā€™re on track to reach by the end of the century.
Again, look at the big picture here.
Chris

Glenn
February 4, 2009 9:10 pm

Chris J,
“1) total CO2/DIC, 2) total alkalinity, 3) salinity, 4) total P, 5) total Si, 6) in situ pressure, 7) in situ temperature, 8) experimentally determined dissociation constants (e.g., K1, K2) for carbonic acid.”
[…]
ā€œpH was assessed using both spectophotometric methods with m-cresol purple (= ā€˜measuredā€™) and in accordance with equilibria given measured values of TCO2 and TA (= ā€˜calculatedā€™).ā€
ā€œThey have a long-term dataset for a huge number of parameters, including DIC, TA, S, T, P, DIP, total silicate, etc. pH can be calculated from these data more accurately than it can be measured with the tools that were available when they started taking this data (namely electrodes). As above, the ā€˜calculatedā€™ pH values are for the mixed depth using these data.ā€
How were all these factors isolated and measured? Was Atomic absorption spectroscopy used? You didn’t respond to my post which questions all this.

Chris J
February 4, 2009 9:44 pm

@ Glenn,
ā€œSteven Goddard (19:28:19) :
This is almost funny. I already provided the documentation of how ph is measured from the HOT site (below). Now Iā€™m not betting the farm on that being correct, but it is more than Chris has done.ā€
Here you are: http://hahana.soest.hawaii.edu/hot/methods/ph.html
ā€œBut his latest reasoning has sent me into orbit. The earlier years werenā€™t measured because they didnā€™t have the instruments,ā€
As I said, the methods did not existā€”spectrophotometric seawater pH methods with m-cresol purple were published in 1992 (Clayton and Byrne, 1992), therefore could not have been used when they started taking data in 1989.
ā€œā€¦the way he claims ā€œcalculatedā€ comes from is superior to the ā€œmeasuredā€, ā€œmeasuredā€ and ā€œcalculatedā€ are taken from different and more depths, anyone could go back and recreate the same resultsā€¦ this all seems to be lipstick on the pig.ā€
Please feel free to double check those claims then, be my guest. Accuracy and precision for pH determination are both better by calculating pH from TCO2, TA, S, P, T, TP, TSi, using the analytical methods they use, than what you get from electrodes. You donā€™t have to believe me you can verify the claim yourself
ā€œAnd none of it makes sense when one looks at the graph.ā€
What do you want me to tell you: I didnā€™t make the figure.
ā€œGoing back and recreating is trivial with the values recorded (if they are), but it is doubtful the actual samples are saved so that they could be retested.ā€
Well of course the water samples havenā€™t been saved, the data has.
ā€œDoesnā€™t legitimize the graph. The only thing that could be tested is the math.ā€
Which is why standards are run along with the samples, to ensure accuracy and precision of the methods WHILE the data are being taken.
ā€œThe ā€œmeasuredā€ has a gap in the middle, so they did have the means at that time, but it is absent. Chris doesnā€™t address that.ā€
There are no spectrophotometric pH data from this time period, to the best of my knowledge. If you know of some, great, please provide the link/reference.
ā€œIncluding two sources of data which come from different depths and including both on one graph would be just downright unprofessional, worse than sloppy.ā€
Why? You canā€™t put more than one dataset on a figure? If youā€™re unhappy with the figure, fine, download the data and create your own.
ā€œIf the method he claims is used for ā€œcalculatedā€ is superior to any other, there would be no reason to include the ā€œmeasuredā€ to the graph at all.ā€
Thereā€™s more than one way to skin a cat, and more than one way to measure pH (with varying degrees of confidence, of course). Again, if you donā€™t like the figure, download the data and create your own.
ā€œCertainly the two do not support a single trend. They are at odds.ā€
Really? Could you please show me the stats that demonstrate the two datasets show significantly different trends? Thanks!
ā€œChris hasnā€™t provided any reasoning for why the two measurement exist on the graph, and neither he nor Phil have responded to any of these concerns,ā€
Why are they on the same figure? Well, my guess would be so that they could put all the available data for the mixed layer on a single figure, instead of having to make two. But far more importantly, why in the world would it matter if these data are on the same or on different figures? What concerns have I not responded to?
ā€œChris hasnā€™t documented any of his claims, yet he accuses you of ignoring data.ā€
Are you joking? What claims have I not documented. Steven IS ignoring data. Heā€™s made the de facto statement that because he doesnā€™t understand how one calculates pH data form TCO2, TA, S, P, T, TP, TSi, heā€™s throwing it out. Sorry, but no, one doesnā€™t get to ignore data because they donā€™t understand it.
ā€œthe graph (select pH comparison):
http://hahana.soest.hawaii.edu/hot/trends/trends.html
http://hahana.soest.hawaii.edu/hot/protocols/chap23.html
ā€œpH is measured electrochemically using a combination
electrode.ā€
ā€œThe pH of seawater samples is calculated using the
electrode slope and isoelectric point and sample temperature.ā€ā€
Agreed, that is curious. For instance, see: http://hahana.soest.hawaii.edu/hot/methods/ph.html
Iā€™m fairly certain that the ā€˜measuredā€™ = spectrophotometric, but let me double check references to be sure.
Chris

Chris J
February 4, 2009 9:53 pm

@ Glenn,
“How were all these factors isolated and measured? Was Atomic absorption spectroscopy used? You didnā€™t respond to my post which questions all this.”
Apologies, I must’ve missed it. There were quite a few posts since I last visited, so was only able to skim them.
You can see methods listed on the website and in the publications. Nutrients are with standard methods with an autoanalyzer, as well a Magnesium induced coprecipitation method for low conc. phosphate. TCO2 was with a SOMMA and TA with a Gran titration. S, T, and P with CTD’s.
Atomic absorption spectroscopy might be used for things like some of the funky organics (no idea as I don’t work with anything remotely related to those data), but nothing related to carbonate chemistry.
Chris

Steven Goddard
February 4, 2009 10:34 pm

Chris J,
The point you are missing about the ocean system is that it contains large amounts of CaCO3 which buffer the alkalinity. Any push towards lower pH causes CaCO3 to dissolve, bringing the pH back up again. That is one reason why 5.2pH or less rainwater can continuously fall in the ocean, without any change in ocean pH. BTW – If ocean water did not circulate efficiently (as some have claimed) there would be an acidic layer near the surface, due to the rain. Instead, we find that pH decreases with depth.

Bill D
February 4, 2009 10:56 pm

George E. Smith (14:08:20) :
1. ā€œā€ foinavon (13:02:16) :
George E. Smith (12:07:00)
saw tooth; and that suggests to me that the southern CO2 uptake, is likely more ocean related, than land plant growth.
So you see, I was not trying to be smart alecky; but hinting that the waveform isa clue to the mechanism.
But as I said, if you took it as frivolous comment on your post please accept my apology; it wasnā€™t intended that way at all.
George\
George:
The problem is here that we should not just be looking at time series that and guessing about plausible explanations. Scientists have long had reasonably good estimates of terrestrial photosynthesis. More than forty years ago they did all of the calculations and found that the seasonal dynamics of atmospheric CO2 match the changes in seasonal changes in photosynthesis and respiration of terrestrial vegetation (and respiration including decomposers like bacteria and fungi). Moreover, no one (published paper) cites credible scientific evidence for an alternative explanation, such as one related to the oceans.
When all scientist who have considered the issue or read any basic text book that addressees the issue agree, then the critics (or a critic if you are the only one) have the obligation to present real data to challenge the consensus. If you are going to argue this point, you should go back to the estimates of terrestrial photosynthesis and respiration. One approach might be to show that estimates of photosynthesis etc. are wrong and that realistic values would not explain the pattern. You should also find data on seasonal estimates of CO2 flux for the worlds oceans. Here again, if you could provide quantitative data that explain most of the pattern this would be of tremendous interest to 10’s of thousands of scientist around the world. If you can really show the oceans are even a significant factor in a convincing way, you should be able to find a climate or atmospheric scientist who work with you on a manuscript. A convincing case should be a Science or Nature paper, something that most scientists only dream about. If you could be a co-author of a paper in one of these journals, you would then have greatly increased credibility in the science community.
I’m not saying that what are considered “known facts” that have been published in textbooks are always correct. However, just a guess based on a very casually “eyeballing” of the data is not a convincing attack. Neither is a simple assertion that you are correct and the general understanding of scientist around the world is wrong.

Chris J
February 4, 2009 11:02 pm

@ Glenn,
“Glenn (21:11:23) :
Chris J,
ā€œThe point I was making evidently did not come across. Calcite and aragonite are chemically different.ā€
No, Chris, they are not. Pure calcite has the same chemical composition as pure aragonite. When mixed with impurities, they are not pure. But when you say ā€œcalciteā€, you shouldnā€™t mean magnesium calcite. It isnā€™t hard to understand, or convey.”
Oh good lord Glenn–“pure” calcite and aragonite (pure being defined as without impurites/inclusions) do not exist. That’s the point! In the real world low-Mg calcite, aragonite, and hi-Mg calcite (of which there is quite a range of compositions) all have chemical differences among them that significantly affect a variety of physical and chemical properties. In addition, the distinct lattice structures impart additional differences in physical properties.
These three minerals are not remotely the same things, physically nor even chemically. They are chemically similar, but certainly not the same.
Chris

Chris J
February 4, 2009 11:08 pm

@ Richard,
“Richard (00:12:39) :
Chris J. has completely owned this thread. Thank you for trying to educate those (Mr. Goddard for example) who wish to deceive, manipulate, and generally misrepresent these processes and their associated evidence.”
Thanks Richard, it’s appreciated. It’s truly sad to see people adopting positions that are so wrong about so much. The thing that is really mind-blowing is that folks are arguing about issues that are entirely old hat: they were settled long, long ago. Instead of bothering to discuss something interesting or cutting edge, we’re wasting time on whether or not burning fossil fuels causes ocean acidification.
What should we move to next, whether the Earth is round or flat? How about whether or not the Sun orbits the Earth, or vice versa? I know, let’s see if we can’t get to the bottom of whether gravity is enough to keep the planets in orbit!
It’s terribly sad that people who pretend to speak on a topic could understand so little about it.
Chris

Alan Wilkinson
February 5, 2009 1:40 am

J Lo, I did the math for seawater a couple of days ago and found you were right then got swamped in something else. I apologize. Cheers.

Richard S Courtney
February 5, 2009 2:35 am

Phil:
In common with Foinavon, you use unfounded assertion and innuendo in attempt to claim that my factual and accurate posts are misleading.
I now write to illustrate your behaviour but ā€“ as with Foinavon ā€“ I will not answer any more of your posts. The facts I have stated are correct and others can easily check them for themselves.
The following are a few examples of your behaviour in your most recent post addressed to me.
You ask me:
ā€œWhy the switch in units to GtC, you wouldnā€™t be trying to mislead would you?
6.5 GtC= 24 Gtonne CO2.ā€
No! I was not ā€œtrying to misleadā€ and the suggestion is an unfounded insult.
I ā€œswitchedā€ to GtC because those are the units used by NASA in the source I cited and I was quoting. Furthermore, GtC are the only reasonable units to use when considering the flows between compartments of the carbon cycle because most of the carbon (e.g. in the oceans and the biosphere) does not exist as CO2 but is released to, and sequestered from, the atmosphere as CO2.
In response to my correct statements saying:
ā€œThe accumulation rate of CO2 in the atmosphere is equal to almost half the human emission. The human emission is about 6.5 GtC/year but the accumulation rate is about 3 GtC/year. However, this does not mean that half the human emission accumulates in the atmosphere, as is often stated.ā€
You asserted:
ā€œNo it means that the total non-anthropogenic sources-sinks must be less than the ā€˜human emissionā€™ by ~3 GtC/year (11 Gtonne CO2)ā€
But your assertion of what ā€œit meansā€ is factually incorrect. We observe in the seasonal variation that ā€œthe total non-anthropogenic sources-sinks ā€œ vary by much, much more ā€œthan the ā€˜human emissionā€™ ā€œ of ā€œ ~3 GtC/yearā€ within each year.
Nobody knows the variation of the individual global sources and global sinks to an accuracy of ~3 GTC per year: we observe the annual residual of their combined variation is ~3 GtC. And we observe that their combined variation is much more than ~3 GtC within each year. Simply, both of the sources and sinks are observed to vary by more than 3 GtC within each year, and either or both of them could be varying to provide the observed annual residual.
And you assert pure science fiction in response to my saying;
ā€œThe system does not ā€˜knowā€™ where an emitted CO2 molecule originated and there are several CO2 flows in and out of the atmosphere that are much larger than the human emission. The total CO2 flow into the atmosphere is at least 156.5 GtC/year with 150 Gt of this being from natural origin and 6.5 Gt from human origin. So, on the average, about 2% of all emissions accumulate.ā€
when you reply with
ā€œAnd these fluxes are ~balanced so they donā€™t show up in the measurements other than to modulate the CO2 uptake on a seasonal basis.ā€
But they are not ā€œbalancedā€ other wise they would not ā€œshow upā€ in the seasonal variation. However, you may have intended to assert that the fluxes fall into ā€œbalanceā€ over an annual cycle. If that was your intended assertion then it is extremely implausible: a ā€œbalanceā€ over the ~1500 years of the thermohaline circulation might possibly exist, but not over a single year.
I could go on, but the methods of you and Foinavon are apparent, and they do not seem to me to be a genuine attempt at resolving the many unknowns in the carbon cycle. Therefore, having stated my views ā€“ so all can evaluate them for themselves – I withdraw from further debate with you and Foinavon.
Richard

Pete D
February 5, 2009 6:06 am

J Peden –
If you increase the H2CO3 by some defined amount and work out the algebra using the equilibria equations you will be convinced!

Steven Goddard
February 5, 2009 6:08 am

Chris J,
Disappointing to see you reduce yourself to to ad hominem attack, flat earth comparisons and self-promotion.
Your last comment pretty much sums up your confused state – your words: “These three minerals are not remotely the same things, physically nor even chemically. They are chemically similar
Besides being self-contradictory, you really have no idea what you are talking about, yet you speak so confidently.
From: http://encarta.msn.com/encyclopedia_761573488/calcite.html
Calcite and aragonite have identical chemical compositions, but the molecules are stacked differently in the crystals. When two minerals have identical chemical compositions but different crystal structures, they are polymorphs of each other. Calcite is generally more stable than aragonite. Over several years, most aragonite will change to calcite. Thus, newly created calcium carbonate deposits may contain some or even a lot of aragonite, but ancient deposits contain little or no aragonite.

Chris J
February 5, 2009 7:01 am

@ Steven Goddard,
Steven, youā€™re so wrong about the things youā€™ve written here (below), itā€™s utterly shocking. Honestly, you nearly made my jaw drop. See below for a bit of reality.
ā€œChris J,
The point you are missing about the ocean system is that it contains large amounts of CaCO3 which buffer the alkalinity. Any push towards lower pH causes CaCO3 to dissolve, bringing the pH back up again.ā€
Steven, do you honestly think I and the rest of the scientific community have not considered the effects of CaCO3 dissolution? Let us entertain your claim that ā€œany push towards lower pH causes CaCO3 to dissolve, bringing the pH back up againā€ for a moment.
If it were true that the addition of CO2 to the ocean when solid CaCO3 is present is simply compensated by CaCO3 dissolution, it would be impossible for atmospheric CO2 to ever change. Think about it: any change in atmospheric CO2 would simply be compensated for by CaCO3 dissolution/precipitation. If the mechanism youā€™re suggesting (fast response time for CaCO3 to change in atmospheric CO2) were real the atmospheric CO2 concentration would have been constant on this planet over its entire history. To be blunt, even a momentā€™s thought would have made you realize how wrong that is. What then is the real response time like?
Rates of CaCO3 dissolution in the ocean are limited both spatially (i.e., most sea water is not in direct contact with CaCO3) and kinetically (CaCO3 dissolves slowlyā€”lots of experimental data here). Rates of dissolution have been measured in a variety of environments (deep sea, carbonate banks, neritic zones, etc.) under a variety of conditions. Given measured rates of dissolution, oceanic circulation patterns, diffusion, equilibration, etc., how long will it take for enough CaCO3 to dissolve (and secondarily silicate weathering) to reestablish the aragonite/calcite saturation state near preindustrial levels, given our current trajectory of CO2 emissions. Are you ready for it?
On the order of 18,000 yrs is needed. To fully reestablish preindustrial rates of CaCO3 accumulation in the open ocean, including in the deep sea, weā€™re looking at 100,000+ yrs (Archer et al.,1998; Archer, 2005; Anderson et al., 2003; Caldeira and Wickett, 2003; Zachos et al., 2005). Reef-building, on the other hand, takes on the order of several million years to recover after such a perterbation (see a discussion in Veron, 2008).
Your contention that CaCO3 dissolution will keep pace with and buffer against CO2 acidification isnā€™t just wrong, itā€™s ludicrous. Donā€™t believe me, read the references (which one wouldā€™ve hoped you would do before you posted).
ā€œThat is one reason why 5.2pH or less rainwater can continuously fall in the ocean, without any change in ocean pH. BTW – If ocean water did not circulate efficiently (as some have claimed) there would be an acidic layer near the surface, due to the rain. Instead, we find that pH decreases with depth.ā€
Again, youā€™re so wrong itā€™s shocking. pH is not a conservative parameterā€”you canā€™t determine the pH obtained by mixing two solutions with a weighted average. Hence, your argument that oceanic pH doesnā€™t fall appreciably despite the addition of pH = 5.2 rainwater is a non sequitur.
In unpolluted rain water the only major acid is carbonic acid, derived from atmospheric CO2 (yes, I know you know this). That water is essentially unbuffered. When you add rain water to sea water youā€™re adding water and a bit of dissolved CO2 (and tiny bits of HCO3- and immeasurably little CO3=, in equilibrium) and thatā€™s it. Since CO2 is less soluble in fresh water than sea water, the addition of rain slightly reduces the TCO2 of that sea water, nudging the system toward higher pH. However, the additional water dilutes the alkalinity, pushing the system toward lower pH. The overall effect for an addition of rainwater is small and is due entirely to the dilution of alkalinity: for a 1 ppt drop from 35 ppt to 34 ppt, pHsws would drop from 8.05 to 8.03 in standard sea water. This effect disappears as soon as the water evaporates and the alkalinity and salinity return to normal. There is no long term effect whatsoever.
The oceans circulate, but they donā€™t do so instantaneously. For an entire trip along the thermohaline conveyor belt it takes ~1500 years, and half that to turn over the entire mixed layer. If the ocean were completely stagnant below the mixed layer the addition of rainwater would do absolutely squat to long term pH. Since the only effect rainwater has on oceanic pH is a dilution effect on alkalinity, and that effect is counterbalanced by evaporation, long term not a darn thing happens.
Honestly man, I would recommend at the very least a rudimentary course in oceanography and aquatic chemistry/chemical oceanography. Your ignorance about the basics here is, frankly, breathtaking.
Chris

gary gulrud
February 5, 2009 8:00 am

“Chris J. has completely owned this thread.”
Like a toddler throwing a fit on the grocery floor.
Given 50,000 Gtons dissolved in the oceans, 100,000 lying at depth in precipitate form, believing a 10 Gton short-circuit in the yearly Carbon Cycle is throwing Gaia out of whack is monomaniacal immaturity. This is a yardstick of simplicity of intellectual achievement.
We have real problems out there.

Steven Goddard
February 5, 2009 8:22 am

It is interesting how the AGW camp simultaneously claims that the oceans have lost their ability to absorb more CO2, and that increased CO2 absorption by the oceans will lead to acidification.
http://www.guardian.co.uk/environment/2009/jan/12/sea-co2-climate-japan-environment
The two arguments are mutually exclusive, but the first one is closer to the truth on short time scales. Increased acidity leads to dissolution of limestone (CaCO3) below the carbonate compensation depth, which leads to reduced acidity and release of CO2 back to the atmosphere.
That is how buffering works.

Steven Goddard
February 5, 2009 8:36 am

Chris J,
You continue to make ridiculous claims. Rainwater doesn’t dilute the oceans. All of the acid rainwater evaporated from the oceans shortly before it fell back in. The system is in near perfect equilibrium over short time scales.
Secondly, the reduction in atmospheric CO2 over geologic time scales is because it has been absorbed into carbonate rock and removed from interaction with the ocean system. Take a trip to the Grand Canyon and observe the thick white layer across the top – named the Kaibab Limestone. A few hundred million years ago, all that CO2 contained in the rock was in the atmosphere – and the sea floor was covered with shellfish and corals. Changes in atmospheric CO2 correspond to changes in ocean temperature and changes in the amount of CO2 sequestered in rock.
The rim of the canyon is formed of a layer about 300 feet thick called the Kaibab Formation. This creamy yellow limestone has fossils in it: sharks, fish, corals, brachiopods, bryozoans, crinoids and sponges, that tell us it formed in a shallow, warm, Caribbean-like ocean.
http://www.hitthetrail.com/geology2.php

Simon Evans
February 5, 2009 8:53 am

Steven Goddard (08:22:24) :
It is interesting how the AGW camp simultaneously claims that the oceans have lost their ability to absorb more CO2, and that increased CO2 absorption by the oceans will lead to acidification.
http://www.guardian.co.uk/environment/2009/jan/12/sea-co2-climate-japan-environment

The article you link to is titled “Sea absorbing less CO2…”
Did you just misread it, Steven? Or do you not understand the language?
The two arguments are mutually exclusive, but the first one is closer to the truth on short time scales.
Not so – the opposite is the case. On the shorter scale the oceans are still absorbing more CO2 than they are outgassing, on the longer scale the opposite is projected. You presume that buffering is effectively instantaneous, or at least very rapid. It is understandable, therefore, that you would think acidification impossible. A false premise will, of course, lead to a false conclusion.

