Ocean pH Accuracy Arguments Challenged with 80 Years of Instrumental Data

Testimony before Congress was based on model hindcast, actual data ignored

Guest essay by Michael Wallace, Hydrologist

Members of the global science and lay communities have begun to learn of the confirmed omission of 80 years of instrumental data from contemporary ocean acidification (OA) scientific products. The missing ~2 million data points comprise a majority of the world’s historical ocean pH measurements.   The data was replaced without disclosure, by a model hind cast. The substituted history, known as the FEEL2899 report (1) was itself used as the technical basis for testimony to the US Congress (2). In turn, OA mitigation research funding was augmented, and the regulation of anthropogenic greenhouse gas (GHG) emissions was strengthened and deepened.

This occurrence of a model-replacing-data-without-disclosure has few publicized precedents of this scale. Already some in media have chosen to headline this as a case of “pHraud” (3). Whatever it is called, a fundamental question remains whether or not this omission will ever be corrected. Currently the major obstacle to rapid correction appears to be a consensus among those in power, that ocean pH cannot (and could never) be instrumentally measured using any conceivable means for any conceivable ocean purpose by any conceivable scientist. Therefore those in power effectively assert that the world must put aside expectations of data accessibility and transparency, and accept the PMEL authors’ formerly undisclosed SeaCarb model hindcast replacement as the entire truth of past ocean pH.

I came into awareness of the ocean pH data omission myself, purely through research activities, which led to personal communications with the authors of the omission (4). I learned through two of those authors some facts concerning the origins, pervasiveness, and structure of the omissions.

Originally I had simply hoped to find somewhere a complete basic ocean instrumental pH time series data set, in order to compare to other ocean and climate indices of interest to me.   Although it was a detour from my primary research, I found it necessary to begin to construct my own time series and geospatial products, based on the new information, obliquely brought to my attention by the PMEL authors towards the end of our communications, which I later downloaded.

I have continued to follow up through ongoing stochastic evaluations of the actual omitted instrumental data (5). I think this information largely speaks for itself and so I’ve adapted some of those evaluations for the attached figure. In addition I’ve traced some of the OA citation pathways in order to focus on the most likely reasons for the existing disconnects between the OA research community and the rest of the aqueous pH measuring communities.

One of the greatest disconnects relates to the question of instrumental measurement accuracy.   In my communications with the FEEL2899 authors from the Pacific Marine Environmental Laboratory (PMEL), they asserted that instrumental ocean pH measurements prior to around 1988 were not sufficiently accurate (4).

Figure 1-a. includes a subset of the FEEL2899 pH time series product as the thick reddish curve. Some aspects of the NOAA World Ocean Database (WOD) (6) global ocean pelagic pH data (GOPpH) are plotted over the same time frame. These include the ten year moving average in blue, and a rounded version of that as open green circles. Please note that although there doesn’t appear to be a clear trend up or down, both of the WOD-based curves suggest an oscillatory behavior, over the period shown.

MWallaceFigure1

NOAA’s WOD pH data are typically published to two decimal places. This is presumably because of the 0.01 pH unit accuracy of the meters utilized. This accuracy is standard for many modern day glass electrode pH (GEpH) meters as well. In addition, the natural global ocean pH (GOpH) values for all depths can range over 4 full pH units.   That yields at least 400 unique possibilities along a continuous ocean pH curve, that can be accurately identified by any pH meter of its time.   Even a measurement taken with an accuracy of only one decimal place yields 40 possible points along that curve. Either accuracy should be more than adequate for initial and publishable GOpH and/or GOPpH trend analyses.

As a rough illustration, I have included the green open circles of Figure 1.a., which are simply the blue curve data rounded to the nearest 0.1 pH unit. The apparent oscillatory pattern of the more refined time series is preserved. This holds even though I’ve already severely restricted the pH range of that data set due to the 10 year averaging filter.

