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

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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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91 thoughts on “NOAA’s Pacific Marine Environment Laboratory Carbon Program goes overboard on ocean acidification – leaves uncorrected error

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.)

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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 ]

  14. 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.

  15. 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

  16. 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.”

  17. 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?

  18. 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

  19. 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.

  20. 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.

  21. 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.

  22. 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.

  23. 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.

  24. 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”.

  25. 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?

  26. 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.

  27. 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

  28. 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.

  29. @ 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.

  30. 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.

  31. 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?

  32. 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.

  33. 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?

  34. 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’.

  35. @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.)

  36. 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!

  37. 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.

  38. 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.”

  39. 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.

  40. 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.

  41. 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.

  42. 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.

  43. 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.

  44. @Chem Prof

    There’s technically right and there’s actually right. Humans use a range of scales for good reasons, and it is important to use the relevant ones for those reasons.

    pH is (negative) log because that is how organisms perceive acidity. They don’t perceive it in a linear scale, so it shouldn’t be quoted in one. No-one, but no-one talks about acidity other than via pH.

    As a Chemical Professor – cough! – you will be aware that there is a p[OH] measure too. So why not quote the alarming story that – oh noes! – hydroxide concentration in the oceans has fallen by 80%. I would hope you would see how stupid it was to use it, regardless of being technically true.
    Scientists should be above misleading statistics in order to add scare value. The end effect is not that they persuade, but that their statements come to be read in the same way we read politicians’ statements. Scientists have a measure of acidity that they should use, not play hocus-pocus with whichever number does their propaganda job better.

  45. The argument about ocean acidification is absolutely stupid if all the co2 in the world were added to the oceans it would still be above the ph of pure water. It would still be on the side of alkaline and not acid. Of course we would all be dead for there would be no plants and no food and as we ourselves are carbon based we would all end up looking like the brains of warmists.

  46. Chem Prof, your arguments (be they hydrogen ion concentration change or pH change) make no difference whatsoever. The change discovered is within the natural variability, IE the null hypothesis, which still stands. When natural variability is buried by the supposed anthropogenic CO2-pH mechanism, post again.

    The sky is not falling just because a walnut hits your head.

  47. Once again the “ocean acidification” canard is resurrected by grant-seeking science charlatans and global warming alarmists. The problem is that in measuring ocean pH, the error bars are larger than the imagined change. Statistically, there is no change in pH.

    WUWT readers have argued and won this point here many times over the past couple of years. “Ocean acidification” is simply one more baseless facet of the catastrophic anthropogenic global warming scare. For a review of how thoroughly “ocean acidification” has been debunked, see these links:

    http://wattsupwiththat.com/2011/01/10/ocean-acidification-chicken-of-the-sea-little-strikes-again

    http://wattsupwiththat.com/2011/11/24/chicken-little-of-the-sea-visits-station-aloha

    http://wattsupwiththat.com/2011/12/28/the-fishes-and-the-coral-live-happily-in-the-co2-bubble-plume

    http://wattsupwiththat.com/2011/12/27/the-ocean-is-not-getting-acidified

    http://wattsupwiththat.com/2011/10/25/the-reef-abides

    http://wattsupwiththat.com/2010/06/19/the-electric-oceanic-acid-test

  48. I wonder what the NOAA response will be, if any. WUWT had a story about this in 2010. The multi-national organisation, Partnership for Observation of the Global Oceans, POGO, issued a press release in 2010 stating:
    “The ocean surface is 30 percent more acidic today than it was in 1800, much of that increase occurring in the last 50 years…

    “The Foundation says the average level of pH at the ocean surface has dropped from 8.2 to 8.1 units, “rendering the oceans more acidic than they have been for 20 million years.”

    Please send $15 billion plus $5 billion per year.

    http://wattsupwiththat.com/2010/11/01/scientists-plead-for-15-billion-ocean-acidification-monitoring-system/

    http://www.ocean-partners.org/about-pogo/partners

    POGO are busy little bees. Over the next year they have scheduled about 36 meetings and workshops in places like India, China, Brazil, Usa, Hawaii, France, Japan, Australia and ….er…. Hull in the UK.

    http://www.ocean-partners.org/meetings-and-workshops

  49. The researchers admit that the alkalinity decreases when cold water from massive upwellings move into the oyster growing areas. It is well known that there are numerous active underwater volcanos and black smokers along the coast that emit CO2 and SO2. The San Juan Plate is nearby and active. These sources may well account for virtually all of the reduced alkalinity.