Steven Goddard
February 5, 2009 9:00 am

BTW Chris – your ignorance of geology, geochemistry and paleontology is – “breathtaking.”
Next educational trip I suggest is to Carlsbad Caverns. There you can see what happens when 5.2 pH rain lands on Calcium Carbonate rock. The acid rain dissolves the rock and leaves big holes behind. Large enough to put a football field in.
The dissolution process also releases CO2 to the atmosphere. Then the water becomes alkaline, and forms stalactites and stalagmites.
Difficult for you to imagine how a thick layer of marine limestone appeared in southern New Mexico? That is called geology, and the sequestration of carbon from the atmosphere. Your simple-minded view of the oceans and the earth as being a static chemical test tube, just doesn’t cut it.

Chris J
February 5, 2009 9:01 am

@ Steven Goddard,
“Chris J,
Disappointing to see you reduce yourself to to ad hominem attack, flat earth comparisons and self-promotion.ā€
Do you understand the nature of an ad hominem attack? An ad hominem attacks the qualities of the person advancing an argument, instead of the argument. I attacked your argument. Your argument attempts to refute long-settled understanding through a series of inaccurate or distorted statements, assumptions, or interpretations, just as flat Earth arguments do.
As for self promotion: I am anonymous here (Iā€™m really a Chris J., but clearly my J. is not public information here). How can an anonymous person self promote?
ā€œYour last comment pretty much sums up your confused state – your words: ā€œThese three minerals are not remotely the same things, physically nor even chemically. They are chemically similar
Besides being self-contradictory, you really have no idea what you are talking about, yet you speak so confidently.
From: http://encarta.msn.com/encyclopedia_761573488/calcite.html
Calcite and aragonite have identical chemical compositions, but the molecules are stacked differently in the crystals. When two minerals have identical chemical compositions but different crystal structures, they are polymorphs of each other. Calcite is generally more stable than aragonite. Over several years, most aragonite will change to calcite. Thus, newly created calcium carbonate deposits may contain some or even a lot of aragonite, but ancient deposits contain little or no aragonite.ā€
Let me speak very plainly: I am an active researcher. My area of research focuses on biomineralization, and secondarily on the effects of ocean acidification on marine organisms. Carbonate chemistry/biomineralization are my areas of expertise. I am telling you very plainly that low-Mg calcite, aragonite, and hi-Mg calcite, while chemically similar, are not identical, and these differences are important. Your citation of an encyclopedia article (written for lay audiences, and over-generalized in this case) is incorrect in stating that calcite and aragonite are chemically identical. If they were a great deal of the information we can glean from such skeletons/shells would not exist. Magnesium and strontium content are among the important differences among these minerals.
ā€œIt is interesting how the AGW camp simultaneously claims that the oceans have lost their ability to absorb more CO2, and that increased CO2 absorption by the oceans will lead to acidification.
http://www.guardian.co.uk/environment/2009/jan/12/sea-co2-climate-japan-environment
The two arguments are mutually exclusive, but the first one is closer to the truth on short time scales. Increased acidity leads to dissolution of limestone (CaCO3) below the carbonate compensation depth, which leads to reduced acidity and release of CO2 back to the atmosphere.
That is how buffering works.ā€
Steven, you either didnā€™t read that article, or didnā€™t understand what you read. The rate of CO2 absorption by the ocean has decreased, not stopped. The ocean is sequestering CO2 slower than it used to, but is still sequestering it. Thatā€™s what the article says, thatā€™s whatā€™s happening, and your misreading of it doesnā€™t change these facts.
Second, you evidently have no understanding of the effects of CaCO3 dissolution on CO2 sequestration. The dissolution of CaCO3 enhances, not reduces the capacity of the ocean to sequester CO2: CaCO3 + CO2 = Ca++ + 2HCO3-
Of course the response time for meaningful dissolution of CaCO3 is far, far too slow to have an significant impact this century, or for many to come (see post above and references therein).
I am again astounded by you lack of understanding, misunderstanding, and outright distortion of the very basics here. If you donā€™t understand even the rudimentary aspects of this chemistry, why did you feel qualified to write about it in the public square?
Chris

Steven Goddard
February 5, 2009 9:04 am

Simon Evans,
Think about your last post.
The IPCC is claiming a much accelerated rate of acidification over the remainder of the century. How can CO2 absorption be slowing down and accelerating at the same time?
Secondly, as I have pointed out repeatedly, the existence of La Nina is proof of the rapid interchange of deep and shallow water in the Pacific. Where do you think the cold water came from?

Chris J
February 5, 2009 9:23 am

@ Steven Goddard,
ā€œChris J,
You continue to make ridiculous claims. Rainwater doesnā€™t dilute the oceans. All of the acid rainwater evaporated from the oceans shortly before it fell back in. The system is in near perfect equilibrium over short time scales.ā€
Exactly the point I made! Your claim was that if the surface of the ocean were not rapidly turned over then rain (pH ~5.2) would reduce the pH of this surface layer over the long term. You were completely wrong, as I explained to you. Rain dilutes seawater, diluting alkalinity, and causes a small reduction in instantaneous pH as a result. This effect is counteracted by evaporation (concentrates alkalinity, raising instantaneous pH). There is no long term trend. That is the point I made to you!
ā€œSecondly, the reduction in atmospheric CO2 over geologic time scales is because it has been absorbed into carbonate rock and removed from interaction with the ocean system.ā€
Youā€™re astounding Steven. Just above you argue that the entire ocean is readily and rapidly buffered against CO2 addition by carbonate dissolution (which is nonsense, as I demonstrate above), and here you argue that the same carbonate minerals have been removed from interaction with the ocean system.
The same minerals that are available to reduce atmospheric or oceanic CO2 via chemical weather (silicates and carbonates) were always available. Long term variation in atmospheric CO2 has resulted due to a combination of geological processes and biological sequestration. Storage in carbonates is only one of the important sinks.
ā€œTake a trip to the Grand Canyon and observe the thick white layer across the top – named the Kaibab Limestone. A few hundred million years ago, all that CO2 contained in the rock was in the atmosphere – and the sea floor was covered with shellfish and corals. Changes in atmospheric CO2 correspond to changes in ocean temperature and changes in the amount of CO2 sequestered in rock.
The rim of the canyon is formed of a layer about 300 feet thick called the Kaibab Formation. This creamy yellow limestone has fossils in it: sharks, fish, corals, brachiopods, bryozoans, crinoids and sponges, that tell us it formed in a shallow, warm, Caribbean-like ocean.
http://www.hitthetrail.com/geology2.phpā€
Steven, sequestration of CO2 in biogenic carbonates increases atmospheric CO2, it doesnā€™t reduce it. How do you not understand this? Only chemical weathering of existing carbonates and silicates draws down atmospheric CO2, not production of carbonates de novo.
Chris

gary gulrud
February 5, 2009 9:44 am

“You presume that buffering is effectively instantaneous, or at least very rapid.”
Steve is correct in his assumption, if it is an assumption on his part.
I don’t remember exact readings but at pH 8.4 where OH- outnumber H+ say 25 to one, all of the CO2 entering a region of interest is immediately converted to carbonate ions.
At current pH, lets say 8.17 for jollies, new CO2 leads to conversion of carbonate ions to bicarbonate ion in greater numbers than any carbonate addition.
Below pH 8, all the carbonate is long gone.

Steven Goddard
February 5, 2009 10:03 am

Chris J,
I can see that you have no understanding of geology whatsoever. So I will start from the beginning.
During the Carboniferous period, huge deposits of carbonate rock formed and were removed from the ocean system. Much of this rock was uplifted above sea level. This corresponded to the 95% drop in atmospheric CO2 seen in the graph above during that period. Carbon was removed from the atmosphere through the formation and sequestration of carbonate rock. Your failure to understand this is somewhat bizarre.
H2O evaporates from the ocean continuously. It combines with atmospheric CO2 to form carbonic acid. Some of the acid rain falls on land, which dissolves silicatesand brings alkali metals like Ca, Na and K into the oceans. These combine with dissolved CO2 to form carbonate rocks.
There are also huge amounts of carbonates currently on the sea floor. These buffer the system from the acid rain and prevent the ocean from becoming acidic.
You wrote – “Only chemical weathering of existing carbonates and silicates draws down atmospheric CO2”
Quite the opposite. When acid comes in contact with carbonates, it releases CO2. Try mixing vinegar and baking soda to see this in action. This happens in caves and karst environments all the time. Some caves contain levels of CO2 that are hazardous to spelunkers.

Chris J
February 5, 2009 10:07 am

@ Steven Goddard,
“BTW Chris – your ignorance of geology, geochemistry and paleontology is – ā€œbreathtaking.ā€
Next educational trip I suggest is to Carlsbad Caverns. There you can see what happens when 5.2 pH rain lands on Calcium Carbonate rock. The acid rain dissolves the rock and leaves big holes behind. Large enough to put a football field in.”
And that the dissolved materials are redeposited elsewhere in the cave (you know, stalagmites/stalactites) or is lost to groundwater and eventually ends up somewhere else (possibly the ocean). I won’t quibble too much over this point, as it’s just not worth it, but only rainwater with substantially lower than normal pH due to the dissolution of NOx and SOx is operationally termed “acid rain”. Normal rainwater is slightly acidic, but is not “acid rain”.
“The dissolution process also releases CO2 to the atmosphere. Then the water becomes alkaline, and forms stalactites and stalagmites.”
Great googly moogly man, you really don’t have a clue how this chemistry works, do you? The dissolution of carbonates does not release CO2 to the atmosphere, it consumes it: CaCO3 + CO2 + H2O = Ca++ + 2HCO3-
The CO2 that is consumed by solvating the carbonates is released to the atmosphere when the carbonates precipitate (to form stalagmites/stalactites): Ca++ + 2HCO3- = CaCO3 + CO2 + H2O
That reaction is forced by evaporation of water from the solutions, concentrating them and causing precipitation of CaCO3 and loss of CO2.
“Difficult for you to imagine how a thick layer of marine limestone appeared in southern New Mexico? That is called geology, and the sequestration of carbon from the atmosphere. Your simple-minded view of the oceans and the earth as being a static chemical test tube, just doesnā€™t cut it.”
Uh, no, it’s not at all difficult to imagine how marine limestone ended up in New Mexico. One part higher sea levels plus two parts geologic uplift gives you marine sediments high and dry. But, how is this related to the discussion anyway?
Chris

SteveSadlov
February 5, 2009 10:09 am

RE: “Take a trip to the Grand Canyon and observe the thick white layer across the top – named the Kaibab Limestone”
Or take a look at the Alps. Immense amounts of fixed carbon in them thar hills! All those “dents” of craggy lime stone.

JamesG
February 5, 2009 10:09 am

Mary Hinge
“Your comment shows what is wrong with the sceptic view. You just donā€™t read the evidence,or ignore it if you do. ”
I’m not ashamed of being skeptical. With a lack of real evidence, the alternative to being skeptical is often to jump to the wrong conclusion.
Your own comments meanwhile show the two main problems with the AGW view:
a) You accept mere opinion as “evidence”. It never is! In a court it would be called “hearsay”. In science it is called “theory”. All opinions ultimately need some sort of backup data. By coincidence, I just read the other day that it was commonly believed by the psychiatric community that cauliflower ears were a sign of insanity. Should anyone have believed their theory simply because it was the majority opinion? As a scientist you should know that attribution is a bit more complex than counting the number of me-too papers. We need real evidence, not more mere opinion.
b) You confuse correlation with causation. We can all very easily correlate any two things that have risen in the past 10 years and say they are related but that is classically bad science. Pollution and tourism have obviously also risen. Every study I’ve seen mentions those and other factors – as indeed did the paper you referenced. We need to find the particular thing that kills the coral though. To do that we need to try to eliminate certain factors by comparisons.
Hence you should now see that the paper you referred to made these two common failings too, whilst still being careful to mention the other factors which you obviously ignored. But singling out global warming (anthropogenic or not) as deserving special attention seems to ignore the facts as my reference to Cuba’s coral and my subsequent comment about real scientific work that says that warming should lead to more coral, not less are both intended to demonstrate.
Using proper scientific methods, all you have to do is look at the data dispassionately and CO2 can very quickly be eliminated as a “stress”. That much is very obvious to me and to many others. As long as certain prominent scientists refuse to do this then we will surely be headed in the wrong direction and we may not prevent a crisis. I hope that isn’t the case.

SteveSadlov
February 5, 2009 10:11 am

Back on my Sigma topic … still no takers for demonstrating Gage R&R for a significant oceanic study of 2 sigma or better.
OK, here’s my final offer, then, liquidation (e.g a complete and utter discrediting) will commence.
1 Sigma.

Steven Goddard
February 5, 2009 10:15 am

Wow 602 responses! Is that a record?

SteveSadlov
February 5, 2009 10:18 am

RE: “on the longer scale the opposite is projected. ”
“Projected” … typical warmista speak.
I think I am going to be ill.

Chris J
February 5, 2009 10:20 am

@ Steven Goddard,
Please, I beseach you, read or re-read my last several mosts above starting with Chris J (07:01:34) : very carefully. You have said the same sorts of things in the last several posts though I have already demonstrated why these points are incorrect (above). Please read these posts (I can appreciate you may not have seen them) and we can continue our discussion.
Chris

gary gulrud
February 5, 2009 10:39 am

Sadlov: I’d take your bet just to be friendly but sadly I’ve no coin to part with.

gary gulrud
February 5, 2009 10:49 am

Hey, Beaker, I got As in Inorganic, my Interior Designer sisters passed Organic. Why do you think any of us would find your jeremiads enlightening? Re-read yourself.

Patrick Henry
February 5, 2009 12:17 pm

This is just too much fun.
The only evidence that has been presented for the oceans becoming more acidic is one highly questionable and erratic graph of “calculated data” from HOTS. All three “measured data” sets (Monterey, Aloha and Kahe) show no meaningful trend towards lower pH, and we know that the carbonate compensation depth wasn’t tremendously different in the Ordovician when CO2 levels were 4,000 PPM and thousands of species of CaCO3 based shellfish and corals thrived.
The AGW crowd claims that ocean CO2 absorption rates are decreasing, while ocean acidification rates (from CO2 absorption) are increasing. Never mind that these are mutually exclusive. (Whatever panic story works best with the current crowd, seems to be the philosophy.)
I’m not impressed.

Glenn
February 5, 2009 1:42 pm

Chris,
ā€œthe graph (select pH comparison):
http://hahana.soest.hawaii.edu/hot/trends/trends.html
http://hahana.soest.hawaii.edu/hot/protocols/chap23.html
ā€œpH is measured electrochemically using a combination
electrode.ā€
ā€œThe pH of seawater samples is calculated using the
electrode slope and isoelectric point and sample temperature.ā€ā€
Agreed, that is curious. For instance, see: http://hahana.soest.hawaii.edu/hot/methods/ph.html
Iā€™m fairly certain that the ā€˜measuredā€™ = spectrophotometric, but let me double check references to be sure.
*************
I’ve no reason to doubt that the measured data reflects the spectrophometric method. The problem is in what you claim as the third method (which you don’t even name) as being the method used to create the continuous record and trend on the graph. You asked me to verify your claim, yet I have already provided the link to how ph is claimed to be calculated. I will assume that because you think that curious, that the method used continuously from 1989 to the present is not the one you claim, but one of two methods you claim are as or less accurate. Yet you said earlier:
“They have a long-term dataset for a huge number of parameters, including DIC, TA, S, T, P, DIP, total silicate, etc. pH can be calculated from these data more accurately than it can be measured with the tools that were available when they started taking this data (namely electrodes).”
So which is method have they been using continuously from 1989 to the present (the trend line), “electrodes” or your “calculated” method you describe in Chris J (17:52:34)? I’m asking you, since the quote above clearly shows that you thought that “electrodes” were used, not the “calculated” method you later claimed.
Now maybe it is true that they were taking ph reading from “electrodes” in 1989, but somewhere down the road they started “calculating” from saved flasks and changed all the data to reflect what you claim is more accurate data, but that the chart doesn’t give us a hint of that, athough the chart does show another dataset from another method.
Perhaps you are right, since you have made the claim, or at least to my mind implied that is what has happened, that all these “parameters” are still available for testing by “calculation”, there is no indication of that being the case, nor have you provided any documentation of that, and the references both provided by you and me to the HOT website do not reflect that, rather what has been provided from that site contradicts the claim that the continuously graphed data is from “calculated” methodology.

SteveSadlov
February 5, 2009 2:31 pm

0 Sigma. In other words, there is no signal in the noise.
As I suspected.

Glenn
February 5, 2009 3:21 pm

Chris J,
“Oh good lord Glennā€“ā€pureā€ calcite and aragonite (pure being defined as without impurites/inclusions) do not exist.”
Then do not include CaCO3 in chemical formulations.

Glenn
February 5, 2009 3:51 pm

Chris J (10:07:30) :
Next educational trip I suggest is to Carlsbad Caverns. There you can see what happens when 5.2 pH rain lands on Calcium Carbonate rock. The acid rain dissolves the rock and leaves big holes behind. Large enough to put a football field in.ā€
And that the dissolved materials are redeposited elsewhere in the cave (you know, stalagmites/stalactites) or is lost to groundwater and eventually ends up somewhere else (possibly the ocean). I wonā€™t quibble too much over this point, as itā€™s just not worth it, but only rainwater with substantially lower than normal pH due to the dissolution of NOx and SOx is operationally termed ā€œacid rainā€. Normal rainwater is slightly acidic, but is not ā€œacid rainā€.
ā€œThe dissolution process also releases CO2 to the atmosphere. Then the water becomes alkaline, and forms stalactites and stalagmites.ā€
Great googly moogly man, you really donā€™t have a clue how this chemistry works, do you? The dissolution of carbonates does not release CO2 to the atmosphere, it consumes it: CaCO3 + CO2 + H2O = Ca++ + 2HCO3-
*********************************
You may have noticed that Steven did not mention or refer to carbonic acid as being responsible for Carlsbad, and you assumed that he was talking about CO2 in water, but you were aware that sulfuric acid was involved in the formation of the caves. Is this dissolution process incorrect?
CaCo3 + H2SO4 = CaSO4 + H2O + CO2

Steven Goddard
February 5, 2009 4:26 pm

Hi Chris,
Most people learn in primary school science class, that if you mix acid and baking soda or acid and limestone together, you create copious amounts of CO2. Since you seem to have forgotten that, here is a explanation which might help out.
http://library.thinkquest.org/3347/vinegar+bsoda4.html
What actually happens is this: the acetic acid (that’s what makes vinegar sour) reacts with sodium bicarbonate (a compound that’s in baking soda) to form carbonic acid. It’s really a double replacement reaction. Carbonic acid is unstable, and it immediately falls apart into carbon dioxide and water (it’s a decomposition reaction). The bubbles you see from the reaction come from the carbon dioxide escaping the solution that is left.

Chris J
February 5, 2009 4:43 pm

@ Glenn,
ā€œChris J,
ā€œOh good lord Glennā€“ā€pureā€ calcite and aragonite (pure being defined as without impurites/inclusions) do not exist.ā€
Then do not include CaCO3 in chemical formulations.ā€
Glenn, one uses mole fractions, e.g., Ca80Mg20CO3 for 20 mol % MgCO3 hi-Mg calcite.
ā€œYou may have noticed that Steven did not mention or refer to carbonic acid as being responsible for Carlsbad, and you assumed that he was talking about CO2 in water,ā€
Glenn, you cite the pertinent passage in your post:
ā€œNext educational trip I suggest is to Carlsbad Caverns. There you can see what happens when 5.2 pH rain lands on Calcium Carbonate rock. The acid rain dissolves the rock and leaves big holes behind. Large enough to put a football field inā€
Thatā€™s carbonic acid in rain water Glenn. He specifically mentioned CO2 in rain water in reference to CaCO3 dissolution at Carlsbad.
ā€œbut you were aware that sulfuric acid was involved in the formation of the caves. Is this dissolution process incorrect?
CaCo3 + H2SO4 = CaSO4 + H2O + CO2ā€
Ha, yes Glenn, I am aware of the role of sulfuric acid in the cave formation, and yes that is the correct overall equation for the reaction of CaCO3 with H2SO4. That, however, is not what Steven arguedā€”I responded to his argument.
Chris

Steven Goddard
February 5, 2009 4:50 pm

Here is another fun one. Even if you use some of that “impure” limestone Chris has been warning us about ad nauseum (or just about any other carbonate containing material) the release of CO2 is the same:
http://www.backwoodshome.com/articles/shober32.html
If you live in a section of the country where there is limestone, this is a great recipe for fun. Simply drop a limestone pebble into the acidic vinegar and watch it begin to bubble and boil! This happens because the limestone is so alkaline (the opposite of acid) that the two substances go to war, creating carbon dioxide gas bubbles as the stone is eaten away. This project will also work if you live in a section of the country where there are talc mines (chalk or talcum powder) or beaches (sea shells) or chicken houses (egg shells!).

