NOAA's Pacific Marine Environment Laboratory Carbon Program goes overboard on ocean acidification – leaves uncorrected error

This letter to Dr. Richard A. Feely of NOAA’s Pacific Marine Environment Laboratory Carbon Program in Seattle, WA was sent by Chuck F. Wiese on Wednesday. Chuck also asked me to post it on WUWT but I wanted to see if NOAA would fix the error on the web page first. It is now Saturday, and they haven’t, so I think a public notice is appropriate. I suppose I’m not surprised though, since Dr. Feely lists “Nobel Peace Prize (co-shared with Al Gore and other members of IPCC) – 2007” on his web page. I suppose anyone who lists Al Gore along with the gross errors he makes, such as his laughably non-reproducible “high school physics” of CO2, would not bother to correct their own gross errors. – Anthony

==============================================================

Dear Dr. Feely:

I exchanged e-mails with you a while back over a story that ran in the Oregonian on April 12, 2012. It was about “ocean acidification” that was supposedly killing off what would otherwise be healthy oyster harvests here in the Northwest, The story can be found here:

http://www.oregonlive.com/pacific-northwest-news/index.ssf/2012/04/oregon_state_research_traces_o.html

An OSU researcher who gave the story to the Oregonian, Alan Barton, had incorrectly asserted that the ocean pH had risen 30% because of human CO2 emissions and gave that as the reason the oyster harvests had been suffering. And he qualified that statement by stating that the ocean pH had moved .1 unit towards acidity over the last century.

But as you know, the equation for the pH of an aqueous solution is logarithmic and defined as pH = -log[ H+ ] . As you also know, there are 14 orders of magnitude that define the pH scale from zero to fourteen units as per this equation. So a movement of .1 units towards acidity cannot equal a 30% increase in acidity as claimed in this article. It is actually .1/14 or only 7/10ths of 1%. In order for there to be the increase cited, the researchers solved it for the hydrogen ion concentration and computed that change instead and called it the change in acidity. So if we moved .1 units towards acidity from the alkaline 8.2 to 8.1 oceans and compared the change, we have [delta H+] = 8 E-9/6 E-9 = 1.33 or a 33% increase in the hydrogen ion concentration, not an increase of 33% in the pH. None the less, that is how the story was reported and it is wrong.

Since the natural variation of ocean pH can be up to 5% in either direction, I am speculating that in order to make the story seem legitimate, a gross exaggeration of fact was needed to sell it and hence the switch and bait tactic was used with the pH equation.

You agreed with me in my premise that hydrogen ion concentration makes up the pH but it is not defined by that number because the number of ions in an aqueous solution of water are very large. That was the whole idea behind creating a logarithmic scale with the 14 orders of magnitude to define it. I reported this to the Oregonian readership and thought the issue was settled. But then I found this:

http://www.pmel.noaa.gov/co2/story/What+is+Ocean+Acidification%3F

In this explanation offered by NOAA, of which you are a senior scientist, we are back to the trickery of claiming the ocean acidity has increased by 30%. Are you aware of this NOAA information page? It needs an immediate correction. The ocean pH has been changing everywhere within natural variations. There is no provable decrease that can be identified with atmospheric CO2 that is related to human activity. Does Jane Lubchenco understand this? She has made numerous and completely false assertions that the up welling ocean water off of the Northwest coasts ( that will be on the rise because of the switch to cold phase PDO in 2007 that will run thirty years and likely decrease the pH additionally ) is attributable to human caused climate change. There is absolutely no proof of this and as far as meteorologists can tell, the mid and north Pacific Hadley cell summer circulation has intensified on schedule and is behaving perfectly normally in the cold phase of this ocean cycle. Either you or Lubchenco need to correct this page. It is misleading the public.

Sincerely,

Chuck F. Wiese

Meteorologist

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ChE

It’s even more complicated than that, because there are buffers involved.
BTW, the original reason for the logarithmic scale isn’t to take into account the wide range of concentrations, it’s because the electrochemical potential of a pH probe is logarithmic; i.e. the millivolts from a probe are directly proportional to pH. It was an easy way to measure without converting the other way.

Does Jane Lubchenco understand this?
She understands that she could announce the Pacific will turn into hydrogen sulfide in 30 years and not a single Letter-to-the-Editor would ever see print.

Mass fraud. Science’s version of Wall Street and the City Of London. Go LONG on piano wire.

Absolutely correct, Chuck. Their lazy attitude towards correct science displays a tendency all too familiar.

robert barclay

It is being assumed by these people that the ocean obeys the second law of thermodynamics, it does not because of surface tension. You can not heat water from above on this planet which may be why the oceans are still here. If surface tension stops heat what chance has a co2 molecule of passing through. As far as I can make out the only thing that penetrates the oceanic surface tension is the sun’s rays. Because of surface tension AGW can not exist.