    Moreover, it is well know that Pacific oysters are intolerant to relatively small decreases in water temperature. A few degrees below the norm means death to oysters and their ability to reproduce. When water warms, the oysters begin to grow again. I have observed this phenomenon several times while cruising along the British Columbia coast and visiting well known prolific oyster growing warm water fiords. Oysters come and go when water temperatures vary by a few degrees F.

    The researchers make no mention of the influence of reduced water temperature on oyster viability, which can falsify the hypothesis. Moreover, they appear to have ignored the impact from underwater activities that put massive amounts of CO2 and SO2 into the water. These acid making gases may well be the primary cause of reduced alkalinity and also falsifies their hypothesis.

    My layman’s understudying of scientific method is that those advancing a hypothesis have the burden of proving it, and disclosing and disproving contradictory facts, data and research. I suspect the cost of analyzing and quantifying sources of absorbed CO2 in sea water may be enormous, that is assuming that it is feasible.

  50. Mike Jackson says:
    June 30, 2012 at 10:03 am
    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.

    Presumably the CO2 concentration went up from 280 ppm in 1750 to 390 ppm today or about 39%. If you were in a room where the CO2 was 280 ppm and then went into a room where the CO2 was 390 ppm, do you think you would notice? Now as for the pH discussion here, any change of 0.1 in the pH changes the hydrogen ion concentration by 26%, but there is a world of a difference between a change of pH from 1.1 to 1.0 versus from 8.2 to 8.1. 26% of peanuts is still peanuts.

  51. Pamela Gray says:
    June 30, 2012 at 1:39 pm

    Pamela, you’re the poster child for my previous comment.

  52. Gary Pearse says:
    June 30, 2012 at 10:45 am

    “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.”

    Chem Prof’s 30% increase is reminiscent of our long lost friend R. Gates who was fond of crowing about a “40% increase of CO2″. Technically correct but as many pointed out to him, a 40% increase of squat is still squat. Anytime I see percentages being used my skeptic alarm goes off loud and clear.

  53. The reason the change in pH is meaningless in this situation is that in a pure system where only H+ is considered to be driving pH, the change is one gram of hydrogen ions in one billion liters of water. So if things have now become dangerous at the part per trillion level of change life should hve been wiped out billions of years ago.

  54. Man Bearpig says:
    June 30, 2012 at 12:22 pm
    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.

    Rather, it’s a Machiavellian attempt to deceive with a technically correct obfuscation. The average reader will think that we’re 7/10ths of the way to an acid ocean.

    “A truth that’s told with bad intent / Beats any lie you can invent”

    If this were an ad that employed this deception, liberals would be screaming about it.

  55. Chem Prof misses the point, it’s NOAA’s carefully chosen misleading words that can leave many readers with a misunderstanding.

    NOAA states: “Since the beginning of the Industrial Revolution, the pH of surface ocean waters has fallen by 0.1 pH units.”

    To many readers, the pH scale is a meaningless scientific figure, so a science writer is expected to interpret this pH figure into a figure or statement of impact that the reader can understand.

    Here is NOAA’s follow up sentence which, to the general public reader, is in the form of an interpretive impact explanation: “Since the pH scale, like the Richter scale is logarithmic, this change represents approximately a 30 percent increase in acidity.”

    To many non-scientific readers this implies a hugely significant increase in environmental impacts – 30% more acidic ! NOAA compound the misleading nature of this statement by not making it clear that this is a reference to a percentage change in hydrogen ion concentrations.

    NOAA don’t need to use the misleading acidity figure – their follow-up paragraphs (under the heading “The Biological Impacts”) are adequate for explaining the claimed impacts.

  56. The whole sea water PH measurement story is a false numbers game.

    Anytime someone states a percentage number, your first question should always be a percentage of what?

    Geez, it’s a 30% increase! Oh, and just what constitutes a 100% totality? Assuming that 100% is the whole enchilada, the absolute total sum. In my mind and in the minds of many people, 30% is a change of magnitude almost 1/3 of the total.

    But but, says the alarmists, our 30% number is relative. It represents a percentage change from a ridiculously low number to another ridiculously low number so the ‘relative’ change looms very large.