Chris J
February 5, 2009 5:12 pm

@ Steven Goddard,
Hi Steven,
ā€œHi Chris,
Most people learn in primary school science class, that if you mix acid and baking soda or acid and limestone together, you create copious amounts of CO2. Since you seem to have forgotten that, here is a explanation which might help out.
http://library.thinkquest.org/3347/vinegar+bsoda4.html
What actually happens is this: the acetic acid (thatā€™s what makes vinegar sour) reacts with sodium bicarbonate (a compound thatā€™s in baking soda) to form carbonic acid. Itā€™s really a double replacement reaction. Carbonic acid is unstable, and it immediately falls apart into carbon dioxide and water (itā€™s a decomposition reaction). The bubbles you see from the reaction come from the carbon dioxide escaping the solution that is left.ā€
Steven, the reaction of a carbonate (or NaHCO3 as described in the link) with an acid OTHER than carbonic acid is not the same as the reaction of a carbonate with CO2.
For an acid besides carbonic we have:
CaCO3 + HxA = Ca++ + H+ + A- + CO2 + H2O
You get dissolved calcium, protons, the conjugate base of the acid, CO2 and water.
For the reaction of a carbonate with CO2 we have:
CaCO3 + CO2 + H2O = Ca++ + 2HCO3-
Getting to the big picture though, youā€™ve claimed above that the dissolution of CaCO3 will neutralize the addition of CO2 to sea water. You claim here that the dissolution of CaCO3 produces CO2. So, youā€™re suggesting that the dissolution of CaCO3 simultaneously sequesters and produces CO2?
Time to open a textbook. May I recommend Aquatic Chemistry by Stumm and Morgan.
Since youā€™ve not responded to any of the points I raised above I assume we are in agreement, yes? The dissolution of CaCO3 sequesters CO2 via the reaction above, but the timescale required to reestablish arag/calc saturation state and the CCD similar to the preindustrial after the slug of CO2 we are on track to produce will require on the order 100,000 yrs. The response time is far too slow to meaningfully affect oceanic pH or other chemistry parameters this century.
Chris

Chris J
February 5, 2009 5:42 pm

@ Glenn,
Hi Glenn,
ā€œIā€™ve no reason to doubt that the measured data reflects the spectrophometric method. The problem is in what you claim as the third method (which you donā€™t even name)ā€
Iā€™m not sure it has a name: itā€™s the calculation of in situ pH given measured values for all of the parameters I list. I mean, what should we call that: ā€˜pH calculated using all pertinent data and dissociation constantsā€™?
ā€œas being the method used to create the continuous record and trend on the graph. You asked me to verify your claim, yet I have already provided the link to how ph is claimed to be calculated.ā€
No no no Glenn, that is not a calculated pH, that is a measured pH. pH can be measured with electrodes, as in the link you provide (not terribly accurate), with an indicator dye, e.g., m-cresol purple (very accurate), or calculated with the mentioned data (very accurate).
ā€œI will assume that because you think that curious, that the method used continuously from 1989 to the present is not the one you claim, but one of two methods you claim are as or less accurate.ā€
No Glenn, the ā€˜calculatedā€™ dataset is exactly as I state above. My understanding was that the ā€˜measuredā€™ dataset was measured using the m-cresol purple method. Your link to a measured electrode method has made me question my memory here, so Iā€™ll have to go back to the references to double check on which of the two methods was used to produce the ā€˜measuredā€™ dataset.
ā€œSo which is method have they been using continuously from 1989 to the present (the trend line), ā€œelectrodesā€ or your ā€œcalculatedā€ method you describe in Chris J (17:52:34)? Iā€™m asking you, since the quote above clearly shows that you thought that ā€œelectrodesā€ were used, not the ā€œcalculatedā€ method you later claimed.ā€
The ā€˜calculatedā€™ dataset from 1989 to present is calculated from the data I mention aboveā€”that Iā€™m sure about. The ā€˜measuredā€™ dataset I believe was created using the m-cresol purple method. As above, Iā€™ll have to go back to the references to determine if Iā€™m remembering correctly that they used the m-cresol purple method to produce this dataset, or if Iā€™m misremembering and they used electrodes.
ā€œNow maybe it is true that they were taking ph reading from ā€œelectrodesā€ in 1989, but somewhere down the road they started ā€œcalculatingā€ from saved flasks and changed all the data to reflect what you claim is more accurate data, but that the chart doesnā€™t give us a hint of that, athough the chart does show another dataset from another method.ā€
Huh-uh, this Iā€™m certain about: the ā€˜calculatedā€™ data are calculated from the array of parameters mentioned above, which they took over the entire period. The only question here is did they use the m-cresol purple method or electrodes to produce the ā€˜measuredā€™ dataset. Iā€™m not 100% sure at the moment. Agreed, the chart doesnā€™t make this clear. Detailed methodologies are in the published papers (and maybe somewhere on the site), which Iā€™ll have to dig out when I get a chance. Also, I doubt very much the samples were saved very longā€”thereā€™s usually only enough space in most labs for the samples youā€™re about to run, certainly not years worth of half run water samples (which wouldnā€™t be good with so much water removed anyway).
ā€œPerhaps you are right, since you have made the claim, or at least to my mind implied that is what has happened, that all these ā€œparametersā€ are still available for testing by ā€œcalculationā€, there is no indication of that being the case, nor have you provided any documentation of that, and the references both provided by you and me to the HOT website do not reflect that, rather what has been provided from that site contradicts the claim that the continuously graphed data is from ā€œcalculatedā€ methodology.ā€
All of the data you need are right there on the site. In the same place you were downloading the pH data you can select all of the parameters you need to calculate pH (as above) and then perform the calculations.
I donā€™t understand your claim that thereā€™s no indication that the ā€˜calculatedā€™ dataset was produced with CTD, nutrient, DIC, and TA data. It says ā€˜calculatedā€™ right on the graphic. If you go to any of the papers theyā€™ll mention this briefly and cite the references that show the pertinent information for calculation. I realize that this probably is very foreign to someone that does not work with seawater chemical analyses, but these are very standard methods used at thousands of labs around the world.
Chris

Glenn
February 5, 2009 5:45 pm

Chris J
ā€œNext educational trip I suggest is to Carlsbad Caverns. There you can see what happens when 5.2 pH rain lands on Calcium Carbonate rock. The acid rain dissolves the rock and leaves big holes behind. Large enough to put a football field inā€
Thatā€™s carbonic acid in rain water Glenn. He specifically mentioned CO2 in rain water in reference to CaCO3 dissolution at Carlsbad.
******************
Er, no, he, didn’t, Chris. He didn’t mention CO2 specifically, he didn’t mention CO2 at all. And there’s more than carbonic acid in acid rain.
“Glenn, one uses mole fractions, e.g., Ca80Mg20CO3 for 20 mol % MgCO3 hi-Mg calcite.”
Then include that in all chemical formulations, if pure calcite does not exist.

Chris J
February 5, 2009 5:47 pm

@ Steven Goddard,
“Here is another fun one. Even if you use some of that ā€œimpureā€ limestone Chris has been warning us about ad nauseum (or just about any other carbonate containing material) the release of CO2 is the same:
http://www.backwoodshome.com/articles/shober32.html
If you live in a section of the country where there is limestone, this is a great recipe for fun. Simply drop a limestone pebble into the acidic vinegar and watch it begin to bubble and boil! This happens because the limestone is so alkaline (the opposite of acid) that the two substances go to war, creating carbon dioxide gas bubbles as the stone is eaten away. This project will also work if you live in a section of the country where there are talc mines (chalk or talcum powder) or beaches (sea shells) or chicken houses (egg shells!).”
See above Steven. CaCO3 cannot simultaneously sequester and produce CO2 upon reaction with CO2. See Stumm and Morgan, 1996 for an extensive discussion of carbonate chemistry.
Chris

Steven Goddard
February 5, 2009 5:47 pm

Chris,
You are a piece of work. Take a piece of limestone and stick it in a dilute acid. You will see lots of CO2 bubbles coming up. The fact that you don’t understand it, doesn’t change reality.

Glenn
February 5, 2009 5:48 pm

http://en.wikipedia.org/wiki/Carbon_dioxide
“Carbon dioxide is soluble in water, in which it spontaneously interconverts between CO2 and H2CO3 (carbonic acid).”
http://en.wikipedia.org/wiki/Carbonic_acid
“It has since been shown, by theoretical calculations, that the presence of even a single molecule of water causes carbonic acid to revert to carbon dioxide and water fairly quickly.”

Glenn
February 5, 2009 5:55 pm

Steven Goddard (16:50:10) :
“Here is another fun one. Even if you use some of that ā€œimpureā€ limestone Chris has been warning us about ad nauseum (or just about any other carbonate containing material) the release of CO2 is the same:”
Shoot, just drop a tums into coke and watch the fizz and calcium condensing.

Glenn
February 5, 2009 6:02 pm

http://en.wikipedia.org/wiki/Bicarbonate
“The flow of bicarbonate ions from rocks weathered by the carbonic acid in rainwater is an important part of the carbon cycle.”

Editor
February 5, 2009 6:12 pm

Chris J (09:01:14) :

@ Steven Goddard,
ā€œChris J,
Disappointing to see you reduce yourself to to ad hominem attack, flat earth comparisons and self-promotion.ā€
Do you understand the nature of an ad hominem attack? An ad hominem attacks the qualities of the person advancing an argument, instead of the argument. I attacked your argument.
As for self promotion: I am anonymous here (Iā€™m really a Chris J., but clearly my J. is not public information here). How can an anonymous person self promote?

It would be nice to know why you hide behind an initial, but since it’s unlikely I’ll ever have you as a Chemistry professor I suppose it doesn’t matter. I do recommend that you take the time to learn how to be a teacher without attacking and denigrating your students. I generally skip over your posts, there are plenty of other posters who are worth reading. It’s rather a pity, as I’m fond of limestone caves. New Hampshire would be a better place it if had some limestone. And more species of snakes. And no black flies.
Thank you for taking the time to provide examples of ad hominem attacks. You must be a real joy at the dinner table:

Besides being self-contradictory, you really have no idea what you are talking about, yet you speak so confidently.
Steven, you either didnā€™t read that article, or didnā€™t understand what you read
I am again astounded by you lack of understanding, misunderstanding, and outright distortion of the very basics here. If you donā€™t understand even the rudimentary aspects of this chemistry, why did you feel qualified to write about it in the public square?

Instead of attacking arguments and then stepping up to attacking the messenger, try simply explaining the science and stop there. Try asking questions of the messenger that are designed to let _him_ discover any mistakes, people are generally more willing to admit a mistake when they find it themselves than when being berated by claims like “you really have no idea what you are talking about.”

Glenn
February 5, 2009 6:48 pm

Chris J (17:42:44) :
“I donā€™t understand your claim that thereā€™s no indication that the ā€˜calculatedā€™ dataset was produced with CTD, nutrient, DIC, and TA data. It says ā€˜calculatedā€™ right on the graphic.”
Such a long post to basically say “nuh uh” and “I’m certain about this”.
I’ve reproduced the below a few times, yet you don’t understand why I am questioning the “calculated” data?
http://hahana.soest.hawaii.edu/hot/protocols/chap23.html
ā€œpH is measured electrochemically using a combination
electrode.ā€
ā€œThe pH of seawater samples is calculated using the
electrode slope and isoelectric point and sample temperature.ā€
You are claiming the ph trend graph does not represent either of these methods, right?

Steven Goddard
February 5, 2009 8:27 pm

Chris,
I have been trying to figure out what is confusing you, and think I am getting a grasp on it. It seems to derive from this equation, which has apparently lead you to the belief that that limestone formation releases CO2 (even though it obviously sequesters it.)
Ca++ + 2HCO3- -> CaCO3 + CO2 + H2O
Hopefully this explanation will help.
Start out with two CO2 molecules and make two carbonic acid molecules
2CO2 + 2H2O -> 2H2CO3
The two carbonic acid molecules decompose to two bicarbonate ions
2H2CO3 -> 2HCO3- + 2H+
And those two bicarbonate ions form one CaCO3 molecule and one CO2 molecule when combined with a calcium ion.
Ca++ + 2HCO3- -> CaCO3 + CO2 + H2O
So we started out with two CO2 molecules, and ended up with one. In other words, half of the CO2 we started with was sequestered in limestone.
Remember that cement manufacture releases huge amounts of sequestered CO2, when the limestone is heated.

Glenn
February 5, 2009 9:35 pm

Steven,
And on that note, lets remember that there is a pH buffering
system that limits seawater pH, many say to between 7.5 and 8.4.
That should enforce the idea that there can be no “acidification” process.

MartinGAtkins
February 5, 2009 9:41 pm

However itā€™s considered that the K/T boundary is associated with another impact whose crater hasnā€™t been found.

If the crater can’t be found then other supporting evidence needs to be produced. Has it?
Abstract
PJ Mayhew et al. (2007) A long-term association between global temperature and biodiversity,
Our findings may have implications for extinction and biodiversity change under future climate warming.
We can dismiss this paper as It’s conjecture built on a preconceived notion.
Keller G (2005) Impacts, volcanism and mass extinction: random coincidence or cause and effect? Austral. J. Earth Sci 52 725-757.
(Iā€™ve reproduced the abstract below [***] )”

Sorry but I need the full paper to study before I can research their findings.
Wignall P (2005) The link between large igneous province eruptions and mass extinctions Elements 1, 293-297
Abstract: ā€œIn the past 300 million years, there has been a near-perfect association between extinction events and the eruption etc
This is smoke and mirrors, throughout earths history there have been large
tectonic and geothermal events. You will always find them somewhere near extinctions and not so near.
I do not do science through abstracts. I need to study the full paper. All to often I see this tactic used by AGW proponents. Abstracts are only a preface to the work. They are not intended to be used as factual a representation of any scientific certainty in any field.
Current understanding is that the Chicxulub impact is the best candidate so far. In order for that not to be the case then compelling evidence needs to be produced to the contrary. That means field research, not theory.
Wignall Et al State.
The best links between extinction and eruption are seen in the interval from 300 to 150 Ma.
So these researchers are dealing with extinctions as a job lot. Yes very scientific. And this.
such as release of methane from gas hydrate reservoirs or shut-down of photosynthesis in the oceans, are probably required to achieve severe green-house warming.
Shutting down photosynthesis would lead to a massive decay in vegetation and that would lead to methane and CO2 levels to rise at a precipitous level.
Present day evidence shows volcanic action leads to cooling and the blocking of solar radiance. It also shows that warming leads to elevated CO2 and Methane levels. Not the other way round.

MartinGAtkins
February 5, 2009 9:44 pm

My last message was for.
foinavon (05:17:36) :

Bill D
February 5, 2009 11:06 pm

JamesG (10:09:37) :
Mary Hinge
ā€œYour comment shows what is wrong with the sceptic view. You just donā€™t read the evidence,or ignore it if you do. ā€
Iā€™m not ashamed of being skeptical. With a lack of real evidence, the alternative to being skeptical is often to jump to the wrong conclusion.
Your own comments meanwhile show the two main problems with the AGW view:
a) You accept mere opinion as ā€œevidenceā€. It never is! In a court it would be called ā€œhearsayā€. In science it is called ā€œtheoryā€. All opinions ultimately need some sort of backup data.
James:
In science, a ā€œtheoryā€ is the highest level of understanding, backed by much hard data. This might include: ā€œthe theory of gravityā€, the ā€œtheory of evolutionā€, ā€œthe atomic theory of matterā€, the ā€œgermā€ theory of infectious disease, etc. The use of the word ā€œtheoryā€ by scientists is very different from the everyday use in popular culture. In most cases, what you talk about as ā€œscientific theoryā€ is backed up by hundreds or thousands of data-filled scientific reports.
You need a research library or subscriptions to access much of this literature, although more and more is available on line. A good starting point would be to read a text book to get an overview, before reading more technical data-filled articles. Just because you havenā€™t done a literature search does not mean that the scientific evidence (including much quantitative data) does not exist. What you dismiss as conjecture is often based on great volumes of data that you have missed or ignored.

Steven Goddard
February 5, 2009 11:39 pm

Here is a summary which hopefully end all of the ridiculous claims that have been made on this thread.
Limestone formation – sequesters CO2 and increases the amount of H+ (i.e. increases acidity)
2CO2 + 2H2O -> 2H2CO3
2H2CO3 -> 2HCO3- + 2H+
Ca++ + 2HCO3- -> CaCO3 + CO2 + H2O
Limestone dissolution – releases CO2 and reduces the amount of H+ (i.e decreases acidity)
CaCO3 + CO2 + H2O -> Ca++ + 2HCO3-
2HCO3- + 2H+ -> 2H2CO3
2H2CO3 -> 2CO2 + 2H2O
This shows how the ocean pH is buffered. As acidity increases, limestone dissolves, releasing CO2, removing H++, and increasing pH.
I tried this out in a beaker last night. I put some pure optical calcite (CaCO3) in vinegar. It released lots of CO2 bubbles, until enough of the H+ was removed to bring the pH up to a point where the dissolution stopped. (More CO2, higher pH.) This is why it is extremely difficult to lower the ocean pH, and why you can’t make the oceans chemically absorb a lot more CO2. There are billions of tons of CaCO3 in the ocean which buffer the system.

JamesG
February 6, 2009 5:49 am

Bill D
You just demonstrated another trait common to AGW theorists, viz:
3) Ignore the substantive argument in order to pick on a single word or phrase and pedantically debate it’s meaning.
Yes, while some theories are indeed backed up by data, many more are not. And this particular one – that the coral die-off is largely due to CO2 – has no real foundation. In place of data we have biased opinion and illogical thought processes.
Ok, coral exists in a narrow temperature range, so of course it’s perfectly valid to say that higher temperatures will kill some coral. Yes you can show that in experiments. But that is only half of an argument. The remaining half is that other areas that were previously too cold should now produce more coral, as indeed the scientists I referred to in the Nat Geo reference above have clearly said. All things being equal, warmer seas should therefore produce slightly more coral, not less. Any die-off from a tiny rise in tropical sea temperatures, which as it happens, stopped 5 years ago according to the latest, most-advanced instruments, just does not explain the coral die-off.
Conversely, the massive exodus of people to coastal regions in recent years (20% per year in the USA and many parts of Asia) explains it perfectly. Hence also the reason why Cuba is relatively unaffected by coral die-off (excepting of course in the 3% of it’s coast which is heavily populated).
None of this is too difficult to work out – and many scientists are saying it too but their voices aren’t heard above the activist din until they say something like “of course global warming is very important too”. I suspect that if you link your research to CO2, and even better if you have a catastrophic prediction, then you extend your chances of getting more funding. This is likely the only real positive feedback loop in the whole charade.

Steven Goddard
February 6, 2009 7:38 am

To make it even simpler. Almost all of the carbon sequestered in limestone (CaCO3) started out as CO2 in the atmosphere. There are huge volumes of limestone in the crust of the earth, making up nearly 10% of all sediments. The formation of these limestones has removed massive amounts of CO2 from the atmosphere over time.
These facts should be painfully obvious to anyone calling themselves a scientist. It is well known that cement manufacture returns sequestered carbon to the atmosphere, and there are numerous theories floating around about how subduction of limestones into volcanoes has caused spikes of CO2 in the past.
(Typo in my previous post – should read “H+” not “H++” )

gary gulrud
February 6, 2009 7:54 am

“CaCO3 cannot simultaneously sequester and produce CO2 upon reaction with CO2.”
Misplaced in this presentation is that one balanced equation for a fluence between the atmosphere and the geologic leg of the Carbon Cycle is somehow exhaustive. A mindlessly simplistic notion.
In fact, the weathering of exposed calcite is predominantly, by many orders of magnitude, a return of CO2 to the oceans. Any combination of direct fluences with the atmosphere is a bit player.

February 6, 2009 9:39 am

Steven Goddard (23:39:15) :
Here is a summary which hopefully end all of the ridiculous claims that have been made on this thread.

No it doesn’t because it is itself a ridiculous claim!
Limestone formation – sequesters CO2 and increases the amount of H+ (i.e. increases acidity)
2CO2 + 2H2O -> 2H2CO3
2H2CO3 -> 2HCO3- + 2H+
Ca++ + 2HCO3- -> CaCO3 + CO2 + H2O
Limestone dissolution – releases CO2 and reduces the amount of H+ (i.e decreases acidity)
CaCO3 + CO2 + H2O -> Ca++ + 2HCO3-
2HCO3- + 2H+ -> 2H2CO3
2H2CO3 -> 2CO2 + 2H2O
This shows how the ocean pH is buffered. As acidity increases, limestone dissolves, releasing CO2, removing H++, and increasing pH.

No it doesn’t because you’re not talking about seawater, any discussion of which has to include alkalinity!
I tried this out in a beaker last night. I put some pure optical calcite (CaCO3) in vinegar. It released lots of CO2 bubbles, until enough of the H+ was removed to bring the pH up to a point where the dissolution stopped. (More CO2, higher pH.) This is why it is extremely difficult to lower the ocean pH, and why you canā€™t make the oceans chemically absorb a lot more CO2. There are billions of tons of CaCO3 in the ocean which buffer the system.
And when it starts raining acetic acid (pKa ~4.75, pH vinegar ~2.4) we should worry about that! However, since we’re discussing rain with CO2 dissolved in it (pH ~5.6) falling on the ocean your ‘bait and switch’ tactic should be ignored.
‘A little knowledge is a dangerous thing’ and on this subject Steve you only have a little knowledge!

Simon Evans
February 6, 2009 9:54 am

Steven Goddard (09:04:15) :
Simon Evans,
Think about your last post.
The IPCC is claiming a much accelerated rate of acidification over the remainder of the century. How can CO2 absorption be slowing down and accelerating at the same time?