Chem Prof

I don’t think that Chuck is incorrect in this instance. The pH scale is open-ended, not limited to the range 1.0 to 14.0. That is not a huge error in itself, but the fact that the ocean is buffered amplifies the significance of the 30% increase of hydrogen ion concentration, not diminishes it. This is a large change in acidity, contrary to claims made here.

Chem Prof

Please be careful to distinguish between hydrogen ion concentrations and pH. While these are interconvertible, they are not identical.
If your speed where to increase from 50 mph to 100 mph, the logarithm (base 10) of your speed double from about 1.7 to 2.0, roughly an 18 percent increase. I think a judge would be very unimpressed by your argument that you were only faster by 0.3 log units.

Chem Prof

IPad auto-corrupt is the Bane of us all.

Pamela Gray

This is rather funny. If there is one thing farmers and ranchers know how to do, it’s measure pH. Some things need soil less alkaline, some things need soil that is very sweet, and some things need soil that stays in the middle of neutral. But we are talking small movements one way or the other. pH that changes by 30% towards acidic would be…crazy!!!! You would have dead fish floating on the water for heaven’s sake. And just plain ol’ flat-earth rednecks would know this! How embarrassing.
If she wants to get ahold o’ me, I’ll aks my neighbor Bubba if’n he could walk her through the process of pH measurement. Ya know, we git these kits down at the Grain Growers fer next to nothin so I’m sure he would do it fer ya.

Things like this go to the heart of credibility. Uncorrected errors damage the reputation of the parent and wall as the credited author. It goes way beyond this though. There is a huge move in Canada to make sure only PR people speak for any Federal organization. The present control freak Prime Minister does everyone a great disservice by attempting to control the message. Foolishness like this are the result of such an approach. People who have few if any clues about things such as physics and chemistry create or miss the error specifically if it supports their bias. It is simply another form of the big lie. Niccoló Machiavelli, would be proud.

Pamela Gray

Chem Prof, how large? In pH terms please, not in hydrogen ion terms.

The oceans are infinitely buffered. That is why rainwater (<5.2 pH) can continuously fall on the surface of the ocean all day long with no change in the ocean's pH — not even on the surface of the ocean — because, it mixes so quickly and thoroughly (in fact, the pH of the ocean actually decreases the deeper you go). Any a move toward a lower pH would simply cause CaCO3 to dissolve and bring the pH right back up.
"Ocean pH is not governed by physico-chemical rules. Marine organisms control their calcium carbonate properties organically behind membranes. Increased CO2, in any case, evolves from sea water because of inverse solubility. CO2 dissolves in cold water and bubbles out of warm water. That's why CO2 trails natural warming," ~Dr. Francis T. Manns
and,
"Objective scientists realize that coral, foraminifera and shellfish have deep mechanism that have evolved over 100s of millions of years as CO2 has fluctuated far wider than we see in the atmosphere today. Google Ernst-Georg Beck for a synoptic paper on 180 years of CO2 measurements in the atmosphere, some by Nobel Prize-winning chemists. The UN IPCC has cooked the books. CO2 was as high as 400 ppm on 1940 before the recent cooling period," Manns wrote. (Ibid.)

Phil C

I sent the following to the person in charge of the NOAA website:
“Dear Mr. Greely,
I just read the article “What is Ocean Acidification”. It contains a gross error in the change of pH of the ocean. A pH change of .1 corresponds to a change in hydrogen ion concentration of ..007%. Acidity, in chemical terms, refers to a pH of less than 7. So a correct description of what has happened is that “the ocean has become .007% less basic”, not “30% more acidic”.
The section on Pteropods shows a meaningless experiment. The pteropods don’t exist in a sterile solution of water at pH 8.0. The oceans include millions of tons of carbonate salts and are in contact with millions of tons more. A more realistic experiment would be to put a lump of limestone(calcium carbonate) in the beaker too.
The section on the mis-named ocean acidification is overblown too. A recent study by the Scripps Institute says: “They found that in some places, such as Antarctica and the Line Islands of the south Pacific, the range of pH variance is much more limited than in areas of the California coast subject to large vertical movements of water known as upwellings. In some of their study areas, they found that the decrease in seawater pH being caused by greenhouse gas emissions is still within the bounds of natural pH fluctuation. Some areas already experience daily acidity levels that scientists had expected would only be reached at the end of the 21st Century.”
Such a wide variation in ocean pH indicates mainly that we don’t know very much about how or why it changes, the reason for the new Scripps study.
Articles like this should be based on sound science and not inflated speculations. Hopefully in the future the rhetoric will be tone down to a level that is more in line with established facts”
I don’t expect the article to be re-written though.