    What? Says the the questioners (us) just what is that percentage as a total of the whole? On a scale from 0 – 14 the percentage change from 8.1 to 8.2 or versus-visa is truly trivial. So is trying to relate ph measurement to the richter scale. Ion changes per liter of water just don’t relate to 700 km of faulted continental crust slipping slipping meters. Yeah yeah, it’s all relative.

    Wow, I just bought some super magnets. I bought the 4.5mm size. They’re 28.5% bigger than the 3.5mm magnets! I’m just overwhelmed by the massive increase in magnet power! /sarc

  57. As popularized by Mark Twain and others: “There are lies, damn lies, and statistics.” Someone should bring Darrell Huff’s 1954 book, “How to Lie with Statistics” out of mothballs, and update it with all the ‘scientific’ examples that are currently rife in the arena of AGW scaremongering.

  58. Chem Prof says:
    June 30, 2012 at 9:42 am
    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.
    ======================================================================
    The article kind of sounds like they were using the scariest sounding way to report the number. “30%” sounds much bigger than “0.1”.
    Pretty common trick if you’re trying to influence rather than simply report.
    I don’t know the actual numbers here but when they try to demonize insurance companies they report their profits grew by, say, $10,000,000,000. If they are not out to demonize then they report their profits grew by, say, 1%. The honest thing would be to report both.

  59. So it seems that it’s just more lazy scientists at work. The global Ph is not the problem. It’s a local problem that might take some research and effort to work out. Unfortunately the oyster farmers succumbed to temptation, went to the worst possible place for accurate information, and got the party line…..global warming. They’ll get no sympathy from me.

  60. 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? 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.

    You do not appear to have been paying attention during your Nucleonics class in engineering school and have gotten yourself unnecessarily excited.

    Lets look at the radiation released at Fukushima: 13,600 TBq of Cesium-137. There was some Iodine-131 and some Cesium-140 released as well but this has half-lifed itself out of significance. The ocean volume is 1386000000 cubic kilometers. Dividing the released radiation by the ocean volume: 13,600 TBq/1386000000 km3 = .0000098 Bq m-3. For comparison, the ocean background radiation is 2-3 Bq/m-3 for Brazil and 35.2 Bq m-3 for the Baltic Sea. The radiation from Fukushima isn’t just insignificant – it is barely measurable.

    The ICRP in 1928 adopted the linear no-threshold model for radiation and there is no conclusive science evidence that it is a valid model. There is a lot of evidence that it is not. Normal background radiation is 2 mS (milliSieverts) per year – 15% is produced by your own body. This is a global average, the rate varies by location: the US background rate is 3.6 mS/yr, the Australian rate is 2.4 mS/yr, and the rate for Ramsar, Iran(whose residents have an abnormally low cancer rate) 260mSv . The radiation level for optimum health is 120-200 mSv (milliSievert) annually (hormesis hypothesis). The radiation level has to reach 2 Sieverts/year before cancer mortality is as high as the death rate from normal background radiation. Allowing radiation levels up to 2 Sv/yr will save lives.

    The reason that there is no news is there is no disaster. The lost of equipment, power (due to damaged equipment) and contamination of the nearby land does get reported. What is really amazing is the TEPCO (Japanese) staff bravely dealt with reactors that had gone uncooled for 24 hours.and managed to contain them. I doubt American staffs would have done as well.

  61. I’ve experienced a 100% increase of Labatt Blue content in my body since I started reading this comment thread. Incidentally, I was so intrigued by the scientific discussion that I neglected my second open bottle for a while. Otherwise I’d have been tempted to go to the source one more time and my mathematical models suggest that I would have suffered a catastrophic 200% volume increase.

  62. I have three problems with the statement about a “30% increase in pH”. First, we have no observations saying it has changed that much, just claims without actual data to support them.

    Second, applying percentages to logarithmic scales doesn’t work. The scales are logarithmic for a reason.

    Third, and more to the point, they have not provided the critical context. Suppose we use pH. The pH according to the article has changed by 0.1 pH units. To give a sense of how big a deal that is, here’s a graph of the pH of the intake water at the Monterrey Aquarium:

    SOURCE

    Looking at that, should we be concerned about a claimed change since 1750 of 0.1 pH units?

    I say even if it were real it’s lost in the noise, it changes much more than that in a couple weeks in Monterrey.