Of course it can’t be, but I think you are making an oversimplified assumption that the rate of acidification is linearly related to the rate of absorption.
The relative proportion of the three forms of DIC (CO2, HCO3/ā€“ and CO3/2ā€“) reflects the pH of seawater and maintains it within relatively narrow limits. This
DIC operates as a natural buffer to the addition of hydrogen ionsā€”this is called the ā€˜carbonate bufferā€™. If an acid (such as CO2) is added to seawater, the additional hydrogen ions react with carbonate (CO3/2ā€“) ions and convert them to bicarbonate (HCO3/ā€“). This reduces the concentration of hydrogen ions (the acidity) such that the change in pH is much less than would otherwise be expected (Annex 1).
When atmospheric CO2 dissolves in seawater, the oceans increase in acidity but, because of the carbonate buffer, the resultant solution is still slightly alkaline.
The capacity of the buffer to restrict pH changes diminishes as increased amounts of CO2 are absorbed by the oceans. This is because when CO2 dissolves, the chemical processes that take place reduces some carbonate ions, which are required for the ocean pH buffer (Annex 1).
(my bold)
http://royalsociety.org/displaypagedoc.asp?id=13314
Secondly, as I have pointed out repeatedly, the existence of La Nina is proof of the rapid interchange of deep and shallow water in the Pacific. Where do you think the cold water came from?
Well the cold water self-evidently didn’t come from somewhere that had previously been instantaneously mixed! Moreover, the deeper water welling up is richer in CO2 (organic matter having decomposed as it sinks), so the effect of that circulation is to decrease the pH of near-surface water. Furthermore, this circulation does not extend to the deep ocean sea bed.
Given that CO2 enters the oceans by exchange across the airā€“sea interface, it follows that analysis of the distribution of CO2 uptake show highest values (and
therefore the greatest pH change), in near-surface waters. As it takes many centuries for the downward mixing of CO2, little of the CO2 derived from human
activities has yet reached the deep oceans. When averaged for the oceans globally, about 30% of the anthropogenic CO2 is found at depths shallower than
200 m, with 50% at depths less than 400 m, leading to the conclusion that most of the CO2 that has entered the oceans as a result of human activity still resides in
relatively shallow waters.
(Ibid.)
You may take the view that complete ocean mixing is effectively instantaneous whilst oceanographers tell us it takes tens of thousands of years. You view has radical implications way beyond ocean acidification, of course, since we would need to completely reconsider all modelling of the oceans. You might like to consider the fact that your view of such rapid mixing implies that the oceans have already ‘warmed through’ far more than has been thought. You can’t have rapid chemical mixing of the entire ocean by means of circulation, as you suggest, without having rapid thermal mixing. So perhaps, Steven, you might ‘think about your last post(s)!

Steven Goddard
February 6, 2009 10:05 am

Phil,
It is astonishing to me that you continue this. The entire premise of the BBC claim is that “acidification” of the ocean to a pH of 7.8 or so will lead to dissolution of carbonate shells. You have completely lost track of that and are now arguing that “5.6 pH rainwater” can not dissolve calcite. You are carelessly arguing that the BBC is wrong.
But even worse is your ridiculous claim that rainwater can’t dissolve limestone. Of course it can – that is how limestone caverns form. It will not dissolve calcite as fast as vinegar, but the process is the same. Rainwater dissolves all kinds of rocks. That is how the minerals got in the ocean, and what makes mountains erode to the sea.
BTW – Rainwater is pH 5.2 or lower. Please stop the FUD. You have no idea what you are talking about and are continuing to make a mockery of science.

HasItBeen4YearsYet?
February 6, 2009 10:53 am

@ Phil. (09:57:57) :
“The absorption of CO2 depends on the Revelle factor of the sea water.”
The absorption of CO2 depends on ocean chemistry that the dimensionless Revelle factor (buffer factor) facilitates calculating in the range under consideration. It’s just an engineering type of shorthand to account for complex processes that one doesn’t want to have to recalculate each time to solve a problem, like the Prandtl number in fluid dynamics.
In any case, please note that Roger Revelle (of the Revelle and Suess, 1957 paper that intrduced the concept of the Revelle factor), Gore’s “mentor,” says that Gore is full of it (not in such colorful language, but in words to the same effect).
http://motls.blogspot.com/2007/04/gores-guru-dr-roger-revelle-disagreed.html
Please read the reference given for what Revelle says, here…
http://www.nationalpost.com/story.html?id=58e0c50c-1631-46ca-8719-778c0973526e
It’s from the series “The Deniers” I referenced in a comment above, and in it he lists some of the benefits that elevated CO2 can have for the planet.
Thanks for bringing that into the discussion.

February 6, 2009 11:02 am

Steven Goddard (10:05:27) :
Phil,
It is astonishing to me that you continue this. The entire premise of the BBC claim is that ā€œacidificationā€ of the ocean to a pH of 7.8 or so will lead to dissolution of carbonate shells. You have completely lost track of that and are now arguing that ā€œ5.6 pH rainwaterā€ can not dissolve calcite. You are carelessly arguing that the BBC is wrong.
But even worse is your ridiculous claim that rainwater canā€™t dissolve limestone. Of course it can – that is how limestone caverns form. It will not dissolve calcite as fast as vinegar, but the process is the same. Rainwater dissolves all kinds of rocks. That is how the minerals got in the ocean, and what makes mountains erode to the sea.
BTW – Rainwater is pH 5.2 or lower. Please stop the FUD. You have no idea what you are talking about and are continuing to make a mockery of science.

It’s you who is ‘making a mockery of science’ with your ridiculous post comparing the effect of adding vinegar to CaCO3 with adding a CO2 solution to seawater! You don’t know what you’re talking about and you continue to ‘bait and switch’ when cornered. You have zero credibility on this subject. You post your schoolboy science up against PhDs in the subject with the arrogance of a true believer!

gary gulrud
February 6, 2009 11:21 am

“ā€˜A little knowledge is a dangerous thingā€™ and on this subject Steve you have a little knowledge!”
And you have not attempted to demonstrate this opinion as fact. All I see is bluster, no content reasoning from assumptions to conclusions employing facts in the public view.
Like I said above, my sisters, at UW-Madison were required to pass Organic chemistry for degrees in Interior Design.
I’ve seen no evidence of similar rigor in your background over the past couple of weeks. “Absence of evidence does not guarantee evidence of absence”, but the scales are sickenly tilted.

Bill D
February 6, 2009 11:38 am

JamesG (05:49:14) :
Bill D
You just demonstrated another trait common to AGW theorists, viz:
3) Ignore the substantive argument in order to pick on a single word or phrase and pedantically debate itā€™s meaning.
Yes, while some theories are indeed backed up by data, many more are not. And this particular one – that the coral die-off is largely due to CO2 – has no real foundation. In place of data we have biased opinion and illogical thought processes.
James:–first, I am hardly an AGW theorist, as all of my scientific publications are based on lab and field experimentsl and this research mainly deals with lake food chains, and population studies. My research has a very strong emphasis on collecting data to test hypotheses. I find that you and some others on this blog have the trait of ignoring vast amounts of the scientific literature, most of which is based on experiments and hard data.
Second, the coral literature shows that most of the die-offs have been closely tied to high extreme temperatures. I agree that acidification has only recently become an issue and that it is not the main cause for coral die offs and extinction risks. Thus, I agree that most of the die offs have been due to sea warming, rather than acidification. Scientists who study the effect of warming on corals are concerned about climate, but their research does not depende on the cause of the warming, only that it has occurred and that corals are still at risk. Most scientists are not confident that the warming of the last few decades will suddenly reverse, although it would be great if this were true.
The extent of acidification is relatively easy to predict if we can predict atmopheric CO2. Numerous experiments have already confirmed that corals are harmed by decreases in sea water pH. I also agree that eutrophication and other pollution problems associated with human populations are also harmful to corals. However, when you look at georgraphic patterns coral die offs in the Carribian, Indian and Pacific Oceans, it is easy to see that the pattern is not caused by local human populations. In fact, during the last 20 years when the coral die offs have become more severe, human pollution draining into ocean waters has stabilized or declined.

SteveSadlov
February 6, 2009 12:19 pm

More speculation by Bill D. “The models predict that XXXXXX” – run for the hills!

maksimovich
February 6, 2009 1:15 pm

Bill D (11:38:31)
“The extent of acidification is relatively easy to predict if we can predict atmopheric CO2. Numerous experiments have already confirmed that corals are harmed by decreases in sea water pH. I also agree that eutrophication and other pollution problems associated with human populations are also harmful to corals. However, when you look at georgraphic patterns coral die offs in the Carribian, Indian and Pacific Oceans, it is easy to see that the pattern is not caused by local human populations. In fact, during the last 20 years when the coral die offs have become more severe, human pollution draining into ocean waters has stabilized or declined.”
Lets look at the science here then.
UV Exposure of Coral Assemblages in
the Florida Keys
Richard G. Zepp
Bleaching, through interactions with other factors such as sedimentation, pollution, and bacterial infection, can contribute to the destruction of large areas of a reef with limited recovery, and it may be induced by a variety of stressors ranging from exposure to unusually warm temperatures, salinity, and solar radiation. Recent research has implicated both the UVR (280 ā€“ 400 nm) and PAR (400-700 nm) components of solar radiation in various responses of coral reefs to global change. Changes in solar UV reaching the coral reefs have been caused by human alterations of atmospheric composition such as depletion of the ozone layer. In addition, changes in the composition of the water over the reefs can have important effects on the penetration of UV and visible light to the reef surface. Such changes can be caused by shifts in runoff of UV-absorbing substances from land, clarification of the water under doldrum conditions associated with global warming and changes in organisms that live near coral reefs that produce sunlight-absorbing substances. This report provides a review of past work that has been conducted on light exposure of coral reefs, in particular in the UV region. The report then describes a case study of factors that are affecting UV exposure of the coral reefs in the Florida Keys. The intended audience of this report is coral ecologists, optical oceanographers and managers and EPA environmental scientists and ecologists who must routinely analyze and estimate stressors for ecological or human health exposure assessments.
Abstract
Recent studies have indicated that solar radiation can be a significant stressor of coral assemblages in tropical and subtropical marine environments. Here the scientific literature related to the interactions of solar radiation with coral reefs is reviewed, with emphasis on harmful effects of solar UV radiation (UVR). Results of a case study of coralsā€™ UV exposure in the Florida Keys also are presented in the report. UV exposure was quantified using diffuse attenuation coefficients that were determined using downwelling vertical profiles of UV and visible radiation from sites located at the Upper, Middle and Lower Keys and the Dry Tortugas. For comparison, absorption and fluorescence spectra of the filtered water samples from these sites were measured. Absorption and diffuse attenuation coefficients were highly correlated in the UV-B (290-315 nm) spectral region and ratios of absorption to diffuse attenuation coefficients were > 0.9 throughout this spectral region. Absorption coefficients in the 300 to 500-nm spectral region could be closely described by a nonlinear exponential function. These results indicated that the penetration of solar UV into waters over the coral reefs in the Florida Keys is controlled by the chromophoric component of dissolved organic matter (CDOM) in the water. Analyses of the dependence of underwater UV irradiance on changes in atmospheric ozone or in the UV attenuation coefficients of the water over the reefs indicate that: (1) the dependence on ozone or UV attenuation coefficients can be quantified using radiation amplification factors (RAF); RAFs can be computed using a power relationship for direct UV damage to DNA or for other UV damage to the photosynthetic system of the zooxanthellae associated with corals; (3) UV damage of both types is more sensitive to changes in water UV attenuation coefficients than total ozone, especially damage to the photosynthetic system; (4) RAFs for direct DNA damage to corals caused by changes in ozone are reduced by UV light attenuation in the waters overlying the reefs.
http://www.epa.gov/AthensR/publications/reports/Zepp600R03095UVExposureCoral.pdf
So simply we can assertain that changes in water clarity are the primary mechanism for coral bleaching.

February 6, 2009 1:56 pm

gary gulrud (11:21:06) :
ā€œā€˜A little knowledge is a dangerous thingā€™ and on this subject Steve you have a little knowledge!ā€
And you have not attempted to demonstrate this opinion as fact. All I see is bluster, no content reasoning from assumptions to conclusions employing facts in the public view.

On the contrary it is Steve who continually blustered in the face of evidence and references from Chris J. and me.
Like I said above, my sisters, at UW-Madison were required to pass Organic chemistry for degrees in Interior Design.
Iā€™ve seen no evidence of similar rigor in your background over the past couple of weeks. ā€œAbsence of evidence does not guarantee evidence of absenceā€, but the scales are sickenly tilted.

Only by your bias. In fact a former grad student and former post doc from my lab of mine are now professors at UW-M although your sisters are unlikely to have come across them considering their major.

Steven Goddard
February 6, 2009 4:34 pm

Phil,
Please tell us how limestone caverns form, if you believe it is not due to rainwater dissolution.
If what you say about your background is true, it is terribly sad that your university keeps a professor who is [snip – no ad homs – Anthony]

Editor
February 6, 2009 6:46 pm

Steven Goddard (10:05:27) :

Phil,
It is astonishing to me that you … now arguing that ā€œ5.6 pH rainwaterā€ can not dissolve calcite.
BTW – Rainwater is pH 5.2 or lower. Please stop the FUD. You have no idea what you are talking about and are continuing to make a mockery of science.

From decades old memory before acid rain became all the rage, I recall that that rainwater was 5.7. Perhaps extra CO2, NOx, and SO2 have brought the pH of typical rain down to 5.2. I’ve heard of acid rain in the pH 3-4 range, so 5.2 would be an easy achievement.
Poking around with Google, I see a lot of 5.6 and 5.7. The closest thing to real science is http://www.treesearch.fs.fed.us/pubs/11066 and it refers to a cooling tower changing local rain pH from 3.4 to 4.6 to a range of 4.0 to 4.8. This was in 1974 at the 710 MW Chalk Point power plant in southern Maryland, prime acid rain dumping ground I would think.

February 6, 2009 8:15 pm

Steven Goddard (16:34:28) :
Phil,
Please tell us how limestone caverns form, if you believe it is not due to rainwater dissolution.

Why, what possible relevance is it to what happens in seawater? Chris J. and I have been trying to explain that to you but you just won’t listen. It’s way more complicated than you attempt to present it, for example a change in seawater composition to pH 8.0, alkalinity 2 mequ/l, salinity 33 0/00, temperature 20ĀŗC, and calcium 10% low from nominal would put aragonite at the verge of dissolution.
When you discussed this reaction:
Ca2+ + 2 HCO3- ā†’ CaCO3 + CO2 + H2O
you stated that during CaCO3 precipitation CO2 is liberated. However, in seawater your conclusion that [CO2] in solution is increased by one mole per mole CaCO3 ‘sequestered’ is incorrect. The correct analysis takes into account that of TCO2 and TA decrease in the ratio 1:2 and the buffer capacity of seawater. So the seawater gets more acidic because the decrease in alkalinity outweighs that of total carbon and [CO2] increases. At surface ocean conditions (TCO2=2000 Ī¼mol kg-1, pH=8.2, T=15Ā°C, S=35), [CO2] increases by only ~0.03 Ī¼mol per Ī¼mol CaCO3 precipitated.
Note that you have been abusive to both Chris J. and me.

Steven Goddard
February 6, 2009 8:59 pm

Ric,
I took the number of 5.2 from Wikipedia Clean or unpolluted rain has a slightly acidic pH of about 5.2
It doesn’t make any difference though if it is 5.2 or 5.5, the level of acidity only affects the rate at which the calcium carbonate dissolves. A good read from the University of Waterloo.
http://www.science.uwaterloo.ca/~cchieh/cact/applychem/waternatural.html
“The solubility increases as the pH decrease (increase acidity). This is compounded when the water is saturated with carbon dioxide, CO2. Saturated CO2 solution contains carbonic acid …. Rainwater is saturated with CO2, and it dissolves limestones. When CO2 is lost due to temperature changes or escaping from water drops, the reverse reaction takes place. The solid formed, however, may be a less stable phase called aragonite, which has the same chemical formula as, but a different crystal structure than that of calcite.”

Chris J
February 6, 2009 10:46 pm

@ Steven Goddard,
Steven, your incapacity to grasp even the basics of carbonate chemistry here is getting very old. Youā€™re wrong again (see below).

ā€œHere is a summary which hopefully end all of the ridiculous claims that have been made on this thread.
Limestone formation – sequesters CO2 and increases the amount of H+ (i.e. increases acidity)
2CO2 + 2H2O -> 2H2CO3
2H2CO3 -> 2HCO3- + 2H+
Ca++ + 2HCO3- -> CaCO3 + CO2 + H2Oā€
Steven, you produced 2H+ in your second equation and didnā€™t include them in the third (overall) equation. Have we just demonstrated that matter CAN be created and destroyed? (no, of course not)
The way youā€™ve written the equation we get the removal of 1 unit of C from solution and no change in alkalinity, which is incorrect. In reality the precipitation of CaCO3 removes 1 unit of C from solution and 2 units of alkalinity.
Recall that TCO2 = CO2* + HCO3- + CO3=
Ac = HCO3- + 2CO3- + OH- – H+
The correctly written equation is:
Ca++ + 2HCO3- = CaCO3 + 2H+ + CO2 + H2O
For a given change in TCO2 and Ac the corresponding concentrations for all DIC species (and pH) are easily calculated. See Stumm and Morgan, 1996, Lewis and Wallace 1998, Millero, 2006, etc. for discussions of how to calculate the entire system from TCO2 and Ac (and other parameters).
As you can readily see in any of these, precipitating CaCO3 from solution results in an INCREASE in dissolved CO2.
Letā€™s talk in hard numbers. Here are some numbers for you: A solution initially has 1000 umol/kg TCO2 and 1000 ueq/kg Ac (@ 25 C, 1 atm). 50 umol/kg worth of CaCO3 precipitates so as to reduce Ac by 100 ueq/kg, and TCO2 by 50 umol/kg. The concentration of dissolved CO2 in the solution goes way, way up:
1000 umol/kg TCO2, 1000 ueq/kg Ac => [CO2] = 11.10 umol/kg, pCO2 = 327 uatm
950 umol/kg TCO2, 900 ueq/kg Ac => [CO2] = 51.99 umol/kg, pCO2 = 1531 uatm
The precipitation of CaCO3 here INCREASES [CO2] by 468%!
These calculations done as per Lewis and Wallace, 1998.

ā€œLimestone dissolution – releases CO2 and reduces the amount of H+ (i.e decreases acidity)
CaCO3 + CO2 + H2O -> Ca++ + 2HCO3-
2HCO3- + 2H+ -> 2H2CO3
2H2CO3 -> 2CO2 + 2H2Oā€
Wrong again. This is the reverse of the above reactions:
950 umol/kg TCO2, 900 ueq/kg Ac => [CO2] = 51.99 umol/kg, pCO2 = 1531 uatm
1000 umol/kg TCO2, 1000 ueq/kg Ac => [CO2] = 11.10 umol/kg, pCO2 = 327 uatm
The dissolution of CaCO3 here REDUCES the [CO2] by 468%!

ā€œThis shows how the ocean pH is buffered. As acidity increases, limestone dissolves, releasing CO2, removing H++, and increasing pH.ā€
No, this shows that Steven has no understanding of the most basic aspects of carbonate chemistry. Honest to goodness Stevenā€”they teach this stuff to undergraduates. How do you not understand this?

ā€œI tried this out in a beaker last night. I put some pure optical calcite (CaCO3) in vinegar. It released lots of CO2 bubbles, until enough of the H+ was removed to bring the pH up to a point where the dissolution stopped.ā€
And acetic acid is not the same thing as carbonic acid Steven! When you add acetic acid to CaCO3 the H+ from the acetic acid is neutralized by CO3= to produce HCO3- and CO2, while itā€™s conjugate base (acetate) accumulates. When you add CO2 to CaCO3 the dissociation of H2CO3 into H+ and HCO3- increases the HCO3- concentration while the H+ is neutralized by CO3= to produce HCO3-. The dissolution of CaCO3 REDUCES the concentration of dissolved CO2 because it consumes CO2 from the solution!
Do the same experiment with some CaCO3 and CO2 in a closed system. Over time the CaCO3 dissolves, consuming CO2, just as above.