Chem Prof

The original article is correct. A decrease in pH by 0.1 pH units corresponds to a 25.6% increase in relative hydrogen ion concentration, roughly 30 percent to one significant figure.

Jimbo

Sorry mods tips and notes slow.
Climate Wars

“Climate-related natural disasters, economic growth, and armed civil conflict
The analysis of conflict onset shows that climate-related natural disasters do not increase the risk of armed conflict.”
http://jpr.sagepub.com/content/49/1/147.abstract

H/t Marc Morano

John West

Absolutely incredulous.
A pH of 8.2 = 0.00000000630957 mol/L H+ ion.
A pH of 8.1 = 0.00000000794328 mol/L H+ ion.
pH H+ mol/L
0 1
1 0.1
2 0.01
3 0.001
4 0.0001
5 0.00001
6 0.000001
7 0.0000001
8 0.00000001
9 0.000000001
10 0.0000000001
11 0.00000000001
12 0.000000000001
13 0.0000000000001
14 0.00000000000001
BTW: pH is not strickly from 0 to 14, you can have negative pH, for example, a 66 degree Baume (~93%) sulfuric acid’s H+ concentration is way higher than 1 mol/L hence has a negative pH.
@ Chem prof (yea, right): Where do you “prof” (cough, cough) “chem”? I’d like to send a link to your department head.

I must be very stupid but if Chem Prof is right and ocean pH is currently around 8.1 then for it to become acidic the relative hydrogen ion concentration would have to increase by about 280%.
How would this be possible and at what point would the sea consist entirely of hydrogen ions?
Sorry if I’m letting my scientific ignorance hang out but I suspect that the “denizens of the deep” would be struggling to tell the difference between pH of 8.2 and a pH of 8.1.
On the other hand I would have thought that a 25.6% increase in just about any component part of the sea would have been evident to even the dimmest of sea creatures.

Gary

A pH of 8.2 = 0.00000000630957 mol/L H+ ion.
A pH of 8.1 = 0.00000000794328 mol/L H+ ion.
0.00000000794328 / 0.00000000630957 = 1.2589 -> a 26% increase – roughly 30%
.1 log increase in always roughly 26%
.3 log increase/decease doubles / halves (+100% / -50%)
[ decibels are also on a log scale (10 times the log of sound) a 3dB increase or decrease is a doubling / halving ]

Chem Prof

I got onto a real computer and compiled, corrected, and amplified my comments. Here they are, more or less in order:
I don’t think that Chuck is correct in this instance. The pH scale is open-ended, not limited to the range 1.0 to 14.0. That is not a huge error in itself, but the fact that the ocean is buffered amplifies the significance of the 30% increase of hydrogen ion concentration, not diminishes it. This is a large change in acidity, contrary to claims made here.
Please be careful to distinguish between hydrogen ion concentrations and pH. While these are inter-convertible, they are not identical.
If your speed were to increase from 50 mph to 100 mph, the logarithm (base 10) of your speed would increase from about 1.7 to 2.0, roughly an 18 percent increase. I think a judge would be very unimpressed by your argument that you were only faster by 0.3 log units, and would certainly disagree with any assertion that your speed had increased by merely 18%.
The original article is correct. A decrease in pH by 0.1 pH units corresponds to a 25.6% increase in relative [ and I emphasize RELATIVE] hydrogen ion concentration, roughly 30 percent to one significant figure.
I have no idea what John West’s complaint is.

I think Chem Prof is correct. pH is logarithmic to base 10.
10^0.1 = 1.259
This could loosely be described as a 30% increase.
John West, I’m not sure why you’re having a go at Chem Prof.
794328 / 630957 = 1.259

David L. Hagen

Chuck F. Wiese
If “acidity” is understood as the hydrogen ion concentration, then a 0.1 pH unit decrease change in pH from 8.2 to 8.1 is an increase in hydrogen ion concentration from 6.3096 E^-9 to 7.9433 E^-9, or 1.2589. pH is the negative log (base 10) of the hydrogen ion concentration a (sub H^+).
i.e., a 26% (25.89%) increase, not a 30% increase in hydrogen ion concentration.
(PS from a chemistry point of view, I don’t see a problem understanding “acidity” as hydrogen ion concentration.)
The greater issue is people do not understand that to become “acid”, the ocean acidity would have to increase 15,850%.
Far more importantly, is the importance of “chemical buffers” in the Ocean that will effectively prevent the ocean from becoming “acidic”.
See Tom Segalstad’s web site http://www.co2web.info/
especially 4. Chemical Laws for Distribution of CO2 in Nature