    Now, let’s provide some context for the changes in Monterrey in percentage terms. In a few weeks, the water there goes from a pH of 7.7 to a ph of 8.2. According to the method used in the article and approved of by the “chem prof”, that’s a change of about 316% in a few weeks … and we’re supposed to be upset by a claimed (not observed but claimed) increase of 30% in 250 years?

    Really?

    That’s why context is crucial, whether you measure in pH units as you should, or in percentages as makes no sense … either way you need context.

    w.

  63. I’m not going to sit here and point out the stupidity of using percentages on a PH scale but it got me thinking can anyone think of a valid use of percentages in pure science (You know science applied to real world data and measurements and not pulled out your ear to prove your worth your grant), or is it just used by bankers to push up and down the price of the stock markets and bonds, etc or stats guys to keep themselves in jobs (Mr McIntyre has changed my mind on stats guys though)?

  64. J. Philip Peterson says:
    June 30, 2012 at 12:44 pm
    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.

    Same reason for not posting of “the coldest and wettest April to June in at least 100 years” in UK.

    We are, officially, still in a drought!!!!!!!!

  65. “””””…….Bill Tuttle says:

    June 30, 2012 at 8:36 am

    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……”””””

    Jane Lubchenko did a famous (reported here) demonstration (experiment) to show that corals can grow in ordinary (fresh) tap water, including presumably its chlorination, and dental fluoridation, if you simply dye the water blue with an ordinary “laboratory blue dye”.
    You chemistry whizzes (I ain’t one) can explain why you go around dyeing things blue with “ordinary laboratory blue dyes”.
    Back in school when I was actually forced to do some chem experiments, we used some gunk called phenolpthalene; or words to that effect, to determine the pH of some solution or other, similar to litmus paper I guess, but we never deliberately dyed anything blue to grow corals in it.
    Then friend Jane chilled the hell out of the blue tap water with dry ice to show that corals won’t grow in cold tap water. As I recall the cold tap water went yellow; which I assume explains why sometimes snow is yellow and they don’t recommend eating yellow snow; evidently it kills corals too.

    Jane never did her experiment with ordinary ocean water that corals DO grow in. Like why didn’t she just import some Aussie ocean water from the Great Barrier Reef, where corals grow. Toss her “ordinary laboratory blue dye” in there, and then toss some dry ice in to chill it, to see if the corals could survive. If the hcilled GBR ocean water doesn’t go yellow when you chill it, then maybe the corals won’t dye (that’s die).

  66. “””””…..E.M.Smith says:

    June 30, 2012 at 1:51 pm

    Shell fish don’t have a problem with acid water anyway:

    http://chiefio.wordpress.com/2012/03/08/clams-do-fine-in-acid-water/.

    Fresh water clams are an existence proof that acid water ( up to 4.x pH) does not harm them…..”””””

    I am somewhat of an expert on fresh water clams, and their effectiveness in growing in acid water; to wit, the California Sacramento/San Joachin/Mokelume Rivers Delta system.

    A few years ago, while fly fishing for striped bass with my son, in a secret location, in Frank’s Tract, I actually made a total of 25 casts, for a total of 24 grabs with 24 successful landings, and live releases, with an unbroken string of 21 grabs and hookups in 21 successive casts.

    Heck no they weren’t striped bass, they were fresh water clams. Every one of them had the pointy end of my fly in its mouth; excuse me, shell ! I guess the bed of clams were just sitting there on the bottom, open to catch food coming by in the current, and every one of them grabbed my fly, as it brushed over them. The clams were about one inch diameter, and the fly was about four inches long. For the record, it was a chartreuse and white Clouser, tied on a 3-0 hook. Every one had it’s shell closed on the hook point; which evidently is the tasty part of a Clouser. Yes I did feel the grab, and set the hook on them, but none suffered any damage.

    It’s still a secret location, because my son and I have never been able to find that clam bed again; maybe I scared them all off to some other place.

  67. Willis Eschenbach says:
    June 30, 2012 at 11:22 pm

    I have three problems with the statement about a “30% increase in pH”. First, we have no observations saying it has changed that much, just claims without actual data to support them.