ā€œ(More CO2, higher pH.) This is why it is extremely difficult to lower the ocean pH, and why you canā€™t make the oceans chemically absorb a lot more CO2. There are billions of tons of CaCO3 in the ocean which buffer the system.ā€
Wrong yet again Steven. The timescale necessary for CaCO3 and silicates on land to dissolve and reestablish a similar saturation state and CCD in the ocean is on the order of 100,000 yrs, as you can see here: Archer et al., 1998; Archer, 2005; Andersson et al., 2003; Zachos et al., 2005.
Chris

Chris J
February 6, 2009 10:51 pm

@ Steven Goddard,
Steven, your incapacity to grasp even the basics of carbonate chemistry here is getting very old. Youā€™re wrong again (see below).
ā€œHere is a summary which hopefully end all of the ridiculous claims that have been made on this thread.
Limestone formation – sequesters CO2 and increases the amount of H+ (i.e. increases acidity)
2CO2 + 2H2O -> 2H2CO3
2H2CO3 -> 2HCO3- + 2H+
Ca++ + 2HCO3- -> CaCO3 + CO2 + H2Oā€

Steven, you produced 2H+ in your second equation and didnā€™t include them in the third (overall) equation. Have we just demonstrated that matter CAN be created and destroyed? (no, of course not)
The way youā€™ve written the equation we get the removal of 1 unit of C from solution and no change in alkalinity, which is incorrect. In reality the precipitation of CaCO3 removes 1 unit of C from solution and 2 units of alkalinity.
Recall that TCO2 = CO2* + HCO3- + CO3=
Ac = HCO3- + 2CO3- + OH- – H+
The correctly written equation is:
Ca++ + 2HCO3- = CaCO3 + 2H+ + CO2 + H2O
For a given change in TCO2 and Ac the corresponding concentrations for all DIC species (and pH) are easily calculated. See Stumm and Morgan, 1996, Lewis and Wallace 1998, Millero, 2006, etc. for discussions of how to calculate the entire system from TCO2 and Ac (and other parameters).
As you can readily see in any of these, precipitating CaCO3 from solution results in an INCREASE in dissolved CO2.
Letā€™s talk in hard numbers. Here are some numbers for you: A solution initially has 1000 umol/kg TCO2 and 1000 ueq/kg Ac (@ 25 C, 1 atm). 50 umol/kg worth of CaCO3 precipitates so as to reduce Ac by 100 ueq/kg, and TCO2 by 50 umol/kg. The concentration of dissolved CO2 in the solution goes way, way up:
1000 umol/kg TCO2, 1000 ueq/kg Ac => [CO2] = 11.10 umol/kg, pCO2 = 327 uatm
950 umol/kg TCO2, 900 ueq/kg Ac => [CO2] = 51.99 umol/kg, pCO2 = 1531 uatm
The precipitation of CaCO3 here INCREASES [CO2] by 468%!
These calculations done as per Lewis and Wallace, 1998.
ā€œLimestone dissolution – releases CO2 and reduces the amount of H+ (i.e decreases acidity)
CaCO3 + CO2 + H2O -> Ca++ + 2HCO3-
2HCO3- + 2H+ -> 2H2CO3
2H2CO3 -> 2CO2 + 2H2Oā€

Wrong again. This is the reverse of the above reactions:
950 umol/kg TCO2, 900 ueq/kg Ac => [CO2] = 51.99 umol/kg, pCO2 = 1531 uatm
1000 umol/kg TCO2, 1000 ueq/kg Ac => [CO2] = 11.10 umol/kg, pCO2 = 327 uatm
The dissolution of CaCO3 here REDUCES the [CO2] by 468%!
ā€œThis shows how the ocean pH is buffered. As acidity increases, limestone dissolves, releasing CO2, removing H++, and increasing pH.ā€
No, this shows that Steven has no understanding of the most basic aspects of carbonate chemistry. Honest to goodness Stevenā€”they teach this stuff to undergraduates. How do you not understand this?
ā€œI tried this out in a beaker last night. I put some pure optical calcite (CaCO3) in vinegar. It released lots of CO2 bubbles, until enough of the H+ was removed to bring the pH up to a point where the dissolution stopped.ā€
And acetic acid is not the same thing as carbonic acid Steven! When you add acetic acid to CaCO3 the H+ from the acetic acid is neutralized by CO3= to produce HCO3- and CO2, while itā€™s conjugate base (acetate) accumulates. When you add CO2 to CaCO3 the dissociation of H2CO3 into H+ and HCO3- increases the HCO3- concentration while the H+ is neutralized by CO3= to produce HCO3-. The dissolution of CaCO3 REDUCES the concentration of dissolved CO2 because it consumes CO2 from the solution!
Do the same experiment with some CaCO3 and CO2 in a closed system. Over time the CaCO3 dissolves, consuming CO2, just as above.
ā€œ(More CO2, higher pH.) This is why it is extremely difficult to lower the ocean pH, and why you canā€™t make the oceans chemically absorb a lot more CO2. There are billions of tons of CaCO3 in the ocean which buffer the system.ā€
Wrong yet again Steven. The timescale necessary for CaCO3 and silicates on land to dissolve and reestablish a similar saturation state and CCD in the ocean is on the order of 100,000 yrs, as you can see here: Archer et al., 1998; Archer, 2005; Andersson et al., 2003; Zachos et al., 2005.
Chris
Ack, I messed the font up in the above post. Can a mod please delete when they have a chanceā€”this post is the same, but (hopefully) fixed.

Chris J
February 6, 2009 11:02 pm

@ Steven Goddard,
Also Steven, if the ocean is well mixed, as you argue, and CaCO3 as calcite and aragonite very quickly dissolve to neutralize the addition of CO2, due explain why the surface ocean is predominately supersaturated with respect to both by a substantial degree (5x+ for calcite in the tropics, 3x+ for aragonite in the tropics) and understaturated in the deep see (calcite satutration horizon ~4500 m in the Atlantic, <700 m in the Pacific; aragonite saturation horizon ~2500 m in the Atlantic, < 500 m in the Pacific).
If what you say is true and the ocean very quickly comes to equilibrium with calcite/aragonite upon perterbation (e.g., addition of CO2) then why is most of the ocean out of equilibrium?
Chris

Steven Goddard
February 7, 2009 5:42 am

Chris J,
It continues to astonish me that you come back and push the same nonsensical points over and over again. Perhaps we need to go back to the basics, though it is becoming apparent that you are not interested in thinking this through or coming up with a sensible answer.
Since the early days of the planet’s formation, CO2 and H20 has been released from volcanoes. If not for the process of limestone formation, we would have a very different atmosphere, with a high concentration of CO2. This obvious fact alone should make you realize that you are wrong.
Rainwater is acidic because of this equation.
2CO2 + 2H2O -> 2H2CO3
Acid rainwater dissolves silicate rocks, which moves Ca++ ions into the ocean, where they combine with CO2 to form limestones. That is why earth has a low level of CO2. CO2 is sequestered in limestones. Every geologist and geochemist who has studied this problem for the last 100 years or so has come to the same conclusion. This is not under any dispute. You bury yourself in equations that you misinterpret, and come to nonsensical conclusions.
There is nothing missing from my equations. The Ca++ obviously comes from the dissolved silicate rocks I just described. Do you need to have every detail spelled out for you?
2CO2 + 2H2O -> 2H2CO3
2H2CO3 -> 2HCO3- + 2H+
Ca++ + 2HCO3- -> CaCO3 + CO2 + H2O

Steven Goddard
February 7, 2009 5:54 am

Furthermore, when you dissolve limestone you reduce acidity and release CO2. Take a piece of limestone and stick it in acid. The limestone visibly releases CO2 and neutralizes the acid – causing the CO2 bubbling to stop over time. Every primary school science student has seen this in their classroom, or at least used to when children were still being taught science. The fact that anyone claiming to be a scientist would attempt to dispute this, leaves me stunned.
CaCO3 + CO2 + H2O -> Ca++ + 2HCO3-
2HCO3- + 2H+ -> 2H2CO3
2H2CO3 -> 2CO2 + 2H2O

Steven Goddard
February 7, 2009 6:14 am

Chris,
Again, it astonishes me that you ask why the tropics are saturated and the deep sea undersaturated. If you had any basic understanding of the topic you would be aware that CO2 and CaCO3 solubility in water is lower at higher temperatures. That is why ice cores show higher atmospheric CO2 following planetary temperature trends. As the oceans warm, they release CO2 and precipitate limestone. When they cool, they absorb CO2 and potentially dissolve limestone. It is also why warm beer bubbles over when you open the bottle.
Calcite exhibits an unusual characteristic called retrograde solubility in which it becomes less soluble in water as the temperature increases.
http://en.wikipedia.org/wiki/Limestone
You are attempting to isolate small equations as part of a “closed system,” ignoring the fact that we are talking about a much larger system which includes the earth and sun. This conversation is helping me understand how there could be so much junk science floating around the world of AGW.

Editor
February 7, 2009 6:26 am

Phil. (20:15:56) :

Itā€™s way more complicated than you [Steve] attempt to present it,
So the seawater gets more acidic because the decrease in alkalinity outweighs that of total carbon and [CO2] increases. At surface ocean conditions (TCO2=2000 Ī¼mol kg-1, pH=8.2, T=15Ā°C, S=35), [CO2] increases by only ~0.03 Ī¼mol per Ī¼mol CaCO3 precipitated.

Going back to the “more acidic” means an acid became more so doesn’t work since seawater isn’t an acid. So, let me substitute with “less alkaline”:
So the seawater gets less alkaline because the decrease in alkalinity
outweighs that of total carbon and [CO2] increases.
Sorry, I can’t get past that first line. You have me thinking H+ and OH- dancing in a circular argument then you shift to a black (or clear) solid and [a gas in brackets]. Good thing I got sucked up by computers before getting serious about my ChemE major. What the significance of those brackets? ChrisJ used that too, also TCO2, is that shorthand for Total CO2?

Note that you have been abusive to both Chris J. and me.

I don’t care who started it, none of you are getting recess tomorrow!

Steven Goddard
February 7, 2009 7:04 am

Chris,
You asked “why is most of the ocean out of equilibrium?”
Now that is a good question. The ocean is constantly out of equilibrium because it is part of a dynamic system. Temperatures keep changing, which change solubilities. Chemicals are constantly introduced to the system through river water influx. There are biological processes affecting the chemistry. Layers of silt and mud cover the CaCO3 deposits, isolating them from sea water. Limestones are mechanically removed from the system by uplift and subduction. If not for these processes, the oceans would equilibrate quickly and limestones would cease to form.
Ocean water is not a test tube which can be analyzed in isolation of the incredibly dynamic geological, astronomical, biological and temporal environment it is contained in.
You have given me an excellent idea for an article – thanks.

Chris J
February 7, 2009 7:11 am

@Steven Goddard,
Steven, your bait and switch isnā€™t working. Several times now Iā€™ve demonstrated that youā€™re incorrect in reasoning, explained your error, and explained the correct processes to you only to have you change the subject, or pretend we were discussing something other than what we were. Unfortunately for you, you canā€™t take back what youā€™ve written, and Iā€™m growing tired of your games.

ā€œChris J,
It continues to astonish me that you come back and push the same nonsensical points over and over again. Perhaps we need to go back to the basics, though it is becoming apparent that you are not interested in thinking this through or coming up with a sensible answer.
Since the early days of the planetā€™s formation, CO2 and H20 has been released from volcanoes. If not for the process of limestone formation, we would have a very different atmosphere, with a high concentration of CO2. This obvious fact alone should make you realize that you are wrong.

Which is a completely different process than what we are and have been discussing Steven. Youā€™ve made the claim repeatedly that the precipitation of CaCO3 from solution DECREASES the CO2 concentration of that solution:

Limestone formation – sequesters CO2 and increases the amount of H+ (i.e. increases acidity)
xxxxxxxxxxxx
I have been trying to figure out what is confusing you, and think I am getting a grasp on it. It seems to derive from this equation, which has apparently lead you to the belief that that limestone formation releases CO2 (even though it obviously sequesters it.)

You further claim that the dissolution of CaCO3 INCREASES the CO2 concentration of that solution:

The dissolution process also releases CO2 to the atmosphere. Then the water becomes alkaline, and forms stalactites and stalagmites.

As Iā€™ve shown above (Chris J (22:51:06) : ) the precipitation of CaCO3 INCREASES dissolved CO2 in solution while the dissolution of CaCO3 REDUCES dissolved CO2 in solution. Your claims to the contrary are simply wrong, as Iā€™ve demonstrated above.

Rainwater is acidic because of this equation.
2CO2 + 2H2O -> 2H2CO3

Agreed, but that was never a point of contention.

Acid rainwater dissolves silicate rocks, which moves Ca++ ions into the ocean, where they combine with CO2 to form limestones.

Agreed on the source of Ca++ to the ocean, but that point is completely irrelevant since the sources of Ca++ to the ocean were never a point of contention. Calcium combines with CO3= in the ocean to form CaCO3, not with CO2.

That is why earth has a low level of CO2. CO2 is sequestered in limestones. Every geologist and geochemist who has studied this problem for the last 100 years or so has come to the same conclusion. This is not under any dispute. You bury yourself in equations that you misinterpret, and come to nonsensical conclusions.

Which is not the argument you made above, and is not the point of contention between us! You claimed that CaCO3 precipitation REDUCES solution [CO2] and CaCO3 dissolution INCREASES solution [CO2].
Here you point out that the reaction of CaO with CO2 in silicate minerals consumes CO2, which is absolutely true, but was NEVER the point we were discussing. What weā€™ve been discussing is the effect of CaCO3 precipitation and dissolution on dissolved CO2 in solution.
You canā€™t simply switch to a different topic and claim thatā€™s what you were talking about, at least not when your claims have been documented. Well, I suppose you actually can do that, but I will point it out for everyone to see, as Iā€™m now doing. Your attempted bait and switch is noted, and a failure.
<

There is nothing missing from my equations. The Ca++ obviously comes from the dissolved silicate rocks I just described. Do you need to have every detail spelled out for you?

Once again Steven, the source of Ca++ was NEVER a part of our discussion nor a point of contention, and for one very important reason: it is completely irrelevant. It doesnā€™t matter if Ca++ is derived from CaO in silicate minerals, from CaSO4, from CaCl2, or any other source. The source of Ca++ to the ocean is absolutely irrelevant to any aspect of our discussion, though your attempt at yet another bait and switch is noted.
Previously you also said in response to me:

You wrote – ā€œOnly chemical weathering of existing carbonates and silicates draws down atmospheric CO2ā€³
Quite the opposite. When acid comes in contact with carbonates, it releases CO2.

You are now claiming what I say in my quote, that the chemical weather of carbonates and silicates consumes atmospheric CO2, but in the above passage you said that the reactions have an effect on CO2 that is ā€œquite the oppositeā€ of the claim I made (which you make above) and that the interaction of CO2 with carbonates releases CO2. Hence, youā€™ve previously claimed that the dissolution of CaCO3 with CO2 INCREASES dissolved CO2, but now that Iā€™ve demolished that nonsensical position youā€™ve switched over to accepting that the weathering of silicates and carbonates with CO2 REDUCES dissolved CO2.
Youā€™ve tried to have it both ways here. Iā€™m sorry Steven, but you canā€™t have it both ways, and everyone that might be reading this can easily see through the double-speak youā€™ve attempted.

2CO2 + 2H2O -> 2H2CO3
2H2CO3 -> 2HCO3- + 2H+
Ca++ + 2HCO3- -> CaCO3 + CO2 + H2O

And at the very least Steven, learn to balance chemical equations.
The equilibrium you have here is (combining equations 1 and 3ā€”2 is intermediate to the overall rxn):
2CO2 + 2H2O + Ca++ = CaCO3 + CO2 + H2O
1 Ca++ on both sides (good so far)
2 C on both sides (no worries)
6 O on both sides (great)
4 H on the right side, but only 2 H on the left (uh-oh!)
The balanced equation is:
2CO2 + 2H2O + Ca++ = CaCO3 + 2H+ + CO2 + H2O
While you are entitled to your own opinions, you are not entitled to your own facts, and you certainly arenā€™t entitled to ignore the law of conservation of matter in your argument on chemistry (or anything else, one would suppose).
Chris

Chris J
February 7, 2009 7:37 am

@ Steven Goddard,

Furthermore, when you dissolve limestone you reduce acidity and release CO2. Take a piece of limestone and stick it in acid. The limestone visibly releases CO2 and neutralizes the acid – causing the CO2 bubbling to stop over time. Every primary school science student has seen this in their classroom, or at least used to when children were still being taught science. The fact that anyone claiming to be a scientist would attempt to dispute this, leaves me stunned.

As Iā€™ve said repeatedly Steven, that only works when you use an acid OTHER than carbonic acid since the conjugate base of the acid is allowed to build up. If you dissolve CaCO3 with CO2 you consume the CO2 in the process, resulting in reduced [CO2]. If you disagree, perform the calculation for the dissolution of CaCO3 with CO2. I want the concentrations. Iā€™ve already provided you with them, the least you can do is the same. Either put up orā€¦well, stop talking nonsense.
Do the experiment: drop some CaCO3 into a beaker and bubble in CO2. Do you get bubbles of rising CO2? (I’ll kill the suspense: no, you don’t)

CaCO3 + CO2 + H2O -> Ca++ + 2HCO3-
2HCO3- + 2H+ -> 2H2CO3
2H2CO3 -> 2CO2 + 2H2O

Steven, you just created matter! Where do the 2H+ in equation 2 come from?
You canā€™t just create and destroy protons when it suits you.
Further, these are equilibrium equations Steven. Simply because you can write an equation tells you nothing about which direction the reaction proceeds. For that you need to perform the calculation. Iā€™ve already done so above, and sure enough [CO2] decreases when CaCO3 dissolves. If you disagree, give me (and all of us) some hard numbers.
Chris

Steven Goddard
February 7, 2009 7:52 am

Chris,
I can see why you are not understanding what I am talking about. I am talking about the earth/atmosphere system as a whole, and you think we are talking about an isolated system in a test tube with no boundary conditions.
CO2 is continuously introduced and removed to/from your test tube through a variety of geological and biological processes. That is what is confusing you about conservation of mass.
You make absurd claims like “you’ve previously claimed that the dissolution of CaCO3 with CO2 INCREASES dissolved CO2” I never said anything like that. What I said is that dissolution of CaCO3 by acids releases CO2. Every science student in the world knows this.
Twisting my words and ignoring the big picture is not going to change the science nor make the oceans acidic. What do you hope to accomplish through this bizarre, disconnected academic exercise you are engaged in?

Chris J
February 7, 2009 7:54 am

@ Steven Goddard,

Chris,
Again, it astonishes me that you ask why the tropics are saturated and the deep sea undersaturated. If you had any basic understanding of the topic you would be aware that CO2 and CaCO3 solubility in water is lower at higher temperatures. That is why ice cores show higher atmospheric CO2 following planetary temperature trends. As the oceans warm, they release CO2 and precipitate limestone. When they cool, they absorb CO2 and potentially dissolve limestone. It is also why warm beer bubbles over when you open the bottle.

Thatā€™s precisely the point Steven! You claim that the ocean comes to equilibrium very quickly with respect to calcite/aragonite given changes in [CO2], therefore the ocean will be buffered against the increase in [CO2] during this century. You also observe that the shallow ocean is substantially supersaturated with calcite and aragonite while the deep sea is undersaturated.
So on the one hand, youā€™re claiming that CaCO3 will fall in equilibrium with an increase in [CO2] THIS CENTURY, yet the ocean hasnā€™t come to equilibrium with the increase in [CO2] that occurred between the last glacial maximum and the beginning of the Holocene.
So, the ocean doesnā€™t come to equilibrium in terms of calcite/aragonite saturation with a 100 uatm increase in CO2 that occurs over ~8,000 yrs, but it will come to equilibrium with a 100 (optimistically) to 500 uatm increase that occurs by the end of the century. Interesting. Please do explain your reasoning here.

Calcite exhibits an unusual characteristic called retrograde solubility in which it becomes less soluble in water as the temperature increases.
http://en.wikipedia.org/wiki/Limestone

Ha, yes Steven, I know. The decrease in CO2 solubility actually has little impact since the decrease in pKw with temperature essentially overwhelms that effect. The more important effects are on K2 for carbonic acid and the free energy.

You are attempting to isolate small equations as part of a ā€œclosed system,ā€ ignoring the fact that we are talking about a much larger system which includes the earth and sun. This conversation is helping me understand how there could be so much junk science floating around the world of AGW.

The Earth, for all practical purposes, is a closed system with regard to materials (not radiation) Steven. The C, Ca, H2O, etc. that we have here is not wafting off into space, nor being received from space, at any significant rate.
Chris

Steven Goddard
February 7, 2009 8:10 am

Chris,
Since you obviously have no training in Geology, let’s start with a simple case that you might be able to understand.
Imagine a lake with a thin layer of limestone at the bottom. If nothing else was going on, the lake would achieve chemical equilibrium internally and with the atmosphere above it.
However, that isn’t how things work in the real world. Sediment washes into the lake, which buries the limestone. (This is a classic limestone/shale interleaved sequence.) The sediment isolates the limestone from the lake water, and disrupts the chemical equilibrium. More limestone forms at the bottom, and more CO2 is absorbed from the atmosphere. It is this process which has allowed huge amounts of CO2 to be removed from the atmosphere and sequestered in limestones over the past few hundreds of millions of years.
If you don’t understand geology, you shouldn’t get involved in a geological discussion. There is a big world outside of your test tube, which does follow conservation of mass, but on a large scale.

Chris J
February 7, 2009 8:13 am

Ack, screwed up the text again. If a mod can delete the above screwed-up-text post and leave this non-screwed-up-text post it’d be appreciated!
@ Steven Goddard,

Chris,
You asked ā€œwhy is most of the ocean out of equilibrium?ā€
Now that is a good question. The ocean is constantly out of equilibrium because it is part of a dynamic system. Temperatures keep changing, which change solubilities. Chemicals are constantly introduced to the system through river water influx. There are biological processes affecting the chemistry. Layers of silt and mud cover the CaCO3 deposits, isolating them from sea water. Limestones are mechanically removed from the system by uplift and subduction. If not for these processes, the oceans would equilibrate quickly and limestones would cease to form.