An increase in atmospheric CO2 will namely increase the buffer capacity of ocean water, and thereby strengthen the ocean’s capacity to moderate an increase of atmospheric CO2; maximum buffer capacity for the system CO2 – H2O is reached at 2.5 to 6 times the present atmospheric partial pressure of CO2, depending on temperature and alkalinity (Butler, 1982). According to Maier-Reimer & Hasselmann (1987) the borate system also increases the ocean storage capacity for CO2 by more than 20% over an ocean with the carbonate-system alone.
Furthermore, this carbonate buffer is not the only buffer active in the atmosphere / hydrosphere / lithosphere system. The Earth has a set of other buffering mineral reactions. The geochemical equilibrium system anorthite CaAl2Si2O8 – kaolinite Al2Si2O5(OH)4 has by the pH of ocean water a buffer capacity which is thousand times larger than a 0.001 M carbonate solution (Stumm & Morgan, 1970). In addition we have clay mineral buffers, and a calcium silicate + CO2 calcium carbonate + SiO2 buffer (MacIntyre, 1970; Krauskopf, 1979). These buffers all act as a “security net” under the most important buffer: CO2 (g) HCO3- (aq) CaCO3 (s). All together these buffers give in principle an infinite buffer capacity (Stumm & Morgan, 1970).

Please concentrate on correcting the statement to include something like:
“Chemical buffers in the ocean will prevent it from becoming acidic.”

Tsk Tsk

I hate chemistry, but I agree with Chem Prof here in support of the 30% claim. Acid strength is ultimately just a measure of how fully dissociated the acid is in water. As far as I can tell the accepted definition goes from a min(max?) of 0 pH (or 100% dissociated) to a limit arbitrarily close to no dissociation (infinite pH). Since pH is logarithmic, a 30% increase in the hydrogen ion concentration only gives rise to a 0.1 shift in the pH scale, but the solution is 30% more acidic.
What’s misleading in the NOAA posting is just how small a 30% increase really is as compared to the natural variations of ocean acidity. If pH can change by +/- .5 daily –and I’m no expert on fluctuations of ocean acidity, so please correct me– then I think Chem Prof should reconsider what he defines as “large.”
As an aside, has anyone bothered to calculate just what the ocean pH should be assuming that all of the CO2 we emit goes into solution and the ocean is perfectly mixed? Is the 0.1pH mean shift consistent with that?

Jimbo

Great care has to be taken about claims in PH changes.

“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 30 minute 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. 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. Hence, declining ocean pH may be a more acute issue, at least in some areas, than is currently appreciated. Over 70% of the variability in pH we observed can be related to changes in a small set of factors with known mechansitic links to pH: atmospheric CO2, water temperature, the daily photosynthesis-respiration cycle, phytoplankton abundance, upwelling of high CO2 subsurface water, alkalinity, salinity, and the Pacific Decadal Oscillation. We have begun collaborating with Andrew Dickson, an ocean chemist at Scripps Institute of Oceanography, to expand the parameters we measure and interpret our results in greater detail. ”
http://woottonlab.uchicago.edu/index/global-change/global-change-impacts-on-ecological-networks

Henry Galt

I bet $5 this letter gets DR Feely touchy.

Gary Pearse

Chem Prof: 30% increase in a very low H+ concentration is like the interest on one lefta (100th of a dracma). To increase acidity form 8.2 to 8.1 in volves an increase in [H+] of about 25%. To increase it from 8.2 to 7 involves an increase in [H+] of 1600%. To increase pH from 8.2 to 1.0 requires an increase in [H+] of… wait for it good doctor… 1584893200%. If you still think your 30% increase is significant, you should turn in your doctorate – egad who are these people teaching our children. I certainly wouldn’t call myself “Chem Prof” if you don’t understand pH. Indeed divide your 30 by this figure to get an idea of how insignificant it is.