The real data continue to receive additional confirmatory support. For example, I have been profiling outside natural indexes which appear to correlate with the WOD GOPpH data set (5). These include the Pacific Decadal Oscillation (PDO) and the Otowi stream gage in the US Southwest.   I’ve included part b. of Figure 1 to summarize some of those findings here (7). As shown, my construction of the GOPpH time series shows a higher correlation to a premier continental stream gage (the Otowi gage of the Upper Rio Grande in the US Southwest) than correlations of that gage to the El Niño – Southern Oscillation (ENSO), the Atlantic Multidecadal Oscillation (AMO), and atmospheric CO2 (from Mauna Loa Observatory).

MWallaceFigure1bTo me, this is interesting. I know that the correlation between GOPpH and the Otowi stream gage is not high enough to be useful by itself for forecasting purposes. Yet it would appear to be more justified than ENSO and/or CO2, even though those are the ‘go to’ drivers employed to justify contemporary assertions about hydrology in this region.

In any case, given such reproducible and stochastically interesting outcomes for GOPpH, why do OA researchers consistently maintain that GEpH meters are insufficiently accurate for any conceivable ocean hydroclimatologic use? Why do they also assert that only spectrophotometric (SP) based pH meters are up to the claimed accuracy challenge?

These assertions appear to be largely based upon invalid referencing (8,9) to the document known as “SCOR Working Group 75” (SCOR75) (10). The SCOR75 report contradicts those claims by clearly stating that “Under the best circumstances, the absolute value of pH is only known within 0.01 pH unit”.   Moreover, it appears that the validity of SP based pH measurements is only supported when those measurements are backed up by, of all things, GEpH meter readings. In fact, one of the FEEL2899 authors has contributed to a report where this GEpH specification is repeated many times (8).

Perhaps even these inconsistencies are overshadowed by another twist; why do SP based pH measurements also require the use of conventional pH indicator dyes? Unlike typical applications for SPs, the emission or absorption of the target ion species (hydronium in this context) is not directly measured. Rather, the SPs in this context appear to be nothing more than expensive, exotic, titration- fed colorimeters.

The non-OA community might benefit to know of this pernicious limitation that all ocean scientists are now constrained to.   Is it conceivable that if only for consistency, authorities soon will pressure the rest of us to abandon GEpH meters in favor of a technology that is no more accurate, yet exponentially more expensive and time consuming?

No doubt I have biases, but I believe that the scientific consensus will eventually condense around the omitted NOAA WOD GOpH data as the most practical and useful foundation for any credible and complete ocean pH time series analyses. It is amazingly rich and informative, and appears to align with many independent hydroclimatologic patterns and expectations.

The ocean pH data omission was an unprecedented and disturbing incident in the history of hydrological sciences. Only NOAA can likely correct this. That’s because NOAA contains the source of the problem (the FEEL2899 pH time series product) as well as its solution (the WOD database). To help resolve that paralyzing disorder, scientists and others may wish to consider signing a petition that I have authored at (11). It may seem overly prescriptive, but in some ways it merely asks that the ocean pH data omissions be corrected by NOAA, and that GOpH measurements follow the OA authorities’ own published guidelines.


REFERENCES

  1. Feely, R.A., C.L. Sabine, and V.J. Fabry, 2006, CARBON DIOXIDE AND OUR OCEAN LEGACY http://www.pmel.noaa.gov/pubs/PDF/feel2899/feel2899.pdf
  2. American Clean Energy and Security Act of 2009 U.S. House of Representatives Rept. 111-137 Part 1. 111th Congress. CRPT-111hrpt137.pdf
  3. For example: Noon, M. 2014 article at:http://www.cfact.org/2014/12/22/what-if-obamas-climate-change-policies-are-based-on-phraud/
  4. Wallace, M., 2013 PMEL & Pew Charitable Trust Communications transcript compiled by Wallace. https://dl.dropboxusercontent.com/u/100449329/June2013WallaceResponseToFeel2899EmailString.pdf
  5. Wallace, M. 2014 – present, pH and Ocean Acidification (13 posts), http://www.abeqas.com
  6. NOAA NODC Ocean Climate Laboratory http://www.nodc.noaa.gov/OCL/
  7. Wallace, M. 2014 draft paper parked at: https://www.academia.edu/9071357/The_Relative_Impact_of_the_Pacific_Decadal_Oscillation_Upon_the_Hydrology_of_the_Upper_Rio_Grande_and_Adjacent_Watersheds_in_the_Southwestern_United_States._3_4_5
  8. Dickson, A.G., Sabine, C.L. and Christian, J.R. (Eds.) 2007. Guide to best practices for ocean CO2 measurements. PICES Special Publication 3, 191 pp.
  9. Aßmann S., C. Frank, and A. Kortzinger, 2011, Spectrophotometric high-precision seawater pH determination for use in underway measuring systems. Ocean Science 7, 597-607
  10. Final Report of SCOR Working Group 75, 1992, Methodology for oceanic CO2 measurements. UNESCO technical papers in marine science
  11. http://www.ipetitions.com/petition/restore-the-worlds-ocean-ph-measurements
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197 thoughts on “Ocean pH Accuracy Arguments Challenged with 80 Years of Instrumental Data