Now this is one of the first reasonable things Iā€™ve seen you say. You are exactly correct that most of the ocean is out of equilibrium with respect to calcite/aragonite because of biological and geochemical processes. Were the ocean very rapidly mixed, it would eventually come to equilibrium with respect to calcite, especially in the absence of these processes and CaCO3 precipitation and dissolution would no longer take placeā€”there would be a fixed quantity of accumulated CaCO3.
Of course, CaCO3 has been accumulating in the ocean for hundreds of millions of years and began before biomineralizing organisms evolved (all abiotic and/or biologically induced, like in stomatolites).
The ocean, top to bottom, has been out of equilibrium with respect to calcite for at least this period of time. The only way this is possible is if the processes that set the ocean out of equilibrium (all geochemical/physical in the early oceanā€”biological and geochemical/physical today) operate significantly FASTER than the rate of mixing. If they did not, the ocean would come and would have come to equilibrium.
Iā€™m glad weā€™re in agreement here.

Ocean water is not a test tube which can be analyzed in isolation of the incredibly dynamic geological, astronomical, biological and temporal environment it is contained in.

Ah, I see. The ocean is too complicated to study. Well, letā€™s all toss our hands up and go home guys. It turns out we canā€™t study the ocean (or anything else, presumably) because itā€™s complicated. Ignore the decades to centuries of data. Ignore the countless verified predictions from countless subdisciplines in marine science and oceanography. No matter how accurately our predictions turn out to be when tested, the ocean is just too complicated to study.
In fact, all of science, technology, medicine, etc. is completely useless because the world is complicated. We canā€™t put the universe in a test tube, afterall, therefore we can never know anything useful about it.
If you really believe that, well, good luck to you.

>You have given me an excellent idea for an article – thanks.

>
Ha, glad I could help.
Chris

Chris J
February 7, 2009 8:16 am

In above I mean to say that “net CaCO3 precipitation and dissolution would no longer take place”.

Mary Hinge
February 7, 2009 9:21 am

JamesG (05:49:14) :
Ok, coral exists in a narrow temperature range, so of course itā€™s perfectly valid to say that higher temperatures will kill some coral. Yes you can show that in experiments. But that is only half of an argument. The remaining half is that other areas that were previously too cold should now produce more coral,…

Unfortunately this is not the case. It is not only a narrow temperature range but also a narrow range of sunlight quality. The corals being discussed here rely on symbiotic algae, and these only function effectively with adequate sunlight. Once you move away from the tropics the increased angle the sun hits the water means that the quality of sunlight penetrating se water is much reduced.

Mary Hinge
February 7, 2009 9:22 am

JamesG (05:49:14) :
Ok, coral exists in a narrow temperature range, so of course itā€™s perfectly valid to say that higher temperatures will kill some coral. Yes you can show that in experiments. But that is only half of an argument. The remaining half is that other areas that were previously too cold should now produce more coral,…

Unfortunately this is not the case. It is not only a narrow temperature range but also a narrow range of sunlight quality. The corals being discussed here rely on symbiotic algae, and these only function effectively with adequate sunlight. Once you move away from the tropics the increased angle the sun hits the water means that the quality of sunlight penetrating sea water is much reduced.

Richard Sharpe
February 7, 2009 9:50 am

Chris J (07:11:56) says:

As Iā€™ve shown above (Chris J (22:51:06) : ) the precipitation of CaCO3 INCREASES dissolved CO2 in solution while the dissolution of CaCO3 REDUCES dissolved CO2 in solution. Your claims to the contrary are simply wrong, as Iā€™ve demonstrated above.

I think I understand those words. Precipitation means that solids come out of the solution. I recall doing that in high school chemistry when we mixed that pretty blue CuSo4 or something with some thing like CaCl, although I can no longer remember what would precipitate. I think I understand words like reduces and increases and dissolution as well.
Then in the same posting you say that:

The balanced equation is:
2CO2 + 2H2O + Ca++ = CaCO3 + 2H+ + CO2 + H2O

I am confused, but I must admit to having had only one year of Chemistry in university and it was a long time ago.
However, in the equation you presented above, it would seem that if CaC03 precipitates, it does so by reducing CO2 concentration. It would seem, however, to increase H+.
I just went back and looks again, and you say:

the precipitation of CaCO3 INCREASES dissolved CO2 in solution

but your balanced equation has us starting with two and ending with one molecule of CO2 (which I can only assume is in solution).
Whatā€™s going on? Have I reversed the meanings of increase and reduce all these years? (I cut and pasted from your posting). Is there something else here I am missing?
As a side note, my wife, who is a teacher, came across a teenage male recently who had actually reversed the meanings of ā€˜trueā€™ and ā€˜falseā€™. ā€œYou are a boy!ā€ Yes, that is false! You are a baby! No, that is true.

Bill D
February 7, 2009 11:07 am

maksimovich (13:15:04) :
Bill D (11:38:31)
….
http://www.epa.gov/AthensR/publications/reports/Zepp600R03095UVExposureCoral.pdf
So simply we can assertain that changes in water clarity are the primary mechanism for coral bleaching.
Mak—here is first part of the introduction of the paper that you cited as evidence that UV light causes coral bleaching and that warming is not important. In fact, the authors states in the introduction and discussion that most of the evidence supports warming as the main factor, but my work shows that UV radiation can also be important. Interestingly, the increase in UV radiation is attributed to changes in organic chemicals that block UV light and the author of the paper that you cite attributes the increase in underwater UV light to “climate change.” The author is also very cautious about jumping to conclusions, but supports the hypothesis that climate change is likely responsible for the die offs of corals.
1.1 Coral Bleaching: Impacts of Warming and Light
Photosynthetic coral symbionts, members of the dinoflagellate genus Symbiodinium, provide both color and energy to a wide variety of coral taxa. When these symbionts (zooxanthellae), or their pigments, are expelled or lost from the host coral tissues, the white color of the coral skeleton emerges, leaving a bleached appearance. Bleaching also can involve direct degradation of the pigments in the zooxanthellae. The descriptive term ā€˜bleachingā€™ reflects a breakdown of the symbiosis. Records of coral bleaching from 1870 to the present indicate that the severity, locality, and frequency have reached unprecedented levels (D’Elia et al., 1991; Glynn, 1993) Coral bleaching may be the symptom of coral reef degradation that is most closely linked to climate change (Hoegh-Guldberg, 1999). Although bleaching has been correlated with increased temperatures, many studies have concluded that light exposure may also be implicated as a stressor producing additive or synergistic effects (Shick et al. 1996). Research on the effects of solar radiation have examined photosynthetically active radiation (PAR, 400 – 700 nm spectral range) and ultraviolet radiation (UVR). UV-B radiation (280 – 315 nm spectral range) and UV-A radiation (315 – 400 nm spectral range) are two important components of UVR.
maksimovich
I actually read the EPA study that you linked to above. In early posts I mentioned that high temperatures, reduced pH and high intensities of UV light have all be shown to adversely impact corals.
The EPA study that you cite above focused on UV light. In the introduction, the author states that most of the evidence links bleaching to high temperatures but high UV light also seems to be a factor. This study also notes that high UV light is linked to climate change, something that I was not really aware of.
Scientists know that articles need to be read completely and carefully before they are cited. An important role of scientific reviewers is to point out when articles are cited incorrectly and when important citations are left out. In this case, the conclusions of the authors directly conflicts with your conclusions. I don’t know whether this is because you did not read the paper, or you that you read the paper and assumed that no one else has or would read the paper and would notice that it does not support you conclusion.

Simon Evans
February 7, 2009 11:52 am

Steven Goddard,
As Chris J has said above, anyone who’s followed this thread will be able to figure out who has been talking nonsense, so I rather think it pointless for either of you to keep making the claim.
I wonder if you might like to respond to my relatively simple point above? If the oceans are instantaneously/very rapidly chemically mixed by circulation, as you seem to believe, then it follows that they are instantaneously/very rapidly thermally mixed, does it not? I would like to clarify whether or not you do believe in such rapid circulatory mixing, since the implications of such a belief are rather extraordinary.

Steven Goddard
February 7, 2009 12:42 pm

Simon Evans,
Look at the current map of sea surface temperatures.
http://weather.unisys.com/surface/sst_anom.html
Note the cold area of the equatorial Pacific. This cold water is the result of La Nina, and was pulled up from the deep ocean east along the thermocline along the South American coast – and then blown west by the wind. This process takes several months to years, as evidenced by the frequency of ENSO events.
There is nothing mysterious or controversial about this. How else would cold water make it to the equator?
http://en.wikipedia.org/wiki/El_Ni%C3%B1o-Southern_Oscillation
My question is – Is there any way to have a sane, rational discussion with the AGW groupies?

maksimovich
February 7, 2009 1:04 pm

Bill D (11:07:16)
“Scientists know that articles need to be read completely and carefully before they are cited.”
Indeed we do
3. Conclusions and Management Implications (PAGE 36)
This research has advanced the science of corals as it relates to UV interactions in the following ways:
! It was demonstrated that the UV exposure of coral reefs in the Florida Keys is highly variable and that this variability is linked to climate changes that are occurring over the region. The linkage stems from concurrent changes in physicochemical properties of the waters such as warmer temperatures and increased water clarity.
! We showed that the chromophoric (colored) component of dissolved organic matter (CDOM) in the water over the reefs plays a key role in controlling light exposure. Thus changes in CDOM concentrations caused by climate change and/or land-based human activities can translate into significantly altered UV exposure of coral reefs.
! We identified what may be a major pathway for the large scale impact of El NiƱo events on mass bleaching of corals. Our results suggest that stratification caused by the prolonged periods of low winds and warm temperatures that accompany El NiƱo events can result in significant increases in damaging UV radiation over the reefs. We hypothesize that this increased exposure to UV, in concert with warmer waters, places intense stress on the corals that results in extensive bleaching.
! We elucidated possible biological sources of CDOM in waters close to coral reefs. Changes in these biological sources, such as seagrasses and mangroves, caused by climate change and human activities can have long-term detrimental effects on corals by perturbing UV protective substances in the ocean water.
We also understand the textbooks
TOMMY D. DICKEY AND PAUL G. FALKOWSKI The sea 2002
Chapter 10. SOLAR ENERGY AND ITS
BIOLOGICALā€“PHYSICAL INTERACTIONS IN THE SEA
Page 402
On ecological time scales, the diel and seasonal cycles determine the number of hours of solar radiation incident on each point on the planet, and thus provide an extrinsic natural clock to which almost all organisms (including humans) have adapted. Earthā€™s radiative balance, which is absolutely essential to sustaining life, is dictated by the input of solar energy, atmospheric gas composition, and planetary albedo. These processes are inextricably coupled to the ocean by the hydrological cycle through water vapor and ice albedo feedbacks. These physical systems have coevolved and interact with biological systems. Major biogeochemical processes, such as photosynthesis and nitrogen fixation, are also coupled directly to solar radiation. Solar ultraviolet (UV) radiation can lead to alterations in genetic material, which, in turn, affects the tempo of evolution.Finally, migratory patterns and other behavioral responses in the sea are often keyed to diel, lunar, and seasonal changes in radiation.
Page 403
The interaction with and effect of solar radiation on Earthā€™s energy budget is
strongly dependent on the electromagnetic spectrum. Planetary albedo is only relevant to short-wavelength radiation; hence, all far-red radiation impinging at the top of Earthā€™s atmosphere will either be absorbed by gases in the atmospheric column or will be transmitted to the surface. Some of the short-wavelength radiation impinging on the top of the atmosphere is scattered and reflected back to space, while the majority penetrates to the surface. Over 70% of Earthā€™s surface is covered by liquid water that absorbs about 95% of incident solar irradiance. In its upper 3 m the ocean contains the equivalent heat capacity of the entire atmosphere of the planet (Peixoto and Oort, 1992).
Page 405
As in the atmosphere, the direct physical interactions between solar radiation and
the ocean are wavelength dependent. Water itself effectively absorbs all incident
infrared solar radiation (e.g., Morel and Antoine, 1994), and this direct radiative
transfer process provides roughly half of the heat to the ocean surface waters. An
example of potential interactions between solar radiation and physical and biological
processes is depicted in Fig. 10.2, where the following sequence is illustrated:
(1) forcing of the upper ocean physical condition through the input of solar radiation,
including light, heat, and indirectly momentum at the ocean surface; (2) upper
ocean physical responses, including stratification and turbulent mixing that result in
(3) phytoplankton vertical and horizontal motions, which, in turn, lead to (4) feedbacks on distributions of pigments and photosynthetic available radiation (PAR), and
(5) modulation of the upper ocean heating via phytoplankton and their associated
optical properties. The balance between primary production and grazing determine
the concentration of phytoplankton at any moment in time and both processes must
be considered in biologicalā€“physical interactions.
The interactions among these processes occur on many time and space scales.
Long-term changes (millennia to millions of years) in ocean circulation are driven
by changes in radiative forcing resulting from orbital variations, albedo feedbacks,
and continental configuration (Fig. 10.3). Short-term changes (seconds to decades)
are driven by atmospheric conditions (e.g., aerosols, cloud cover, albedo, and ozone
concentration) and thermal contrasts between continents and the oceans and from
the equator to the poles. Together, both long- and short-term variations in radiative transfer of broadband, as well as visible solar energy, determine the depth of the upper mixed layer, turbulent kinetic energy, and the vigor of large-scale oceanic circulation,which ultimately determines, on a global scale, the distribution and productivity of phytoplankton.
We can see this in simple changes in say cloud cover eg Snell and Sommerville
We also understand the evolutionary process in changes of radiative spectra ,ontological growth,attenuation and amplification of population of species.eg Hutchinson 1961
Changes to absorption and emission of nutrients are also responsive to changes in both the type and spectra of radiation, these inhibit some populations and enhance others.Indeed what we can see is the ecological communities of microflora, changing rapidly to meet their changing levels of nutrients and energy is a Belousov-Zhabotinsky reaction diffusion mechanism.
And if we use say Phytoplankton as an example Recent work by two theoretical ecologists (Huisman & Weissing, 1999; 2001),has shown that competition for resources by as few as three species can result in long-term oscillations, even in the traditionally convergent models of plankton species growth. For as few as five species, apparently chaotic behavior can emerge. Huisman and Weissing propose these phenomena as one possible new explanation of the paradox of the plankton, in which the number of co-existing plankton species far exceeds the number of limiting resources, in direct contradiction of theoretical predictions. Continuously fluctuating species levels can support more species than a steady, stable equilibrium distribution.
Their results show that external factors are not necessary to maintain non-equilibrium conditions; the inherent complexity of the “simple” model itself can be sufficient.
The publication of dubious ‘catastrophic ‘predictions for the oceans ability to maintain its biological role of atmospheric moderation are simply “creationist wastepaper” the ability of biogenic adaptability is already genetically available “banked for a rainy day so to speak”. Been there done that, got the T-shirt and the DNA! Geologicallyā€œancientā€species, which have survived large changes in ocean chemistry, are likely more resilient to predicted acidification ie they retain the evolutionary memory of ā€œpast environmental ezperiencesā€
The high proportion of duplicate genes within plant and algae genomes is indicative of a high rate of retention of duplicate genes (Lynch and Connery, 2000). Gene duplications contribute to the establishment of new gene functions, and may underlie the origin of evolutionary novelty. Duplicate genes can exist stably in a partially redundant state over a protracted evolutionary period (Moore and Purugganan, 2005). A half-life to silencing and loss of a plant gene duplicate is estimated at 23.4 million years such that remnant duplicate genes, which can be reactivated by environmental conditions to encode calcification within coccolithophores under ā€œancestralā€ conditions representative 60 Ma, appears reasonable
An indeed the half life of around 25 my is close to the Lyaponov exponent.
eg Raup, D., and Sepkoski, J., 1986, Periodic extinction of families and genera:
Science, v. 231, p. 833ā€“836.
Bottom line changes in PAR and UV and indeed all radiation are significant drivers in changes in ecosystems.

Bill D
February 7, 2009 1:46 pm

1. So simply we can assertain that changes in water clarity are the primary mechanism for coral bleaching
2. Bottom line changes in PAR and UV and indeed all radiation are significant drivers in changes in ecosystems.
maksimovich (13:04:16) :
Above are the conclusions to two of your recent posts. From my reading of the scientific literature on corals, I would be surprised if any scientists in that field would agree with your first conclusion above. Your second conclusion is much more reasonable and I can say that I agree with it. Certainly for plankton, seasonal changes in light are a big factor. Light is clearly a big issue in comparisons between ecosystems are different latitudes as well.
Interesting that you mention Jeff Huisman, who has done noteworthy experimental and theoretical research on effects of light on phytoplankton communities (as you have noted in your more recent post above). Just this week I read a revised manuscript (in review) where he is one of several co-authors. This study documnts how climate change is affecting plankton communities by altering C:N:P stoichiometry and makes predictions based on theory and data. None of the effects are catastrophic but it is interesting to see climate affecting natural communities in unexpected ways. (I’ve also published a number of articles related to C:N:P stoichiometry, although none that links to climate or eventemperature).
The take home message is that natural systems are complex and showing that one factor is important does not mean another factor is not also important. Indeed, we often see interactive effects, where, for example effects of the negative effects of increased UV light might accentuate the negative effects of warming temperature.

Simon Evans
February 7, 2009 2:18 pm

Steven Goddard (12:42:21) :
Simon Evans,
Look at the current map of sea surface temperatures.
http://weather.unisys.com/surface/sst_anom.html
Note the cold area of the equatorial Pacific. This cold water is the result of La Nina, and was pulled up from the deep ocean east along the thermocline along the South American coast – and then blown west by the wind. This process takes several months to years, as evidenced by the frequency of ENSO events.
There is nothing mysterious or controversial about this. How else would cold water make it to the equator?
http://en.wikipedia.org/wiki/El_Ni%C3%B1o-Southern_Oscillation

You have not answered my question. Further up this thread you have presumed that chemical mixing is instantaneous/very rapid throughout the oceans. Now you are saying something about ENSO, which itself affects only a part of the ocean systems (and which does not mix to the ocean bed), taking ‘several months to years’. So which is it? Is the ocean system instantaneously/very rapidly mixed as you previously claimed or is mixing a process which takes a long time? Oceanographers think that complete mixing takes tens of thousands of years, you have asserted otherwise. Now you appear to be engaging in obfuscation.
My question is – Is there any way to have a sane, rational discussion with the AGW groupies?
I see that you resort to an attempted sneer for want of any other means of defending your contradictions. That gives a very clear view of your position, Mr Goddard (if that is your name). i will not make the mistake again of giving any benefit of the doubt in your particular case.

Simon Evans
February 7, 2009 2:36 pm

[If my apparently lost comment appears then this will be repetitive – apologies if so]
REPLY: Comments with certain verbiage and links automatically end up in the WordPress spam filter, it happens -Anthony
Steven Goddard (12:42:21) :
Simon Evans,
Look at the current map of sea surface temperatures.
http://weather.unisys.com/surface/sst_anom.html
Note the cold area of the equatorial Pacific. This cold water is the result of La Nina, and was pulled up from the deep ocean east along the thermocline along the South American coast – and then blown west by the wind. This process takes several months to years, as evidenced by the frequency of ENSO events.
There is nothing mysterious or controversial about this. How else would cold water make it to the equator?
http://en.wikipedia.org/wiki/El_Ni%C3%B1o-Southern_Oscillation

As will be entirely obvious to anyone reading this thread, you have avoided answering my question, which was:
“If the oceans are instantaneously/very rapidly chemically mixed by circulation, as you seem to believe, then it follows that they are instantaneously/very rapidly thermally mixed, does it not? I would like to clarify whether or not you do believe in such rapid circulatory mixing, since the implications of such a belief are rather extraordinary.”
You can write as many posts as you wish to avoiding answering the question and the avoidance will continue to speak for itself.
I see that, following your obfuscation, you attempt a personal sneer for want of any other means of diverting from your contradictions, viz.:-
My question is – Is there any way to have a sane, rational discussion with the AGW groupies?
That also speaks for itself, and tells me everything I need to know about you, Mr Goddard (if that is your name).