    Willis, I fully agree that a “30% increase in acidity” is an absurd claim and only intended to scare people with large sounding figures. For coastal waters, indeed the pH differences are far more variable and have no influence on fish or corals or clam shells…

    But there are a few longer term observations which show that there is a small decrease in pH in non-coastal ocean waters, be it that the pH is not directly measured, but calculated from DIC and alkalinity changes. See:

    http://www.bios.edu/Labs/co2lab/research/IntDecVar_OCC.html

  68. Instead of arguing about what pH actually means and whether the oceans are turning to HCl /H2CO3or not let us look at the actual observations of ocean surface water pH.
    Whilst not measured everywhere, ocean pH has been found to vary, daily, seasonally and cycically over longer periods, from pH7,4 to pH 8,3. All reported reductions have fallen within this bracket. Water issuing from the deep ocean black smokers, volcanic vents on the ocean ridge system, have a pH of 4.5 or lower but this rapidly increases the further away from the vent the pH is measured. There is a buffer stage at work in the ocean water, the bicarbonate buffer. This is the next stage in the solution of CO2 in the sea water the first stage being the formation of carbonate ion from the CO2/H2O. This bicarbonate stage increases the pH and is continuous. Remember that sea water is an ionic solution not a simple mixture of chemicals so the identification of H+ in it is no surprise.
    It is the bicarbonate ions that molluscs etc use in the formation of shell or skeletal frames. During the early Ordovician CO2 levels were up to 8000ppmv but the ocean pH was similar to today’s and molluscs and corals thrived probably due to the excess bicarbonate building blocks reduced energy required to grow shell to divert energy to grow larger.

  69. Phew! Weren’t they lucky to have chosen the H+ ion concentration as reference, and not the OH- (OH minus) ion concentration?

    Remember that in water the two are firmly related – multiplying the two concentrations gives 10E-14. At a neutral pH of 7 both are 10E-7, and at pH of 8.2 the H+ concentration is 10E-8.2, while the OH- concentration becomes 10E-5.8.

    So, if the water were ‘acidifying’ from pH8.2 down to neutral at pH7.0, some 94% of all OH- ions were already lost, and many would say that pretty much all of OH- is lost already, losing only 6% more cannot possibly have any effect. Therefore it almost couldn’t get any more acidic than that? No catastrophe, everything is safe at this point? Imagine what poor message this would have sent!

    The flaw in thinking is the ignorance about biological/chemical/physical effects being governed by what is correctly measured by pH, namely the electrochemical potential, as the first commenter has already pointed out.

  70. All of the above have an error. pH is NOT described by concentration. It is described by activity. Activity is related to concentration through factors such as as total ionic strength (for dissolved ionic species), the presence of biota, dissolving-but-not-dissolved species, precipitates, colloidal sized solids … all these affect the relation between concentration and activity some in ways that cannot be accounted for with accuracy. A change of 0.1 pH units can be due to the physical properties of a pH electrode, if one is used, or from the abovementioned factors in calculations based on stability constants/phase diagrams. A change of 0.1 pH is in the expected error envelope with seawater – next to nothing. You are all wrong, wrong, wrong.

    Were you not taught Debye–Hückel theory in first year Chemistry?

  71. Geoff, of course activities are the quantities that matter, but at these concentrations of hydrogen ion, it won’t matter if one uses concentrations or activities to calculate the relative increase in [H+] from the given change in pH.

  72. The Debye-Huckel theory, even extended, breaks down at concentrations > 0.1 m. With an ionic strength of 0.7, seawater is outside the realm of normal activity theory and any measurements of pH have to be done empirically-hence the modified pH measurements and revised buffer standards made from artificial seawater discussed above. Assuming that the current average of 8,1 for seawater pH is based on a corrected measurement, how could the measurement from the beginning of the Industrial Age have any meaning in this context when it was made long before theory and accurate measurement were available.

  73. To become acidic the hydrogen ion content of the sea water offshore from Oregon would have to increase 6121% more than the 26% (not 30%) change. The measurement was over a one century period.

    This means that 6121 years from now the ocean near Oregon will become acidic.

    It is hard to really generate a sense of immediacy or panic for a time period greater than the written history of mankind.

  74. Dan Johnston says- “…how could the measurement from the beginning of the Industrial Age have any meaning…”

    Indeed. The 0.1 pH drop has no meaning because it is not based on measurements.