      • So, when the models show the “global ocean mean pH” becoming “acidic”, they are right, but when the data does not, the data must be wrong.

        Do you realize how ridiculous this sounds?

      • Well I will ignore your rhetorical question. It sounds like a “false dichotomy” anyway.

        Data is fine as long as it is good data. Historical data gathered the way the article suggests is not going to be good. Plus you cannot work out a global average by just averaging a bunch of data points, it is more complicated than that.

        You only have the article-writer’s word for it that the “model” is no good. If I thought the writer was trying to be scientific I would say that he needs to prove that claim.

      • So Harry, is the “correct” way to get a global mean by smearing the data points around a 1000km grid cell and then averaging them together?

      • “Data is fine as long as it is good data. Historical data gathered the way the article suggests is not going to be good. Plus you cannot work out a global average by just averaging a bunch of data points, it is more complicated than that.”

        So Harry, using that criteria, the surface temperature data should not be used either.

        I guess the only way to know what is happening in the real world is to consult models since no form of observation is worthy of consideration.

        IMO, those 2 million or so data points may not show an average but they are useful in showing trends. As long as they aren’t “adjusted” by the same folks who manipulate the surface station data in order to better match the incomplete models.

        My interpretation of a “no good” model is one which does not compare well with actual observational data.

      • Why are people so hung up on ‘averaging’ when that is totally meaningless due to the large variances in pH around the measurements being taken. Not to mention the obvious misunderstanding of precision vs accuracy. The only reason I can see it being useful is that politicians can be persuaded by it to provide more funding – as shown in this article. So obtaining funding is the purpose of the modeled average; it is useless from a scientific viewpoint.

      • @ harrytwinotter March 31, 2015 at 6:27 am

        Plus you cannot work out a global average by just averaging a bunch of data points, it is more complicated than that.

        Geeezze, ….harrytwin, …….have you told the IPCC and all the other Global Average Temperature calculating proponents of CAGW about your above stated fact?

      • Warning – subject change! Not to mention what is probably a false-analogy.

        We were actually discussing ocean pH and acidification. Focus people, focus!

      • harrytwinotter

        The models have to be proved wrong??? And you are not allowed to use the available data to do that??? That is crazy!!!!

        So the only way to prove the models wrong is to go into the models and show that their fundamental premises are wrong?

        Wow, people have been trying to get a look inside climate models for years. Not allowed. Has everything about this model been made public?

        A model is at best a hypothesis — the validity of which is determined by comparing it to measured data. What you are demanding is the nullification of that fundamental precept. You are preaching non-science. Like it or not it is fair to say that this model is “faith based”. (Can you hear the song “Give Me That Old Time Religion” playing in the background?)

        Modelers are taking us back to the age of superstition. When models are claimed to produce data then the the models are nothing but superstition and the modelers ignorant savages dancing around camp fires.

        Eugene WR Gallun

      • Eugene WR Gallun.

        That is what I am saying, yes. The article does not say why the models are wrong – it should.

        I ignored the rest of your comment because it was irrelevant gibberish. If you hear a song playing in your head, that is your own affair.

      • harrytwinotter is getting badly beat up here, so I’m reluctant to pile on…

        …OK, not really.