Dan Johnston

Sea water is an entirely different animal than most solutions where pH is measured due to its high ionic strength. I’ve copied a discussion from Wikipedia that outlines the problem:
Seawater
The pH of seawater plays an important role in the ocean’s carbon cycle, and there is evidence of ongoing ocean acidification caused by carbon dioxide emissions.[16] However, pH measurement is complicated by the chemical properties of seawater, and several distinct pH scales exist in chemical oceanography.[17]
As part of its operational definition of the pH scale, the IUPAC defines a series of buffer solutions across a range of pH values (often denoted with NBS or NIST designation). These solutions have a relatively low ionic strength (~0.1) compared to that of seawater (~0.7), and, as a consequence, are not recommended for use in characterizing the pH of seawater, since the ionic strength differences cause changes in electrode potential. To resolve this problem, an alternative series of buffers based on artificial seawater was developed.[18] This new series resolves the problem of ionic strength differences between samples and the buffers, and the new pH scale is referred to as the total scale, often denoted as pHT.
The total scale was defined using a medium containing sulfate ions. These ions experience protonation, H+ + SO42− ⇌ HSO4−, such that the total scale includes the effect of both protons (free hydrogen ions) and hydrogen sulfate ions:
[H+]T = [H+]F + [HSO4−]
An alternative scale, the free scale, often denoted pHF, omits this consideration and focuses solely on [H+]F, in principle making it a simpler representation of hydrogen ion concentration. Only [H+]T can be determined,[19] therefore [H+]F must be estimated using the [SO42−] and the stability constant of HSO4−, KS*:
[H+]F = [H+]T − [HSO4−] = [H+]T ( 1 + [SO42−] / KS* )−1
However, it is difficult to estimate KS* in seawater, limiting the utility of the otherwise more straightforward free scale.
Another scale, known as the seawater scale, often denoted pHSWS, takes account of a further protonation relationship between hydrogen ions and fluoride ions, H+ + F− ⇌ HF. Resulting in the following expression for [H+]SWS:
[H+]SWS = [H+]F + [HSO4−] + [HF]
However, the advantage of considering this additional complexity is dependent upon the abundance of fluoride in the medium. In seawater, for instance, sulfate ions occur at much greater concentrations (> 400 times) than those of fluoride. As a consequence, for most practical purposes, the difference between the total and seawater scales is very small.
The following three equations summaries the three scales of pH:
pHF = − log [H+]F pHT = − log ( [H+]F + [HSO4−] ) = − log [H+]T pHSWS = − log ( [H+]F + [HSO4−] + [HF] ) = − log [H+]SWS
In practical terms, the three seawater pH scales differ in their values by up to 0.12 pH units, differences that are much larger than the accuracy of pH measurements typically required, in particular, in relation to the ocean’s carbonate system.[17] Since it omits consideration of sulfate and fluoride ions, the free scale is significantly different from both the total and seawater scales. Because of the relative unimportance of the fluoride ion, the total and seawater scales differ only very slightly.
The upshot of all this, especially considering the third sentence from the end, is that changes in acidity must be clearly demarcated in terms of which scale is used for measuring pH in seawater. This makes manipulating pH measurements relatively easy and can cause problems when different buffer solutions are used to set the pH meter. It would be nice to see just how the acidity changes (pH measurements) mentioned in the thread were derived. Until that is done, the 30% increase in acidity, buffered or not, is meaningless.

Chuck Wiese

Chem Prof: In all of the work- ups and computations I have seen NOAA and others do when talking about ocean acidity, the units have always been referenced in units of pH. I have never seen work- ups in ion concentration. If you look at mappings of global ocean pH, we see it varies naturaly by up to 5% of pH units in either direction from the mean of 8.2 pH units.
A change of .1 units of pH is well within the natural variability of 5% of 8.2 pH units, so there is no legitimacy to the story if it was looked at in this manner. But if you use ion concentration, you get well outside of the 5% variability of pH units. I suspect that is why they did this. To sell a scary story to the public to convince the voting public action is needed to sequester atmospheric CO2. But the fact of the matter is, there is no case to be made for this with the data provided and they misled the public when they reported the “findings” in this manner.
BTW, my computation of 33% was off of the mean global ocean pH of 8.2 units moving to 8.1 units. Close enough to the relative numbers to see what was done here. And contrary to your claim, hydrogen ion concentration is not a unit of pH. The equation speaks for itself.

Hey Chuck, we’ve known for some time now that these people are liars and frauds. It is sure taking a long time for them to be held accountable though. As for the Oregonian, they sent me free newspapers for several months right up until the day after the recent election. I wonder who was paying for that scam. PS I used the newspapers for firestarter and chicken box liners. I hope I didn’t diminish the intelligence of my chickens. And I voted my consience which does’nt allow me to vote for any liberal and very few so called conservatives. Ron Paul for president is my hope in the political arena as I think with anyone else it will be more of the same corruption.

Will tiny variations in Ph matter in a Pacific now Japan’s nuclear waste dump with hundreds of trillions of bequerels of the most toxic radioactive metals on the planet trickling down through the water column, Pacific-wide? 100% of the Blue Fin Tuna off San Diego have Cesium 137 in them. Ph won’t matter…at all.
Why is the news blackout so total of this disaster? It’s criminal.