    Dennis Ambler posted an article at SPPI on April 27, 2010-

    “The decrease of 0.1 from the “pre-industrial” figure is an average of a calculation from an
    estimate, as quoted in AR4 WG1: “A decrease in surface pH of 0.1 over the global ocean was calculated from the estimated uptake of anthropogenic carbon between 1750 and 1994 (Sabine et al., 2004b; Raven et al., 2005)”
    “The mean pH of surface waters ranges between 7.9 and 8.3 in the open ocean, so
    the ocean remains alkaline (pH > 7) even after these decreases.”

    So, the centennial 0.1 pH reduction is computer model garbage, regardless of the units.
    We don’t even have adequate measurements of the average global pH of the oceans TODAY!

    Jane Lubchenko is no dummy, though. She is responsible for increasing NOAA’s budget as much as possible. She requires misleading or alarmist claims to compete with NASA GISS.

  75. Here are some quotes from the website of Prof J. Timothy Wootton, who is very alarmed about ocean acidification-

    http://woottonlab.uchicago.edu/index/global-change/global-change-impacts-on-ecological-networks

    “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.”

    “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.”

    In other words, after spending 10 years taking pH measurements at one coastal location (Tatoosh Island, Washington), they have no idea what is going on with ocean pH.

  76. Mitch says:
    June 30, 2012 at 12:56 pm

    Gary Pearse: An increase in pH is a decrease in H+ concentration
    pH = 7 –> [H+] = 10^-7
    pH = 8 –> [H+] = 10^-8

    The rest of my comment dealt with an increase in hydrogen (I suppose Hydronium is more correct these days) ion concentration and I slipped up in one sentence – you are correct, of course. My main point was that to go from pH8.2 to pH1.0 required an increase in [H+] of 1,584,893,200%. I was startled that a chem prof of all people would not understand the delta pH significance.

  77. Chem Prof seems to have misunderstood the nature of the complaint. The ion concentration is not the acidity (or alkalinity) as munderstood in pH. It is not used to derive the pH from -log10 of H+ ions.

    The measurements of the ocean are of pH.
    The ion concentration is derived from the pH. Not the other way round.
    And the pH is not that accurate. +/-5% (calibration slope of 95%) is the industry norm; all the buffering standards assume that.

    So 30% change in ion concentration is less than the calibration error that derives the measurement of pH at the pH of the ocean.

    The complaint is right. NOAA is not just misleading, it is wrong.

  78. Last week I posted a comment and links here to a couple of stories in the Seattle Times about the impacts of “acidification” on Willapa Bay oysters. I emailed the reporter with the following questions:

    Craig,

    In reading your article a couple of questions arose.

    1) Can the researchers studying the “acidification” issue distinguish between CO2 from deep ocean upwellings and that from the atmosphere?

    2) Since increasing atmospheric CO2 is a global phenomenon, why is the pH change from it occurring faster in Washington than in Hawaii?

    3) Is anyone taking regular pH measurements for Willapa Bay and if so, with what periodicity?

    He responded back right away. Unfortunately his responses were not that helpful. To my first question he provided a link to a story that said nothing about identifying the source of CO2. To the second he referred me to the part of his story saying that it had to do with how upwellings hit the NW coast. I could tell from his response that the possibility never occured to him that the increase could be primarily these currents. After a followup email to him, he referred me to Dr. Feeley. I’ve been debating whether or not it is worth my time to contact him.

    I get the feeling that the press and perhaps a good number of researchers do not understand the importance of wanting to sift the wheat from the chaff. When nearly everything gets tied back to climate change these days, how is the average citizen supposed to figure out what is a real problem needing to be addressed and what is simply speculation.

  79. This is not about politics. It is about arithmetic and simple arithmetic functions.

    Chuck Weise’s WUWT post says
    nothing about sources of error in measurements of pH,
    nothing about sources or sinks of hydrogen ions in ocean brine,
    nothing about complex equlibria,
    nothing about the effects on hydrogen ion concentration due to other species,
    nothing about non-ideal behavior of hydrogen ion in solution.

    Here are things that he actually wrote:

    (1) “As you also know, there are 14 orders of magnitude that define the pH scale from
    zero to fourteen units as per this equation. ”

    This is incorrect. The pH scale is open-ended.

    (2) 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.

    In fact, the story does not mention pH at all. Lori Tobias quotes Alan Barton
    (hatchery research manager at Whiskey Creek Shellfish Hatchery on Netarts Bay), ‘
    “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.” ‘

    No mention of pH.

