The world’s marine ecosystems risk being severely damaged by ocean acidification unless there are dramatic cuts in CO2 emissions, warn scientists.
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 sound alarming, until you consider that corals became common in the oceans during the Ordovician Era – nearly 500 million years ago – when atmospheric 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 and early Silurian with CO2 levels 10X higher than current levels, and the correlation between CO2 and temperature is essentially nil throughout the Phanerozoic.)
Perhaps corals are not so tough as they used to be? In 1954, the US detonated the world’s largest nuclear weapon at Bikini Island in the South Pacific. The bomb was equivalent to 30 billion pounds of TNT, vapourised three islands, and raised water temperatures to 55,000 degrees. Yet half a century of rising CO2 later, the corals at Bikini are thriving. Another drop in pH of 0.075 will likely have less impact on the corals than a thermonuclear blast. 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.
E.M.Smith (16:47:43) :
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…)
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.
Alan Wilkinson says:
So, J Lo, Alan has shown you his. How about you whack yours down now for us to see.
@ur momisugly 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, today’s stony corals, don’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, I’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 today’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 tetrapod—humans—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.—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 don’t understand this, and therefore shouldn’t be speaking on the subject, or do and are purposefully misleading everyone. I’m not sure it much matters, but I’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 CO2—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 “acid” (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 “ocean acidification”. 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
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.
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.
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.
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?
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.
Dear Mr Watts:
Concerning the recent BBC article titled “Acid oceans ‘need urgent action‘, 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 “I’ll be in touch on the phone in the next day or two”. But the BBC published the article titled “Acid oceans ‘need urgent action‘” which does not mention – and completely ignores – the “helpful” information which I provided.
It seems the BBC is immune to influence by any facts that might alter the BBC’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,
I’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 you’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? I’d be very grateful if so. What’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:
“Would you have time for a conversation on the phone at some point soon? I’d be very grateful if so. What’s the best number to reach you on?”
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 ‘acidification’ 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 – 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 ‘ocean acidification’ (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, it’s most helpful.
I’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
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?
Alan Wilkinson (12:57:13)
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 can’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+ + CO3–
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 doesn’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. It’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 wouldn’t result in a drop in pH! Incidentally, since you are a chemist, why not test this yourself in the lab? It’s a very easy experiment to do….
——————————–
* notice that there is a small approximation here since the full analysis is slightly more complex as we’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.
Maybe Jo saw the name ‘Jaworowski’ and href=”took fright?
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.
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, it’s most helpful.
I’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 “Acid oceans ‘need urgent action‘ that was 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.”
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
J Lo’s equations just don’t add up, something like this
Richard S Courtney (02:14:18)
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
In fact it does. See the Mauna Loa atmospheric CO2 data linked to just above.
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.
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.
Richard S Courtney (03:42:25)
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”.
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…
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 can’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 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.
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).
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.
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.
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
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)
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.
Foinavon:
Sorry, but – as I said on the other thread – you are simply wrong.
You assert:
“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.”
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:
“The 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.”
Mea culpa.
But, as I have repeatedly explained to you on the other thread,
“there are two components to the recent rise in atmospheric CO2 concentration: viz. the variation that is directly related to mean global temperature (i.e. Calder’s ‘CO2 thermometer’) and the steady rise of 0.4 per cent per year. As you say, Calder’s CO2 thermometer seems to be ENSO-related. Hence, it is the steady rise that we need to understand.”
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;
“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.”
Rubbish! The “real world evidence” 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 don’t take back all of it.
As I said,
“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.”
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