        Harry says:

        Data is fine as long as it is good data.

        Agreed. But there’s no really good data on ocean pH, is there? There are models, and so what? That’s why it is such a juicy subject for the climate alarmist crowd. They can say anything. All skeptics can say is ‘show us’. Instead, they keep repeating the “acidification” mantra/narrative. In other words, heads we win, tails you lose.

        Post your “good data”, harry. I want to look at it. Then we’ll see…

      • Harry

        Good to see your scepticism showing through with your comments about historical data. Presumably you will not be mpressed by Sea surface temperature measurements back to 1850?

        Tonyb

      • dbstealey.

        I am not worried about your dog whistle. It appears to be your job on this blog.

      • @harrytwinotter,

        Yet another cryptic post.

        Explain your “dog whistle” comment — if you’re not just trolling.

        And what, pray tell, is my “job”? FYI, no one employs me or tells me what to do. I speak 100% for myself. So… your comment wouldn’t be projection, would it? Is your job to troll, and run interference here?

        As I stated above, you are getting badly beaten up here, and it’s because you can’t seem to man-up and respond.

      • harryotter says:

        You only have the article-writer’s word for it that the “model” is no good. If I thought the writer was trying to be scientific I would say that he needs to prove that claim.

        Wrong again, and I for one have stoped counting. You still don’t understand the meaning of “scientific”. For one thing, it means that skeptics have nothing to prove. So enough with demanding that the skeptical author of this article must “prove that claim”.

        The only ones who have the onus of supporting their “acidification” conjecture are the alarmists who are pushing that narrative; those who produce models, then call those models data. They are the ones claiming that their model works, when it is clear it doesn’t.

        There are no verifiable measurements showing changes in ocean pH that are outside the error bars. The “ocean acidification” scare is just another failed prediction of the climate alarmist crowd. It joins every other failed prediction of theirs, from accelerating sea level rise, to disappearing Polar bears, to Tuvalu disappearing beneath the waves, to vanishing Arctic ice — to the big enchilada itself: runaway global warming. Every one of their predictions was wrong. No exceptions.

        But we can count on their lemmings to jump on any alarmist bandwagon du jour, such as the ocean pH scare. harrytwinotter is just another tedious lemming, hoping he’s right this time — when we can see that he’s simply wrong again.

        And I note that despite my request way upthread, harrytwinotter has still posted no data. But why post any data, when:

        a) your eco-religion doesn’t require it, and

        b) you have no data anyway?

        Wake me when there are testable, verifiable scientific measurements, outside of any error bars, which show conclusively that ocean pH is “acidifying”. That will be the day.

    • Sorry Harry, but I can’t find anything in your “debunking” that actually addresses the claim. Saying that it’s junk is one thing, but there is nothing to say that it is any worse than taking a model based off unmeasured data. Looking at the metadata chart does indicate that it could use improvement. However, presuming that the distributions are fairly random (and thus the biases roughly average), the oscillation between the 50s and 80s would seem to still be valid.

      Now, the idea that you should only average the changes in pH is continuously measured regions is a good one. I would like to see an analysis of that. However, saying that the analysis is flawed hardly counts as a “debunking” of the scandal. This begs the question, the metadata obviously exists to give a location-specific trend analysis, so why didn’t the NOAA reanalyze the data they had instead of substituting it with a model based on CO2 concentration that effectively boils down to circular reasoning?

      Also, that link includes several very good charts on reasons why ocean acidification should not be worried about, namely the huge inter-sea and seasonal variations in pH.

      • Too many straw men for me to comment on, so I won’t. I don’t think you read the debunk I linked to very carefully.

        The bottom line is there is no “scandal”, save for the one Michael Wallace is trying to fabricate.

      • No straw men here. My statement is simple

        1: There is data.
        2: You claim that the analysis is flawed by showing geographical distribution.
        3: However, instead of promoting reanalysis of the data in a superior method (which you just showed could be done), the data was discarded in favor of modeled results.

        The problem is in number 3.

        I did read your link. I AGREE with your link on almost all of its points, aside from the final line (the idea that the gridding and trending is difficult so it should not be done). Most importantly, your link says that the global average pH should not be calculated AT ALL as its a meaningless and highly variable number. However, that is what is being requested.