    Here is a list of every reference to acids, acidification, or acidity in the article:

    “Rising levels of carbon dioxide — which lead to increased acidity in the ocean
    water, or ocean acidification — were making it difficult, if not impossible, for the
    larvae to grow.”

    “The shell [of oyster larvae] is easy to dissolve and sensitive to acidic conditions,
    Barton said, unlike the hard adult oyster shell that’s made of calcite.”

    “Some say it is impossible for the larvae to grow the shell; some say they can, but
    it is really hard to do.They use a lot of energy and don’t grow. Whether it is
    impossible or just difficult, they are still dead. We know that the ocean acidification
    is causing our problem.”

    “The impact of ocean acidification is heightened by upwelling, which occurs when
    winds blowing from the north push the ocean surface waters away from the coastline,
    allowing deeper waters to move to the top. The deeper waters are already higher
    in carbon dioxide from all the decomposition below. Water that upwells is always
    higher in acidity, but our use of fossil fuels has added to the carbon dioxide in
    the atmosphere, in turn increasing ocean acidity, Barton said. ”

    “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.”

    That is it. No mention of pH.

    (3) “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. ”

    This is incorrect. Chuck Weise is correct earlier when he says that pH is defined by the
    equation pH = – Log[H+], where [H+] is the hydrogen ion concentration. Now he says
    it isn’t defined ‘by that number.’ This is just wrong. In fact, pOH and pK, and for that
    matter, pAnything are defined in a similar manner:
    pAnything = -Log(Anything)
    with the corresponding unique inverse relationship
    Anything=10^(-pAnything) .

    This is done in chemistry all the time because the scale of these quantities vary by many
    orders of magnitude.

    How do chemists describe how much of a given substance is present in a solution?
    There are a number of ways, but every single one of them can be related to the molar
    concentration of a substance, that is, moles of substance per liter of solution, which is
    usually written as [X], where X is the substance in solution; It links two quantities:
    (a) the moles of a given material – a specific way of counting the molecules or ions
    of a given type and (b) the volume of the solution measured in liters.

    For example, hydrogen ion concentration, written [H+], represents the moles of
    hydrogen ion in a liter of solution.

    What does Chuck Weise man by “the number of ions in an aqueous solution of
    water are very large” ? I have no idea and it is irrelevant.

    Comments that argue that “It’s even more complicated than that, because there are
    buffers involved” or something like that are missing the whole point of the acid-base chemistry
    of a buffered. The presence of a buffer (another weak acid or base) in significant quantity
    makes it more difficult to change the pH of a solution, not easier. So a signficant decrease
    in the pH of a buffered solution is a clear indication that a significant source of acid has
    been added.

    Some comments represent serious scientific ignorance:
    “It is being assumed by these people that the ocean obeys the second law of thermodynamics,
    it does not because of surface tension.”
    “The oceans are infinitely buffered.”
    “A pH change of .1 corresponds to a change in hydrogen ion concentration of ..007%.”
    “A pH change from 8.2 to 8.1 cannot be truthfully described as ‘becoming ‘more acidic’. ”
    “the acidity isn’t increasing; the alkalinity is decreasing.”
    “pH is (negative) log because that is how organisms perceive acidity. They don’t perceive
    it in a linear scale, so it shouldn’t be quoted in one. No-one, but no-one talks about acidity
    other than via pH.”
    “The reason the change in pH is meaningless in this situation is that in a pure system where
    only H+ is considered to be driving pH, the change is one gram of hydrogen ions in one
    billion liters of water.”
    “Weren’t they lucky to have chosen the H+ ion concentration as reference, and not
    the OH- (OH minus) ion concentration?”
    “Chem Prof seems to have misunderstood the nature of the complaint. The ion
    concentration is not the acidity (or alkalinity) as munderstood in pH. It is not used to
    derive the pH from -log10 of H+ ions…The measurements of the ocean are of pH…
    The ion concentration is derived from the pH. Not the other way round.”
    “As a Chemical Professor – cough! – you will be aware that there is a p[OH] measure too.
    So why not quote the alarming story that – oh noes! – hydroxide concentration in the
    oceans has fallen by 80%. I would hope you would see how stupid it was to use it,
    regardless of being technically true.”
    NOTE: That isn’t true; a 0.1 decrease in pH corresponds to a 0.1 increase in pOH, with a
    corresponding decrease in [OH-] of 20.6%. If you are mystified by this, please note this
    arithemetic: 1.26 x 0.794 = 1.00 .