Editor
February 7, 2009 2:49 pm

Mary Hinge (09:21:14) :

The corals being discussed here rely on symbiotic algae, and these only function effectively with adequate sunlight

I thought of algae while driving to the grocery store. One thing missing from this discussion is the effect on algae and coral’s algae due to an increase in dissolved CO2 and lower pH.
A couple references say more CO2 means declining CaCO3 production, but the science is far from settled. Better references welcome.
From 1999: http://www.thefreelibrary.com/Carbon+dioxide+buildup+harms+coral+reefs-a054419459
From 2008: http://www.physorg.com/news144348139.html and says in part:
“We found that coralline algae, which glue the reef together and help coral larvae settle successfully, were highly sensitive to increased CO2. These may die on reefs such as those in the southern Great Barrier Reef before year 2050,” says Dr Anthony.
On the positive side, some coral species seem able to cope with the levels of ocean acidification expected by the mid-century by enhancing their rates of photosynthesis, says team member Dr David Kline. “This is an important discovery that can buy the reef time while the nations of the world work together to stabilise CO2 emissions,” he says.

maksimovich
February 7, 2009 2:59 pm

Bill D (13:46:15) :
The take home message is that natural systems are complex and showing that one factor is important does not mean another factor is not also important. Indeed, we often see interactive effects, where, for example effects of the negative effects of increased UV light might accentuate the negative effects of warming temperature.
I would be surprised if any scientists in that field would agree with your first conclusion above.
Yes it would effect their funding .
Fortunately we have two Global United Nations Environment Programmes eg
Environmental effects of ozone depletion and its interactions with climate change: Progress report, 2008
http://www.rsc.org/Publishing/Journals/PP/article.asp?doi=b820432m
There are conflicts with the 2 expert panels in a number of areas.This raises some interesting issues, but would sidetrack from the issues here.
Let us discuss the area of UV and ecosystems and changes perceived or otherwise.
For expediency of response I will cut from some papers
The ability of biological species to adapt to adverse environments is one of the paradoxes of Ecological science.How the exclusion of some ā€œplayersā€ from theā€ marketplaceā€ will allow for smaller players to dominate the market due to enhanced adaptability.
To understand this lets pose a simple question ” Is Brown the new green in an ultraviolet world ? ”
Changes to the ozone levels and UV penetration are cyclical over the solar cycles from the 27 day rotation, the 11 year cycle ,the Gleissberg cycle and longer orbital parameters.eg Rozanov 2005
Solar variability is observed on three main time scales: solar rotation (27-day), solar cycle (11year) and the Grand Minima time scale. The magnitude of the variability progressively increases from the short to long scales. Earth’s climate responses are now found on all these scales. The most recognized are the responses to solar irradiance variations. These variations strongly depend on wavelength rising from 0.1% per solar cycle in total irradiance (mostly infrared-optical range) to 10% in UV and 100% per solar cycle in X-ray range. The variations in the total irradiance produce a small global effect. More substantial is the effect of solar UV variability on large-scale climate patterns. These patterns are naturally excited in the Earth’s atmosphere as deviations (anomalies) from its mean state.
How does the distribution of UVB, UVA, and photosynthetically active radiation vary on sensitive surfaces within the biosphere in the agricultural and forest canopies over the growing season? Plants have widely varying sensitivity to solar UV radiation. This can result in shifts in the competitive advantage of one plant species over another and consequently composition and health of both manages ecosystems.
“Daylength is the major environmental factor affecting the seasonal photosynthetic performance of Antarctic macroalgae. For example, the “season anticipation” strategy of large brown algae such as Ascoseira mirabilis and Desmarestia menziesii are based on the ability of their photosynthetic apparatus to make use of the available irradiance at increasing daylengths in late winter-spring. The seasonal development and allocation of biomass along the lamina of A. mirabilis are related to a differential physiological activity in the plant. Thus, intra-thallus differentiation in O2-based photosynthesis and carbon fixation represents a morpho-functional adaptation that optimizes conversion of radiant energy to primary productivity”
It is now known that various of the reproductive- and life history events in Antarctic macroalgae are seasonally determined: microscopic gametophytes and early stages of sporophytes in Desmarestia (Wiencke et al. 1991, 1995, 1996), Himantothallus (Wiencke & Clayton 1990) and P. antarcticus (Clayton & Wiencke 1990) grow under limited light conditions during winter, whereas growth of adult sporophytes is restricted to late winter-spring. Culture studies under simulated fluctuating Antarctic daylength demonstrated that macroalgae exhibit two different strategies to cope with the strong seasonality of the light regime in the Antarctic (Wiencke 1990a, 1990b). The so-called “season responders” are species with an opportunistic strategy growing only under optimal light conditions mainly in summer, whereas the “season anticipators”, grow and reproduce in winter and spring.
By virtue of their fine morphology, have a high content of pigments per weight unit, a high photosynthetic efficiency, very low light requirements for photosynthesis, and they are better suited to dim light conditions than adult sporophytes. This strategy ensures the completion of the life-cycle under seasonally changing light conditions. Low light requirements for growing and photosynthesizing are developed to cope with Antarctic seasonality and constitute adaptations to expand depth zonation of macroalgae.
This suggests that the microalgae have adapted to predicting not only the early spring photosynthetically active radiation, but also high spring flux of UV due to ozone loss as seen by the levels of melanin pigmentation.
Envisat has captured the first images of Sargassum from space reports the ESA. The brown kelp famous in nautical lore for entangling ships in its dense floating vegetation, has been detected from space for the first time thanks to an instrument aboard ESAā€™s environmental satellite.
The discovery was made using the MERIS maximum chlorophyll index (MCI) which provides an assessment of the amount of chlorophyll in vegetation to produce detailed images of chlorophyll per unit area. MERIS is uniquely suited for this because it provides images of above-atmosphere spectral radiance in 15 bands, including three bands at wavelengths of 665, 681 and 709 nanometres in order to measure the fluorescence emission from chlorophyll a.
Chlorophyll is the green photosynthetic compound in plants that captures energy from sunlight necessary for photosynthesis. The amount of chlorophyll present in vegetation plays an important role in determining how healthy it is. Accurately monitoring chlorophyll from space, therefore, provides a valuable tool for modelling primary productivity.
“The 709 band used by MERIS is not present on other ocean-colour sensors. It was essential to our detecting Sargassum,” Gower said. “The MCI index has allowed us to find so many interesting things, including Sargassum and Antarctic super blooms. It really gives us a new and unique view of the Earth.”
In the arctic with similar radiation properties affecting the aquatic biosphere we see similar properties in the growth function of brown alga.
ABSTRACT. The effect of artificial ultraviolet (UV) and natural solar radiation on photosynthesis, respiration and growth was investigated in 14 red, green and brown macroalgal species on Spitsbergen (Norway) during summer 1998. In June, maximum mean solar radiation at sea level was 120 W m-2 of visible (370 to 695 nm) and 15 W m-‘ of UV radiation (300 to 370 nm), and decreased gradually until the end of the summer. In spite of incident irradiance, levels were low in comparison with other latitudes, and UV radiation stress on growth of Arctic macroalgae was evident. Transplantation experiments of plants from deeper to shallow waters showed, for most algae, an inhibitory effect of both UVA and UVB on growth, except in the intertidal species Fucus djstichus. The growth rate of selected n~acroalgaew as directly correlated to the variations in natural solar radiation during the summer. Underwater experiments both in situ and using UV-transparent incubators revealed a linear relationship between the depth distribution and the growth rate of the algae. In almost all species the photosynthetic oxygen production decreased after 2 h incubation in the laboratory under 38 pm01 m-‘ s-‘ photosynthetic active radiation (PAR 400 to 700 nm) supplemented with 8 W m-‘ UVA (320 to 400 nm) and 0.36 W m-‘ UVB (280 to 320 nm) compared to only PAR without UV. Like in the growth experiments. the only exception was the brown alga F. distichus, in which photosynthesis was not affected by UV. The degree of inhibition of photosynthesis showed a relation to the depth distribution, i.e. algae from deeper waters were more inhibited than species from shallow waters. In general, no inhibitory UV effect on respiratory oxygen consumption in all macroalgae studied was detected under the artificial radiation regimes described above, with the exception of the brown alga Desmarestia aculeata and the green alga Monostroma arcticum, both showing a significant stimulation of respiration after 2 h of UV exposure. The ecological relevance of the seasonal variations in the solar radiation and the optical characteristics of the water column with respect to the vertical zonation of the macroalgae is discussed.
Jose Aguilera et al MARINE ECOLOGY Vol. 191: 109-119, 1999
In summary we can conclude that high latitude species are adapted to changes in UV flux. That the response in species with elevated melanin pigmentation is more suited to early levels of available PAR where photosynthesis is present. In other species due to defensive response the populations do not significantly decrease ,however photosynthesis is attenuated due to light limitations (they go deep)

February 7, 2009 4:10 pm

Ric Werme (06:26:51) :
Going back to the ā€œmore acidicā€ means an acid became more so doesnā€™t work since seawater isnā€™t an acid. So, let me substitute with ā€œless alkalineā€:

Since the process involved is the generation of H+ it is correctly described as becoming more acidic.
So the seawater gets less alkaline because the decrease in alkalinity
outweighs that of total carbon and [CO2] increases.
Sorry, I canā€™t get past that first line. You have me thinking H+ and OH- dancing in a circular argument then you shift to a black (or clear) solid and [a gas in brackets]. Good thing I got sucked up by computers before getting serious about my ChemE major. What the significance of those brackets? ChrisJ used that too, also TCO2, is that shorthand for Total CO2?

[X] is chemical shorthand for ‘the concentration of X’.
TCO2 is shorthand for Total CO2, i.e. āˆ‘([CO2], [H2CO3], [HCO3_], [CO3–])

February 7, 2009 4:13 pm

Steven Goddard:

My question is – Is there any way to have a sane, rational discussion with the AGW groupies?

No. Not with all of them.
But don’t let the handful around here get a rise out of you. Keep in mind that out of the many thousands of people who visit this site every month, only about a half dozen or so are the AGW groupies who always run interference. Someone has wired around their On/Off switch, and they’ve blown a fuse.
Most people are reasonable, and that’s why the tide is turning against the dwindling number of believers in the silly catastrophic AGW/CO2 fairy tale.

Ellie in Belfast
February 7, 2009 4:20 pm

Following this thread there has been something bothering me. I havenā€™t read all the comments, so forgive me if Iā€™ve missed some crucial points.
Iā€™m trying to imagine local conditions in an area of reef forming shallow ocean say 1 km2, no more than a few metres deep and with a few metres of atmosphere above it….
So we have more CO2 in the atmosphere above this portion of ocean. More of this CO2 dissolves in the ocean and makes it slightly more acidic. However letā€™s say the temperature of the ocean has also increased, this will result in a release of CO2 from the ocean ā€“ I read somewhere recently a figure of ~60ppm CO2 release for a 1ĀŗC temperature rise.
So the question is, what is the net change in CO2 and net change in pH? Letā€™s assume that the net change in pH is a decrease of 0.1 (8.2 to 8.1) near the average change reported above (0.075).
The next question is ā€“ which is more of a problem for corals etc. ā€“ pH or temperature? ā€“ (OK, so it is probably the combination, but bear with me)
In surface waters the carbonate ion is at supersaturating concentrations. However, as ocean pH falls, so does the concentration of this ion which makes it less available for reef formers (that want to lay down calcium carbonate). This is one of the main ā€˜problemsā€™ cited by the media in reporting ocean acidification.
Another thing to consider is that calcium is also supersaturated (and highly so). Now calcite (calcium carbonate) is more soluble at lower pH, which would be a problem, but it is also less soluble at higher temperatures. Given that increases in CO2 should be accompanied by increases in temperature (if climate alarmists are to be believed) is it possible that if temperature has more of an effect than the pH change, the worst effects as far as ease of CaCO3 precipitation are concerned, could cancel each other out?
So which would win out in terms of effect ā€“ the 0.1 unit decrease in pH or say a 1ĀŗC increase in temperature?

George E. Smith
February 7, 2009 5:10 pm

“”” Bill D (22:56:13) :
George E. Smith (14:08:20) :
1. ā€œā€ foinavon (13:02:16) :
George E. Smith (12:07:00)
saw tooth; and that suggests to me that the southern CO2 uptake, is likely more ocean related, than land plant growth.
So you see, I was not trying to be smart alecky; but hinting that the waveform isa clue to the mechanism.
But as I said, if you took it as frivolous comment on your post please accept my apology; it wasnā€™t intended that way at all.
George\
George:
The problem is here that we should not just be looking at time series that and guessing about plausible explanations. Scientists have long had reasonably good estimates of terrestrial photosynthesis. More than forty years ago they did all of the calculations and found that the seasonal dynamics of atmospheric CO2 match the changes in seasonal changes in photosynthesis and respiration of terrestrial vegetation (and respiration including decomposers like bacteria and fungi). Moreover, no one (published paper) cites credible scientific evidence for an alternative explanation, such as one related to the oceans. “””
Bill; I believe you may have misunderstood my position.
There is no way that I am challenging the plant photosynthesis explanation for the sawtooth cyclic variation of the ML CO2 data; In fact I thought my “seat of the pants” description of how such a saw tooth cyclic variation could arise from such processes, clearly supports the notion that the northern hemisphere plant growth cycle creates that sawtooth data.
But if you look at the three dimensional CO2 data; that being the long term CO2 variation from the North Pole to the South Pole, you see that the ML amplitude of around 6ppm P-P, grows to about 18ppm P-P at the North Pole. (A contact at Scripps in La Jolla, who is a CO2 specialist says it is 18 ppm). But as you move south from ML, the ampliude diminishes greatly and eventually reverses phase; which is to be expected since the southern hemisphere seasons are six months out of phase with the northern ones. Once the phase has reversed, the amplitude never grows very much at at the South pole it is only of the order of 1 ppm P-P and maybe less; and based on the NOAA plot I have it is no longer saw tooth in shape either, but is a much more symmetrical looking waveform. From the graph I have it looks double humped, suggesting that part of the Nothern cycle phase is showing through the southern hemisphere cycle, so there is almost a doubling of the frequency of peaks. It’s abit ragged to describe as sinusoidal.
In any case my suggestion simply was that at the south pole, and in fact for latitudes below around -40 it looks like that, and what may be causing that is simply the seasonal variation in the temperature of the southern ocean; that being the ocean that surrounds Antactica; not the entire southern hemisphere.
What is a mystery to me, is that the largest cyclic amplitude (18ppm) occurs right at the North Pole, where there is no land plant growth of any kind. That leads me to query whether there is significant ocean photosynthesis going on in whatever open waters there are in the arctic (presumably in Spring/Summer), or whether this is the northern forests still able to affect the atmospheric CO2 as far north as the North Pole.
I’m not challenging in any way, what the common wisdom is on the causes of the annual cycling of atmospheric CO2; and I think the sawtooth waveform at ML is a fairly clear indication that such photosynthesis processes are causing that. On the other hand, I would expect ocean surface temperature variations would follow more of a sinusoidal waveform over the year simply from the geometry of the sun arrangement.
The pole to pole assymmetry of the atmospheric CO2 is one of the oddest global phenomena I am aware of

Alan Wilkinson
February 7, 2009 5:20 pm

SImon Evans, circulatory ocean currents are typically 3-5 knots whereas atmospheric currents are an order of magnitude or so greater. A “back of the envelope” expectation might then be that ocean mixing would take around 10-20 times longer than atmospheric mixing.
I can see an argument that vertical mixing in the oceans would be much slower because it has an inherently stable temperature gradient whereas the atmosphere has an inherently unstable temperature inversion structure in many places.
That rather begs the question of whether vertical mixing is necessary to neutralise acidity given coastal waters and land runoff.

Steven Goddard
February 7, 2009 5:53 pm

Simon Evans,
The only comments I have made about mixing speeds of the oceans have been in reference to the empirical turnover as seen by ENSO events, just as in my response to you. If you believe I have said otherwise, feel free to point to a specific quote.
So, please stop making things up – because I am attempting to have a serious discussion here.

JamesG
February 7, 2009 6:12 pm

Mary Hinge
I accept your mild correction but why does nobody take up my Cuba conundrum question? Is it perhaps because I’m right? You can argue chemistry and biology all night: Now we have acidity, UV, light, temperature and heaven knows what other stresses BUT all of those changes are present in Cuba too. The difference clearly seems to be due to human activity near the coast. This is very well acknowledged by the experts studying the coral reefs there. One quote i saw in the NY times from a scientist was that it was “like going back 50 years in time”. It just seems to me you are all missing the point for the sakes of defending the policy rather than the science. Do you realize just how much raw sewage is thrown in the sea replete with industry chemicals, fertilizers and female hormones, or how much fishing boats damage the coral? The very slight change in sea surface temperature has not even happened for at least 5 years. Most increase in the anomaly also actually comes from increased minimum temperatures, while maximums are roughly the same. Most of this tiny temperature change even happens in the north, not the tropics. Do these tiny alterations really lead to such an enormous die-off? Just bear in mind how important it is to get this right. Yes we need extreme focus on environmental issues but we absolutely need to do the right thing for the right reasons.

Glenn
February 7, 2009 7:30 pm

In the “calculation” method of determining ocean ph, is dissolved organic carbon included? I haven’t found a clear explanation of the practical definition is between “inorganic” and “organic” carbon, but maybe its along the lines of the difference in the chemical composition of calcite/argonite.
I’ve discovered that HOT “bottle extraction” data has no dissolved organic carbon record from 1989 through 2002.
http://hahana.soest.hawaii.edu/hot/hot-dogs/bextraction.html
New methods were tested during 2002 for organic carbon, and measurements were recorded from 2003 onward.
http://hahana.soest.hawaii.edu/hot/reports/rep_y4.pdf
I’ve been researching methodologies that determined ocean ph, and it seems that there have been and still are several methods with varying degrees of accuracy, with a history of inaccuracy. Here’s just one example of that
http://globalecology.stanford.edu/SCOPE/SCOPE_16/SCOPE_16_1.5.07_Takahashi_271-286.pdf
In 1992 spectrophotometric techniques were tested and ph values began to be recorded, shown on the “bottle extraction” site referenced above. It is claimed to be a very accurate methodology.
So dissolved organic carbon appears to have not been measured till the spectrophotometric method began in 1992. Looking at the HOT ph graph, it is obvious there is a disconnect between the “calculated” and “measured” ph data, starting when the “measured” data begins.
Was the pre-2002 data too high? Without that data, what would be the trend using both “calculated” and “measured” data? Offhand looks to me like there would no downward trend, or a small number approaching the error of measurement.

February 7, 2009 7:33 pm

What is a mystery to me, is that the largest cyclic amplitude (18ppm) occurs right at the North Pole, where there is no land plant growth of any kind. That leads me to query whether there is significant ocean photosynthesis going on in whatever open waters there are in the arctic (presumably in Spring/Summer), or whether this is the northern forests still able to affect the atmospheric CO2 as far north as the North Pole.
George my interpretation is as follows:
Here’s the monthly data for 2007 from Point Barrow.
388.75 389.57 389.96 389.95 390.43 388.22 380.15 373.23 375.23 381.08 385.86 389.11
You can see that the CO2 concentration starts to drop in June just when the seaice starts to open up, exposing cold water which has been isolated from the atmosphere for about 6 months. Under those conditions you’d expect a rather rapid absorption of CO2, as observed. As you can see the CO2 starts to increase in October and stabilizes by December the same period during which the seaice closes back up. Point Barrow is at the coast and so is influenced by the periodic exposure of the cold water, the South pole on the other hand is far from the coast and influenced by katabatic flow so isn’t subject to the same effects.

Glenn
February 7, 2009 7:34 pm

Forgot to include the ph graph url in my last:
http://hahana.soest.hawaii.edu/hot/trends/trends.html
(select ph comparison)

Glenn
February 7, 2009 10:05 pm

Following up on the HOT ph graph to determine whether the early data could have been too high to accurately reflect ocean changes due to atmospheric CO2,
(ph graph)
http://hahana.soest.hawaii.edu/hot/trends/trends.html
(2003 article)
http://www.nature.com/nature/journal/v424/n6950/full/nature01885.html
“Here we analyse a 13-year time series of oceanic carbon dioxide measurements from station ALOHA in the subtropical North Pacific Ocean near Hawaii4, and find a significant decrease in the strength of the carbon dioxide sink over the period 1989ā€“2001. We show that much of this reduction in sink strength can be attributed to an increase in the partial pressure of surface ocean carbon dioxide caused by excess evaporation and the accompanying concentration of solutes in the water mass. Our results suggest that carbon dioxide uptake by ocean waters can be strongly influenced by changes in regional precipitation and evaporation patterns brought on by climate variability.”
It appears that the “calculated” ph (although I am still in the dark as to exactly how ph was “calculated” by HOT from 1989 – 2002) may have been too high, influenced by natural variability.
I have some some documentation on how ph is “calculated” at least in 2006:
http://hahana.soest.hawaii.edu/hot/methods/dicalk.html
“(DIC) measured using a Single Operator Multi-parameter Metabolic Analyzer (SOMMA) … Total (titration) alkalinity (Talk) was determined using the modified Gran titration method… ”
Apparently it is possible to calculate a ph from basically from those two values. Normalizing and buffer factors are also required, and it seems all this gets quite complex and maybe a tad arbitrary. Of course,
http://www.bios.edu/Labs/co2lab/research/IntDecVar_OCC.html#tab2
“The anticipated rate of change surface ocean CO2 due to the accumulation of anthropogenic CO2 in the atmosphere and the surface ocean buffer factor (assuming that near-surface waters in the subtropical gyres have residence times long enough to equilibrate entirely with the anthropogenic perturbation in atmospheric CO2) can be theoretically calculated.”
I still don’t think I am way off on my suspicions that the HOT ph graph reflects “predicted” change. Set out to prove something and sooner or later you’ll find a way to do it.

Roger Knights
February 8, 2009 12:47 am

Simon Evans (11:52:02) wrote:
“Steven Goddard,
“As Chris J has said above, anyone whoā€™s followed this thread will be able to figure out who has been talking nonsense, so I rather think it pointless for either of you to keep making the claim.”

The exasperation level is getting high here, and shows no sign of resolution. And yet this dispute, or a large part of it, could easily be resolved if there were an acceptable referee who could make a ruling on it. How about an ad hoc panel of presumptively neutral and high-status chemists + geologists, chosen at random from officials or past officials of their scientific societies? This could be useful in resolving–or at least clarifying–other disputes on this site, and maybe other sites too.

Simon Evans
February 8, 2009 4:42 am

Steven Goddard (17:53:30) :
Simon Evans,
The only comments I have made about mixing speeds of the oceans have been in reference to the empirical turnover as seen by ENSO events, just as in my response to you. If you believe I have said otherwise, feel free to point to a specific quote.
So, please stop making things up – because I am attempting to have a serious discussion here.