John West

For anyone interested in the actual chemistry I recommend:
http://www-naweb.iaea.org/napc/ih/documents/global_cycle/vol%20I/cht_i_09.pdf
Take a close look at “Fig.9.10 Schematic representation of an open system, consisting of a water mass in exchange with an infinite CO2 reservoir and with carbonate rock.
The X axis is in PCO2 in the water in atmospheres, remember two things: 1) PCO2 in the water always less than PCO2 in the air it’s in equilibrium with due to Henry’s Law and 2) if they had labeled the X axis in ppm relative to the atmosphere then 10^-5 would be 10 ppm, 10^-4 would be 100 ppm, 10^-3 would be 1,000 ppm, 10^-2 would be 10,000 ppm and so on.
Note the logarithmic relationship between PCO2 and pH; yes another manifestation of the law of diminishing marginal returns strikes.
Also note the Y-axis is alkalinity which is basically a measure of a solution’s ability to resist changes in pH.
There will be those that say this “alkalinity response” will take thousands of years; to them I say download and chart the data from:
http://132.239.122.17/co2qc/batches.html
You’ll see the alkalinity, salinity, and total carbon dioxide vary in conjunction with each other on very short time scales and there has been no trend since they started taking samples in 1990.
Thanks to things like Henry’s Law, the logarithmic relationship between pCO2 and pH, and Carbonate alkalinity we don’t IMO have to worry about “Ocean Acidification”.