        However, there’s a non-sequitor that isn’t being addressed. That being discarding the entirety of the dataset and using model output instead. That’s a giant leap that just cannot be justified. That is the objection raised in this post and that is not addressed in your comments or your link.

      • Benjamin of Houston.

        The straw man is the claim that data was “discarded”.

        I wonder how many have had a look at FEEL2899. It is only a briefing (not a “report” which is another straw man). The “chart” (it actually looks more like a schematic) doesn’t even appear to be a “model” or “hindcast”, it is hand draw (no noise in the data) – my guess it is just there for illustration only.

    • harrytwinotter March 31, 2015 at 6:05 am
      https://quantpalaeo.wordpress.com/2014/12/26/not-phraud-but-phoolishness/

      If this is your example of debunking your argument is in severely weak. The article provided debunks nothing but instead tries to change the subject or claim “complexity” as you miserably attempt to do as well.

      The climate and ocean PH is very complicated but the methodology pursued by Sabine is not, it is transparently stupid. If you have the data you use it, if you have the data but do not trust it, you don’t manufacture data by an unproven method and then claim you have the data. Stupidity can make a comfortable home well in either simplicity or complexity, it is not biased in that regard.

      Stupidity may not be the issue here however as Sabine implicates himself of dishonesty using his own words.

      Sabine responded by saying that it was inappropriate for Wallace to question their “motives or quality of our science,” adding that if he continued in this manner, “you will not last long in your career.”

    • Then why are you still posting here? Oh, sorry when you mentioned hoax I immediately thought of hoaxer, you.

      According to people like you models provide better information than the real data. Some day soon if people like you have their way I wouldn’t be surprised to see everyone forced to wear virtual reality headsets providing everyone with pre-approved model data as opposed to reality. It might be confusing for folks as they die of hypothermia, but models are better than data says the pimps of AGW/Climate change.

    • I have one question each for harrytwinotter and for Michael Wallace.

      Harry2O: Would you agree that the data show that the pH was lower in 1910 than at present time, and that it was approximately the same in 1950 as now? Or are you disputing the accuracy of the data?

      Michael: Part of your alarm seems to rest on the fact that the dataset at NOAA was replaced with a model. Where did you come by your data?

      Thanks,

  1. What a grotesque politico/scientific scandal and our thanks to Michael Wallace for uncovering it and presenting it to the world. This what happens when the scientists get too close to the needs of the funding Government. This is hideously embarrassing for NOAA and for the scientists who work there. How will they respond?

    • A government agency that hide long term ocean ph measurement data (where the ocean ph data in question was attained with tax payer funds) from the scientific community and from tax payers as the long term ph data in question supports the assertion that one’s ph/CO2 ocean model is incorrect, is not embarrassing.

      It is grounds for a change in the senior administrators in the government agency in question and is clear indication that new formal policies are required to ensure government agencies strictly adhere to normal science practices, are completely transparent in terms of data release, data analysis, and provide documented reasons for changes to data, and do not change data unless there is a scientific reason to do so, as opposed to cult science.

      The fact that a government scientific agency replaced the long term ocean ph measurement data with a hind cast forecast from the incorrect ocean ph model is a sad indication of rampant, pervasive, climategate cult science. Government policy that is removed from science, logic, and reason degrades into madness.

      Comment:
      In normal science theories change when data and analysis does not support them. In normal science the objective is to solve scientific puzzles. In cult science, there are hidden agendas which stop the normal progress of science. In cult science data is hidden and papers are blocked to protect the cult’s theories. In cult science, the cult has an agenda.

  2. Instrumental Data! we don’t need to no instrument data we got ‘models’ which are better than reality .
    Once again the mistake is to think that you prove them factual wrong they you won the argument, the trouble is it is not a argument based on facts , although it should be .

  3. Michael: I went looking for pH series a few months ago. IIRC there were very few actual in situ time series – Monterey and Hawaii. Could you point me to a source on the geographic distribution of these measurements and the periods that they cover..