I am referring to your implication that observed ocean circulation expedites mixing to the extent of allowing the sea bed to buffer CO2 uptake at a fast enough rate, as indicated in these posts:

Steven Goddard (06:50:57) :
One of the arguments being propagated is that low mixing rates between shallow and deep water prevents pH buffering. However, we know that under normal Pacific Ocean conditions, cold deep water is continuously dragged to the east up the thermocline along the South American Coast, and is replaced by warm water sinking in the mid-Pacific. Under La Nina conditions this becomes even more exaggerated.
Steven Goddard (22:34:02) :
Chris J,
The point you are missing about the ocean system is that it contains large amounts of CaCO3 which buffer the alkalinity. Any push towards lower pH causes CaCO3 to dissolve, bringing the pH back up again. That is one reason why 5.2pH or less rainwater can continuously fall in the ocean, without any change in ocean pH. BTW – If ocean water did not circulate efficiently (as some have claimed) there would be an acidic layer near the surface, due to the rain. Instead, we find that pH decreases with depth.
Steven Goddard (09:04:15) :
Simon Evans,
Think about your last post.
The IPCC is claiming a much accelerated rate of acidification over the remainder of the century. How can CO2 absorption be slowing down and accelerating at the same time?
Secondly, as I have pointed out repeatedly, the existence of La Nina is proof of the rapid interchange of deep and shallow water in the Pacific. Where do you think the cold water came from?

The point is crucial. All discussion of rainwater falling on limestone, etc. etc., is moot if the buffer of the ocean floor is not rapidly exposed to the increasing CO2 concentration. It is not disputed that eventually the buffer would do its stuff, but if the current pace of CO2 increase exceeds the rate of the buffer then there is a change in the system, which is not discounted by the fact of atmospheric CO2 concentration having built to higher levels before at a much slower pace.
Another poster mentioned tritium traces which, as I’ve already said, indicate that ocean mixing to depth is far from ‘rapid’ on the time scales that are of concern in respect of the pace of acidification. In terms of CO2 mixing, see the following paper:
http://www.sciencemag.org/cgi/content/abstract/305/5682/367
– which found that 50% of anthropogenic CO2 is held in the top 400 m despite this making up only about 10% of the ocean volume. Most of the deep waters, especially those 1 km + deep, have yet to receive any anthropogenic CO2.
Waving your hand at ENSO upwelling doesn’t cut it. You might want to believe that the oceans mix fast enough for the buffering to keep pace, but the evidence tells us this is not so.

maksimovich
February 8, 2009 6:01 am

Simon Evans (04:42:45)
“El Nino also drastically reduced the amount of carbon dioxide this ocean region adds to the atmosphere. Unlike most parts of the world’s oceans, the equatorial Pacific is normally a major contributor to atmospheric carbon dioxide due to the carbon-dioxide-rich deep ocean waters brought to the surface here and the relatively low levels of biological activity.
The researchers calculate that the amount of carbon dioxide released to the atmosphere by the equatorial Pacific during the year of El Nino conditions was 700 million metric tons of carbon less than the previous year. This is equivalent to half of the United States’ total annual carbon dioxide emissions from fossil fuel burning. ”
http://svs.gsfc.nasa.gov/stories/elnino/press.html

J. Peden
February 8, 2009 10:10 am

Pete D (11:45:37) :
J Peden, Foinavon:
If there is still debate on this, a little General Chemā€¦
1) H2CO3 = H+ + HCO3- with Ka1 = [HCO3-][H+]/[H2CO3] = 4.2E-7
2) HCO3- = H+ + CO32- with Ka2 = [H+][CO32-]/[HCO3-] = 4.8E-11
overall equilibrium constant, K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-]

K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-]
Pete D, try out this argument:
pKa = pH at which an Acid is exactly one half dissociated. In other words, at pKa, concentration of Acid = concentration of Conjugate Base formed from the Acid. They are “half and half”, existing in a ratio of 1:1.
pKCarbonic Acid/H2CO3 = 6.1
Therefore, at pH of solution = 6.1, [H2CO3] = [HCO3]. In other words at pH = 6.1, H2CO3 has exactly half-dissociated to produce an equal concentration of HCO3 – and it will stay exactly half-dissociated as long as pHsoln. = 6.1.
But at pHsoln. greater than 6.1, H2CO3 is more than half-dissociated. In other words, as the pH of the total solution increases, decreasing total [H+], existing H2CO3 more readily donates a proton H+, and so as to also produce more HCO3-.
Such that, [HCO3] >> [H2CO3]
Now looking at your equation, K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-]
For H2CO3 at pHsoln. > 6.1, [HCO3] > [H2CO3]
Therefore, [CO3] must increase in order to keep K constant when more H2CO3 is added to the solution, again, because any added H2CO3 at pHsoln > 6.1 will end up more than half-dissociated. Effectively, more HCO3 is added to the solution than H2CO3 at any pHsoln. > 6.1.
So for every addition of H2CO3 to a solution of pH > 6.1, in particular by increasing dissolved CO2, [CO3] must increase – in order for K to remain constant.
Therefore, in the Oceans, where pH = 8.1, addition of more dissolved CO2 must increase CO3.
Imo, once again, when more H2CO3 is added to a solution of pH > 6.1, it is simply not possible to get more net H2CO3 formed/added than HCO3 formed, because at these pH’s, H2CO3 more than half-dissociates, so more HCO3 is formed net than H2CO3 is increased.
Therefore, by equation K, CO3 must increase net to keep K constant, regardless of the “strength” of equation 2 in tending to form HCO3 from CO3 and H.
That’s what K says [to me], in solutions of H2CO3 whose pH’s are > 6.1.

Simon Evans
February 8, 2009 10:20 am

maksimovich (06:01:09) :
Simon Evans (04:42:45)
ā€œEl Nino also drastically reduced the amount of carbon dioxide this ocean region adds to the atmosphere. Unlike most parts of the worldā€™s oceans
, the equatorial Pacific is normally a major contributor to atmospheric carbon dioxide due to the carbon-dioxide-rich deep ocean waters brought to the surface here and the relatively low levels of biological activity….
I’ve added some bold! Besides which it’s rather obvious, isn’t it, that CO2-rich waters upwelling will increase the acidification pressure at surface levels and decrease the exposure of CO2 to the sea floor carbon buffer? How on earth is the observation of ENSO behaviiour supposed to answer the point that ocean floor buffering is globally a very slow process whilst near-surface CO2 absorption is developing rapidly?

Alan Wilkinson
February 8, 2009 4:15 pm

J Peden, take the partial derivatives and I obtained this equation:
d( [CO3=] ) = (K1 * K2 / [H+]^2 * ( d( [H2CO3] ) – ( [H2CO3] / 3 * [H+] ) * d( [H+] )
In seawater ballpark values are:
[HCO3-] 1.86E-03
[CO3=] 1.20E-04
[H+] 1.62E-08
[H2CO3] 2.00E-05
K1 1.45E-06
K2 1.09E-09
So [H2CO3] / 3 * [H+] = 411
And K1 * K2 / [H+]^2 = 5.97
So an increase in acidity has 400 x the impact of an equivalent increase in dissolved CO2 and therefore forces carbonate lower. This is amplified further by the high degree of dissociation of H2CO3 in seawater.
This was the calculation I was going to use to show J Lo the error of his ways but instead it convinced me I should do the math next time before I open my mouth!

Pete D
February 9, 2009 9:08 am

J Peden –
You are confusing yourself. Use the equilibria and work out the algebra.
If you start with the values listed by Alan Wilkinson (16:15:09) and increase the amount of dissolved CO2 by 10% (by increasing [H2CO3] to 2.20e-5 M), you get an increase in [H+] to 1.79e-8 M (pH = 7.75 as opposed to the initial pH = 7.79). This is accompanied by a negligible increase in [HCO3-] (because it is so high to begin with), but also by a significant decrease in [CO3=] from 1.20e-4 to 1.09e-4. Alan is right about doing the math. Equilbrium for multiprotic acids in a buffered system can be difficult to think about without doing the math!

J. Peden
February 9, 2009 9:24 am

Alan Wilkenson:

So an increase in acidity has 400 x the impact of an equivalent increase in dissolved CO2 and therefore forces carbonate lower. This is amplified further by the high degree of dissociation of H2CO3 in seawater.

Yes, I understand that this is “their” argument – “increase in acidity” forces H + CO3 to the net formation of HCO3 with a decrease in CO3 – but I don’t see how they overcome mine, that K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-] must remain constant, and when adding CO2/H2CO3 to solution at pH > 6.1, more HCO3 is formed than H2CO3 results, meaning [CO3] must increase if K is to remain constant.
Another wrinkle from http://chimge.unil.ch/En/ph/1ph67.htm, slightly modified, i.e. H3O to H3O-1 and H3O-2, and adding 1] and 2] as notations:

Both protons of Carbonic Acid, H2CO3 are weakly acidic:
1] H2CO3 + H2O = HCO3 + H3O-1 pKa1 = 6.1
2] HCO3 + H2O = CO3 + H3O-2 pKa2 = 10.3
What is the pH of a solution of carbonic acid ?
The hydrogenocarbonate ion HCO3- is amphoteric [able to both donate and receive H+ effectively], thus
pH = 1/2[pKa1 + pKa2] = [6.1 + 10.3]/2 = 8.2 [near Oceans’]
independently of the concentration of Carbonic Acid!

pH doesn’t change regardless of Carbonic Acid concentration.
“Their” argument is that with the addition of CO2/H2CO3, H3O-1/”acidity” increases ~ “a lot”, causing the H3O-2 component to combine with CO3 so as to decrease [CO3], also because pKa of HCO3 = 10.3 [btw, which is nothing new to the interactions].
Still, if pH doesn’t change, “their” argument seems to make sense – increased H has to go somewhere – except that it contradicts the constancy of K, where, according to my argument, [CO3] must increase if CO2/H2CO3 is added at pHsoln > 6.1.
So what happens to the added H3O-1 instead of acting to decrease [CO3] net, which allows pH and K to remain constant, and [CO3] to increase net as per K?
I say it just forms H2O:
H3O + OH = 2H2O
In other words, I essentially don’t care about the extra “acidity”/H+ – unless it results from a source of acid other than CO2/H2CO3. I’m saying K must remain constant, so that the extra H from H2CO3 must simpy form H2O – that is, enough to keep pH constant, while allowing a net increase in CO3.
Also, imo, “their” argument also seems to state that decreasing CO2/H2CO3 in solution increases CO3.

J. Peden
February 9, 2009 10:19 am

Equilbrium for multiprotic acids in a buffered system can be difficult to think about without doing the math!
Thanks, Pete, I might be wrong. But right now I don’t see how “the math” avoids the math problem that K = Ka1/Ka2 = [HCO3-]^2 / [H2CO3][CO32-] presents, given that at pHsoln > 6.1, adding H2CO3 results in more HCO3 formed net than H2CO3 remains after its addition – HCO3 increases more than H2CO3 – since at pHsoln > 6.1, H2CO3 is more than half dissociated, and likewise for any more added H2CO3, making the net increase in [H2CO3] necessarily more “neglible” than the increase in [HCO3]. So that to keep K constant, [CO3] must increase.
This is a math problem, too. Maybe these “neglibles” don’t really count in calculating or describing [CO3], but K says they do. Instead, do we just ignore K?

Pete D
February 9, 2009 12:35 pm

J Peden – I do not ignore K, but K is simply a relationship between Ka1 and Ka2 that helps to show the effect of raising one concentration. It is much clearer if you write down the equations and do the math yourself as you are pretty confused as to how acid-base equilbria are acting in this system (this is not to demean you in any way!). Or ask a chemist or chem eng to show you!

Chris J
February 9, 2009 2:53 pm

J Peden,
Your calculation for of the ratio K1/K2 = [HCO3-]^2/{[H2CO3][CO3=]} is fine. I think the point that is confusing you is that, since the concentration of HCO3- is so high an increase of X in [H2CO3] results in only a proportionally small increase in HCO3-.
For example, @ 35 ppt, 1 atm, 25 C, 2300 ueq/kg TA (standard sea water) you’ll get these concentrations for DIC species at pHsws = 8.05, 7.95, 7.85 (K1 and K2 from Dickson and Millero, 1987; K2 for HSO4- from Dickson1990):
All conc. in umol/kg
pHsws = 8.05
CO2* = 10.79
HCO3- = 1761.60
CO3= = 219.03
pHsws = 7.95
CO2* = 14.28
HCO3- = 1851.07
CO3= = 182.82
pHsws = 7.85
CO2* = 18.73
HCO3- = 1928.75
CO3= = 151.31
For all sets you get the same K1/K2 = 1312.71. From pHsws = 8.05 to pHsws = 7.85 the concentration of CO2* increases by only 7.94 umol/kg while HCO3- increases by 167.14 umol/kg. However, CO2* increases by 74% while HCO3- only increases by 9%.
Your calculation was fine, but your reasoning of the effects of an increase in CO2* on the rest of the system was off, having not performed the calculations.
Well, there’s really been a whole lot of discussion about nothing here hasn’t there. The chemistry works just as expected, and is easily replicated at whatever set of conditions one likes. It’s a bit perplexing that it’s taken so much ‘debate’ to get to this point, but at least we got here.
Also, @ Alan Wilkinson: good on ya. We need more folks like yourself.
Best,
Chris

J. Peden
February 9, 2009 10:32 pm

Chris J:
Your calculation was fine, but your reasoning of the effects of an increase in CO2* on the rest of the system was off, having not performed the calculations.
Thanks, Chris. Maybe I’ll see if I can make the calculations using H2CO3 as the input, instead of specifying pH then calculating the species – as it appears you might have done? – “youā€™ll get these concentrations for DIC species at pHsws = 8.05, 7.95, 7.85”
And, again just shooting from the hip, another one of my problems is that looking at your pH calculations, they are all too low, at least if you use the H.-H. calculation as per human acid-base chemistry where [H2CO3] can be ignored, change in [CO2] is often the culprit/driver, and:
pH = 6.1 + log [HCO3]/[dissolved CO2]
But I’ll give it a rest!

Pete D
February 10, 2009 5:36 am

J Peden-
I think I see the source of your confusion…the H-H equation gives you pH at equilibrium. So you need to use the equilibrium calculations to determine [HCO3-] and [CO2] (or [H2CO3]) before you use the H-H equation. It doesn’t seem like you are doing the equilibrium calculations before you plug in your concentrations and just trying to rationalize what will happen. The other complication is that at a pH~8.1 you are right between the pKa of Ka1 (for H2CO3) and Ka2 (for HCO3-), so there is a significant contribution from each equilibrium to the concentrations of each species in solution. By focusing only on Ka1, you are neglecting the effects of changes in H+ on the concentrations in the second equilbrium equation. It really helps to do the math instead of shooting from the hip. You would save yourself a lot of time and understand things a lot better!

maksimovich
February 11, 2009 9:19 pm

Simon Evans (10:20:44) :
“Iā€™ve added some bold! Besides which itā€™s rather obvious, isnā€™t it, that CO2-rich waters upwelling will increase the acidification pressure at surface levels and decrease the exposure of CO2 to the sea floor carbon buffer? How on earth is the observation of ENSO behaviiour supposed to answer the point that ocean floor buffering is globally a very slow process whilst near-surface CO2 absorption is developing rapidly?”
Overlooked your response sorry.
Here is a better description
“Phytoplankton are the base of the marine food chain, providing food for little sea animals called zooplankton, which in turn feed fish and other creatures. Any change in phytoplankton numbers alters the ocean food chain.
The computer model showed that during El NiƱo periods, warm waters from the Western Pacific Ocean spread out over much of the ocean basin as upwelling weakens in the Eastern Pacific Ocean. Upwelling brings cool, nutrient-rich water from the deep ocean up to the surface. When the upwelling is weakened, there are less phytoplankton, making food more scarce for zooplankton that eat the ocean plants.
During La NiƱa conditions as in 1998, the opposite effect occurs as the easterly trade winds pick up and upwelling intensifies bringing nutrients like iron to the surface waters, which increases phytoplankton growth. Sometimes, the growth can take place quickly, developing into what scientists call phytoplankton “blooms.”
In a study published in the January 2005 issue of Geophysical Research Letters, Wendy Wang and colleagues at the University of Maryland Earth System Science Interdisciplinary Center, College Park, Md., found that changes in phytoplankton amounts due to El NiƱo and La NiƱa not only affect the food chain, but also influence Earth’s climate.”
http://www.nasa.gov/vision/earth/lookingatearth/plankton_elnino.html
What we are observing is not only the perturbation of the photic region in a local event,this also occurs globally eg in the arctic and antarctic and in semi enclosed basins.
First let us observe a natural law. Living organisms operate in what is described as far from equilibrium.
eg in “Theoretical Biology” E. Bauer confidently stated that biology was not applied physics or chemistry. He also stated that “all special laws, which would be revealed in certain fields of biology would display the general laws of motion, appropriate to living matter” [4, p.8]. The urgent problem of theoretical biology was, according to E. Bauer, the development of general laws of motion for living matter.
“Only living systems never reach equilibrium, for they constantly work against stability” [4, p.43]. According to Bauer, the source of free energy(orā€ the work of structuring forces” and “structural energy” are the synonyms) is the nonequilibrium of molecular structure of living matter
What is the source of the nonequilibrium of “living matter”? Firstly it is the activation of molecules of food caused by levelling processes. Energy of these molecules maintains nonequilibrium (here the molecules of living matter in “active, deformed state” are considered [4, p.127]. However, the unavoidable result of metabolism is, according to E. Bauer, the lowering of the potential of free energy of nonequilibrium. “The more intensive metabolism is, the higher rates of the free energy depletion are. This free energy of living matter exists because of the deformed nonequilibrium structure of its molecules” [4, p.129]. “During assimilation the structural energy of a system can be used. This energy is necessary for the reconstruction of nonliving substance” [4, p.144].The total amount of energy that can be assimilated is limited. This amount of energy is species-specific parameter of organism (Rubner constant) (see [4, p.131; 37] and is “proportional to the free energy of an ovicell” [4, p.130].
This means that the problem of the source of living matter’s nonequilibrium cannot be reduced to the possibility of nonequilibrium’s replenishment with free energy of food. Another source of nonequilibrium is required. The utilization of this source should regulate the organism’s ability to make up for free energy losses with food. Concerning deeper nonequilibrium one can propose several possibilities of its origination in organism. They might be the following:
– the law of nonincrease (or conservation) of structural energy and transfer of it from generation to generation;
– the possibility of external replenishment of structural energy during the origination or fertilization of the ovicell in addition to an explanation of Bauer’s theory, according to which fetal cells, possessing maximum initial potential, originate due to dying or, in other words, dissimilation of the body tissues” [4, p. 144].
– to reject the idea of the impossibility of structural energy replenishment during the life period, and then to find the ways of such replenishment, for instance, the mechanism of structural energy assimilation by autotrophs and its farther spreading in the biosphere through the food chains.
In the second and third proposals, and in other cases, allowing the structural energy replenishment, the question about the sources of such replenishment remains.
When considering the problem of understanding the stable nonequilibrium principle, another problem arises, that is the search for the sources of nonequilibrium. This problem is connected with time, its flow and becoming. One of the possible hypotheses dealing with this problem’s consideration consists of the substantial time construction [28; 29].
In modeling of biological systems that oscillate from state to state seemingly random in appearance, are actually showing self organization of the ecologic community to variation of resource and both evolution and devolution.
Yakushev, E.V. and Mikhailovsky, G.E., 1995. found biological attenuation (modulation)of ph levels during phytoplankton blooms.
The dramatic increase in atmospheric carbon dioxide (CO2) concentrations observed during the past decades can be associated with the natural climatic oscillations or/and with anthropogenic influence. Concern about the potential role of CO2 as a ā€œgreenhouse gasā€ had led to necessity of investigation of this element global biogeochemical cycle peculiarities. The oceans play an important role in this cycle, containing large reservoirs of dissolved inorganic carbon as gaseous CO2(g), bicarbonate (HCO3-) and carbonate (CO32-) ions. Because of it, the ocean ultimately determines the atmosphere’s CO2 content (Siegenthaler, Sarmiento, 1993). Information about the CO2 system behavior can be obtained by investigations of the processes which affect the carbonate system parameters distribution and variability.
One of the most interesting aspect of this problem is the role of marine biota. When we speak about this, we consider the aggregation of gaseous CO2 into particulate organic carbon (POC), which can be transported into the deeper layers, sedimented on the bottom and thereby excluded from the global cycle and also of the POC mineralization and respiration processes (so-called ā€œsoft tissue pumpā€ (Gruber et al, 1996) . However during the phytoplankton bloom the decrease of CO2 is accompanied by disbalance of the system which can initialize the activity of the other ā€œpumpsā€: (ā€œsolubility pumpā€ – ocean-atmosphere CO2 exchange, and ā€œcarbonate pumpā€ – and formation dissolution of calcium carbonates).
During the bloom the consummation of gaseous CO2 by phytoplankton leads to the disbalance of the carbonate system equilibrium. This results in increased pH values and therefore in changes in the carbonate system balance toward increases in carbonates and additional decreases in gaseous CO2. In other words, during the bloom the upper layer gaseous carbon dioxide decreases for two reasons – consummation of the organic matter synthesis and transformation from gaseous CO2 to CO3, initiated by pH changes.
In this case during the bloom period one can observe decrease of TCO2 and dissolved CO2 while the value of carbonate alkalinity (AlkC) remains constant to fulfill the sea water electricity neutrality equation (Millero, 1995, Dickson, 1992).
eg http://i255.photobucket.com/albums/hh133/mataraka/Image62.gif
The ocean is not an empty “beaker” 65% of the biosphere lives in or under the ocean.