John F. Hultquist

Also in the quote: “. . . the surface waters of the ocean could be nearly 150 percent more acidic, . . .”
How should one interpret the above?
~~~~~~~~~~~~~~~~~~~
My interest in pH is trying to make blueberry plants happy. The little buggers like acidic soil. The irrigation water has dissolved minerals. See the problem?

Dan Johnston

http://en.wikipedia.org/wiki/File:WOA05_GLODAP_pd_ALK_AYool.png
The link above shows a graphic of ocean alkalinity in the 1990’s from Wikipedia. Note the low alkalinity off the NW coast of North America. This makes the 30% increase statement even more bizarre as a “scientific” assertion.

Gerry Parker

Hurrah Wagathon! Someone finally gets it right! Unless you disolve (pretty much the entire planet (ok that’s an overstatement, but not by much)) you’re not going to move the ocean’s pH by much. Look up alkalinity to start. It’s not as easy to move the ocean’s pH as the layman would think. Or that of a 100 gallon saltwater aquarium for that matter.
As with surface temperature and salinity, pH can vary a bit from place to place, and by a bit I mean tenths. Reading some of the crap posted by some folks, you would be shocked to go to some bays and estuaries and take simple water sample measurements and see the resilience of ocean life. Just like the water temperature debate, it is a trivial thing to GO into the ocean where the water temperature swings 25F over the course of a year and observe that it all doesn’t just die, but thrives.
Except maybe you only go to the ocean a few times in your life and don’t realize these things swing widely over the year.
At some point please begin to realize this planet is huge and has been around a long time. It has survived worse than us.
Gerry

dcfl51

Does anyone here know why we keep being told that the pH value of the oceans has changed by 0.1 since the start of the Industrial Revolution ?
Is there a time series of actual measurements going back that far ? If not, how far back does the longest time series go ?
Is this value based on a proxy ? If so, is the causal relationship well established both qualitatively and quantitatively ?
This is a serious question if anyone knows the answer.

Chuck Wiese

@ Dave Hagen: Yes, your numbes are more precise than mine when you include the the numbers right of the decimal point in the mantissa. I just solved for H+ and my Texas Instrument 30XA calculator rounded the numbers in both directions to the nearest whole number. That left precisely the margin of error that reduces the ion increase to 26% rather than 33%. They called it a 30% increase in acidity in the article, but you get the picture.

dp

Tatoosh Island is at the entrance of the Straight of Juan De Fuca. That there is complexity in the ph of the water found there should come as no surprise given the raw sewage from Vancouver Island, the outflow of all the rivers of Puget Sound, and the by-products from the industrial base found in Puget Sound which itself is a bit of a toilet bowl. I think they are wasting their time monitoring the ph of the ocean at Tatoosh as there is zero chance it reflects a global norm. Just my opinion but I suspect they will learn more by talking to the oyster farmers in the area.

Steve in SC

Boys and girls there are no angels on the head of this pin.
Assuming that the ocean has warmed due to CO2 concentration and then saying that the relative alkalinity of said ocean has decreased by this selfsame CO2 leaves one with a circular argument both ends of which are disproved by the physical properties of the CO2 and the ocean.
Perpetual motion anyone?

Hoser

The discussion got pretty pissy. I wonder whether people actually read and understood what others were posting. For example, unless I missed something important, ChemProf was right on. How do we gain by creating a circular firing squad? Let’s focus on the real culprits, not each other… unless you are a troll, then you’re fair game.

Arron

I’ve always been taught to run the numbers. Only this time I don’t know how. According to Wikipedia, the volume of all of the oceans is 1.3 billion cubic kilometres. The letter says the pH change is from 8.2 to 8.1. Does anyone know how much CO2 it would take to change 1.3 billion cubic kilometres of salt water from pH 8.2 to 8.1?

Arfur Bryant

A pH change from 8.2 to 8.1 cannot be truthfully described as ‘becoming ‘more acidic’. Something which is not acidic in the first place cannot become ‘more acidic’.
Saying a change from pH 8.2 to 8.1 is ‘becoming more acidic’ is like saying a grossly obese person who loses a few pounds weight is becoming ‘more anorexic’.

John West

@dcfl51
” I’m not sure why you’re having a go at Chem Prof. 794328 / 630957 = 1.259″
Because even though the numbers do calculate to roughly 30%, it’s incredibly inappropriate to apply percentages with pH.
30% means 30 per 100 but on the pH scale there are many many “hundreds”; if you calculate % change in acidity from say 14 to
0 its like a 100000000000000% change, Making 30% seem much more insignificant than the 30 out of 100 implied by using percentages.
Any real chemistry professor wouldn’t hide behind anonymity and support such a misleading practice, IMO.
(I’m on a mobile device now, so somebody might want to check my zero count.)

Billy Liar

Larry Butler says:
June 30, 2012 at 10:53 am
Will tiny variations in Ph matter in a Pacific now Japan’s nuclear waste dump with hundreds of trillions of bequerels of the most toxic radioactive metals on the planet trickling down through the water column, Pacific-wide?
Larry, why don’t you hide in your basement if you feel that way? No, wait … radon and the daughters of radon (polonium 218 > lead 214 > bismuth 214 > polonium 214 > lead 210 > bismuth 210 > polonium 210 > lead 206(stable)).
Don’t ever let me catch you eating mussels, they accumulate Polonium 210: http://www.radioecology.info/Bergen2008/proceedings/16.%20Carvalho%20O.pdf.
Watch out for other people too, they’re full of radioactive potassium 40 at around 0.1 million bequerels per person: http://www.physics.isu.edu/radinf/natural.htm
Be careful with travel too; some beaches in Brazil and India and an area in China have a high occurrence of monazite, a mineral containing thorium, uranium and radium.
There are megabequerels everywhere – don’t touch that banana!

Man Bearpig

NOAA should know better than this, it is a schoolboy error of such magnitude that it makes a laughing stock of the organisation. Lets hope this gets posted everywhere and show the world what a bunch of amateurs they really are.

dennisambler