    Please note: “I’ve copied a discussion from Wikipedia…” is not the strongest line of
    argument one might take.

    Quite a few comments indicate there is confusion between the ideas of variablity in a
    measurement and an error in a measurement. There is a large variability in the height of
    a human, varying from 0.55 m tall Chandra Bahadur Dangi of Nepal to 2.45 m tall
    Zeng Jinlian of the People’s Republic of China. This natural variation does not preclude
    us from measuring individual height to a precision of 0.001 m or better. And variations
    in human height are worthy of study:

    Chao-Qiang Lai, of the Jean Mayer Institue wrote
    ‘ …”How much variation (difference between individuals)
    in height is attributable to genetic effects and how much to nutritional effects?”
    The short answer to this question is that about 60 to 80 percent of the difference
    in height between individuals is determined by genetic factors, whereas 20 to 40
    percent can be attributed to environmental effects, mainly nutrition.’

    http://www.scientificamerican.com/article.cfm?id=how-much-of-human-height

    He also writes
    Heritability allows us to examine how genetics directly impact an individual’s height.
    For example, a population of white men has a heritability of 80 percent and an average
    height of 178 centimeters (roughly five feet, 10 inches). If we meet a white man in the
    street who is 183 cm (six feet) tall, the heritability tells us what fraction of his extra
    height is caused by genetic variants and what fraction is due to his environment
    (dietary habit and lifestyle). The man is five centimeters taller than the average.
    Thus, 80 percent of the extra five centimeters, or four centimeters, is due to genetic
    variants, whereas one centimeter is due to environmental effects, such as nutrition.

    Notice that one is still able to make a strong scientific statement about a 1 cm height difference
    in spite of a 200 cm wide variation in human height.

    Some commenters hang their hats on the high ionic strength of sea water (it is signficant,
    about 0.73 mole/liter) or the difference between the activity of hydrogen ions and [H+], but
    entirely forget that the activity of a 10^(-8) molar solution is —- 10^(-8) molar ! Debye-Huckel
    theory plays no role in this whatsoever.

    Chuck Weise adds, “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” and misses the point again.

    Some comments are rich with irony:
    “Does anyone know how much CO2 it would take to change 1.3 billion cubic
    kilometres of [buffered – my clarification] salt water from pH 8.2 to 8.1?”
    “Because even though the numbers do calculate to roughly 30%, it’s incredibly
    inappropriate to apply percentages with pH.”
    “To many non-scientific readers this implies a hugely significant increase in
    environmental impacts – 30% more acidic ! NOAA compound the misleading nature
    of this statement by not making it clear that this is a reference to a percentage
    change in hydrogen ion concentrations.”
    Willis Eschenbach:…”applying percentages to logarithmic scales doesn’t work.”

    Exactly.

  80. Chem Prof says:
    “Some comments are rich with irony:”

    “Does anyone know how much CO2 it would take to change 1.3 billion cubic
    kilometres of [buffered – my clarification] salt water from pH 8.2 to 8.1?”
    “Because even though the numbers do calculate to roughly 30%, it’s incredibly
    inappropriate to apply percentages with pH.”
    “To many non-scientific readers this implies a hugely significant increase in
    environmental impacts – 30% more acidic ! NOAA compound the misleading nature
    of this statement by not making it clear that this is a reference to a percentage
    change in hydrogen ion concentrations.”
    Willis Eschenbach:…”applying percentages to logarithmic scales doesn’t work.”

    Exactly.

    Let me some this up with an analogy: Let’s say you’re a company being accused of paying “slave wages”; but you state that you’ve increased wages by 30%. A 30% increase is meaningless without knowing 30% of what. If you’ve increased wages from a penny an hour by 30% that’s still “slave wages”. The press release similarly misleads the average person because they may not know what the total is the 30% is in reference to. It’s unethical zohneristic advocacy, not objective science. But any chem prof would know that it is incredibly inappropriate to apply percentages to pH’s instead of thinking that is somehow ironic.

    BTW: Chem Prof, I’m doubling … nay, tripling the money I’m paying you to post here.

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