This was no error, it is deliberate and part of the “communication of climate change” strategy. Jane Lubchenco has a video on the NOAA website where she adds vinegar to a flask containing a stick of chalk. Lo and behold, it fizzes and starts to dissolve. This is what is happening in the oceans, don’cha know. In 2009, Lisa Suatoni of NRDC, did the vinegar trick in the shockumentary, “Acid Test: The Global Challenge of Ocean Acidification”, fronted by Sigourney Weaver. Appearing in the film was Professor Stephen Palumbi, of Stanford University’s Hopkin Marine Station. He also has a video using the vinegar trick, showing how vinegar will dissolve coral. It is for school children.
Also from Stanford, at the Department of Global Ecology at the Carnegie Institution for Science and another “Acid Oceans” film star is Dr Ken Caldeira, who helped to kick start the current scare in 2003, (Caldeira and Wickett), a paper which was quoted extensively in AR4: Working Group I: The Physical Science Basis, 5.4.2.3 Ocean Acidification by Carbon Dioxide.
“The consequences of changes in pH on marine organisms are poorly known (see Section 7.3.4 and Box 7.3). For comparison, pH was higher by 0.1 unit during glaciations, and there is no evidence of pH values more than 0.6 units below the pre-industrial pH during the past 300 million years (Caldeira and Wickett, 2003). A decrease in ocean pH of 0.1 units corresponds to a 30% increase in the concentration of H+ in seawater, assuming that alkalinity and temperature remain constant.”
Hence we get the claim that “the ocean” has become 30% more acidic since the start of the industrial revolution.
In 2005, the Royal Society published a report entitled, “Ocean acidification due to increasing atmospheric carbon dioxide”. The members of the committee producing that report included one Dr. Ken Caldeira, at that time at Lawrence Livermore laboratory. He was accompanied by scientists from UEA and Tyndall Centre affiliate institutions. This happens all the time, different institution, same people, same data, equals yet more consensus.
See more at http://scienceandpublicpolicy.org/originals/acid_seas.html
The Oregon shellfish story is also a long running one, where once again they try to attribute a natural phenomenon to global warming. In 2008, this story appeared, “Northwest Shellfish Industry in Panic over Die-off of Oysters” (Oregon Live blogspot)
By Ron Morris June 08, 2008
“An invisible microbe that thrives in warm ocean water has undermined the Northwest’s prized oyster supply, killing billions of young larvae that mature into the succulent shellfish known across the world. The bacterium, Vibrio tubiashii, is related to another species that can sicken people who eat raw shellfish. This one doesn’t bother people – it kills shellfish in their larval stage, before they latch onto rocks to grow.”
In 2010, this press release appeared from Oregon State University: “Ocean Acidification Hits Northwest Oyster Farms” Scientists Say Carbon Dioxide in Oceans Could Mean Curtains for Shellfish. (Lubchenco is still on leave of absence from Oregon State as Zoology prof, I believe)
“The scientists went to work and learned that something was making the oceans too acidic and preventing the oyster larvae from growing shells. No shells means certain death. The chemistry is very simple. It is 101. Carbon dioxide makes the water more acidic, that is irrefutable,” said Burke Hales, Oregon State University professor of oceanography.” They didn’t of course mention anything about the Vibrio infection reported in 2008. NOAA scientist Richard Feely confirmed their conclusions: “While the effects are just beginning to be seen in our hatcheries, the oceans are now changing faster than they have ever changed over the last 200 million years,” said Richard Feely of the National Oceanic and Atmospheric Administration, who has been studying ocean acidification for 20 years.”

Steven Kopits

No posting on the record heat, storms?

Peter Pearson

I’m a fan of WUWT, and I worry that Chuck’s letter will not improve WUWT’s credibility. It seems clear that Feely reasonably thinks of ocean acidity in terms of hydrogen-ion concentration. A change of 0.1 in pH is, rounding roughly, a 30% change in hydrogen-ion concentration. No big deal.
In fact, it would be quite peculiar to talk about percentage changes in pH: percentage changes, by definition, refer to changes in the “distance from zero”, but zero on the pH scale has no special significance, being where it is merely because we happen to measure volumes in liters and define a mole to be 6×10^23 things. Talking about percentage changes in pH would be like saying that a temperature of 60 degrees Fahrenheit is 20% warmer than 50 degrees. Yes, you could say that, but it says more about your way of measuring temperature than how hot it is.

jorgekafkazar

The referenced article says this:
“Over the last 100 years we’ve made the ocean a little more acidic than it used to be,” he said. “There is a 30 percent increase in the acidity of the ocean. If you are an oyster lover, that little bit more acid is a big problem. Eventually it will put our hatchery out of business.”
Ignore the fact that 30% is trivially different from 25%. Ignore also the nitpickery that the acidity isn’t increasing; the alkalinity is decreasing. Acidity is the concentration of hydrogen ions in solution. This has, indeed, gone up by roughly 30%. The paragraph above [quoting Barton] is correct, or reasonably close enough to it for normal journalistic standards. Chuck Wiese has created a tempest in a teapot at best and, more likely, has erroneously accused Barton, et al, of error regarding the paragraph.
It is highly unlikely that the oyster problem is due to lower alkalinity, however. I suspect BOD is the culprit.

Steven Kopits says:
June 30, 2012 at 12:25 pm
“No posting on the record heat, storms?”
Same reason for no posting of record cold in other parts of the world such as New Zealand, the South Pole, and Finland – it’s weather.

Mitch

Gary Pearse: An increase in pH is a decrease in H+ concentration
pH = 7 –> [H+] = 10^-7
pH = 8 –> [H+] = 10^-8
NOAA plays with the numbers. Normally, a scientist would use a pH scale to describe the acidity. NOAA uses two units of scale in its statement; pH and concentration. However, the statement implies only the pH scale. This would mislead the general public.

Caleb

Even on a hot day you can lift the CO2 fire extinguisher from the wall, give it a shake, and hear the CO2 inside sloshing about. Under high pressure it is a “liquefied gas.”
A mile down under the sea, in the warm water by deep-sea vents, CO2 exists as a “liquefied gas.” Little trickles come oozing out of the vents and wander off along the sea bottom.
I really can’t think of a better way to dissolve CO2 into sea water than that combination of hot water, high pressure, and warm and liquid CO2.
The funny thing is that the critters down there don’t look like their shells are dissolving. In fact, the crabs seem to be dancing in the flood lights and smiling at the sub’s cameras, happy as the clams.