  4. If this is true, this is unbelievable. However, given what I have seen and found out over the years about science (being used to build the socialist global utopia), I’m not surprised.

    • ‘Socialist Global Utopia’; apologies to George Orwell; Choco rations have been increased from 35 grams to 25 grams per day.

      • I think you will find that Choco rations where never 35 grams your ‘mistaken’ if you look closer you will find the record ‘proves that ‘

  5. I echo John V Wright in thanking Michael Wallace for his tenacious investigation and exposure of the ocean pH fraud by the political activists and CAGW cultists at NOAA. It is yet more evidence (if any more was really needed) that the fundamental problem to be resolved is not scientific per se but political. That is, of the dangerous, man-made Big Government variety.

  6. Interesting that the blue line (10 year moving average) closely aligns with the changing temperature trends during the 20th century which in turn are roughly aligned with varying levels of solar activity, global cloudiness and Jetstream zonality / meridionality.

    I think this link is pertinent:

    http://www.newclimatemodel.com/evidence-that-oceans-not-man-control-co2-emissions/

    Basically, at times of lower global cloudiness, sunlight penetrating the upper oceans drives CO2 out of the water and into the atmosphere which increases PH (more alkaline) as can be seen from1970 to 1990.

    Amazingly, the ocean response to more CO2 in the atmosphere is increased alkalinity and NOT increased acidity presumably because an increase in sunlight drives CO2 out of the oceans and into the air. The chart deals with the top 200 metres which is approximately the maximum depth to which sunlight can penetrate to any significant degree.

    The oceans appear to have become more alkaline during the late 20th century warming spell and only since 1990 have they become more acidic as the warming stopped and according to Earthshine data global albedo has increased again.

    Changes in the PH appear to predate the subsequent climate changes by about ten years which suggests that solar effects on global cloudiness cause an immediate change in the PH trend but it takes about ten years for the effect of those changes in trend to show up fully in PH, CO2 and cloudiness changes.

    So the PH started to rise in about 1970 (more alkaline) but the climate shift towards warming was not noted until the late 70s and PH started to fall around 1990 (more acidic) but the climate shift (cessation of warming) was not noted until around 2000 (I have often said I first noticed jet stream changes back towards more meridionality from 2000).

    PH started to rise around 1920 (more alkaline) and global warmth increased into the 1930s.

    PH peaked around 1945 and then started to fall (more acidic) followed by the global cooling fears of the 1950s and 60s.

    It appears that the AGW based theory of oceanic acidification is the reverse of reality and confusion has been caused by the ten year time la.

    Lower global cloudiness drives CO2 out of the oceans (top 200 metres) so that the air then contains more CO2 but the oceans hold less and become more alkaline rather than more acidic.

    • agreed. Ocean pH is correlated with temperature/ocean cycles, not CO2. This is strong evidence that the ocean overturning rate drives temperatures and ocean pH. Which is of course why it was not presented to Congress. Anyone that presented this to Congress would have found themselves very unpopular with the White House, and found themselves added to the Official Deniers List, their funding cut off, and their career on the fast track to the toilet. The Global Warming deal in Paris is to be the crowing achievement of Barry’s legacy. Nothing can be allowed to derail this.

      • The ocean overturning rate is an interesting modification to the basic principle because a period of solar induced outgassing will result in lower CO2 concentration in the water entering the thermohaline circulation which takes 1000 years or so to complete.

        There is also the issue of semi independent ocean oscillations in each ocean basin.

        Thus there might well be longer term atmospheric CO2 trends hiding behind the shorter term variations observed since 1910 on the above chart.

    • It appears that the AGW based theory of oceanic acidification is the reverse of reality and confusion has been caused by the ten year time la[g]

      [spell correction of “lag” is mine]

      Well, it depends how you did your signal analysis and how noisy the underlying signal is. Was the Moving Window Average truly moving, or a choppy boxcar? Was the average put into the beginning, middle, or end of the 10 year decimation interval? If it’s not identical for both the pH and PDO signal then it’s just sampling error on the 10 year average and could account for the causation/lag issue.

      If the underlying signal is very noisy at high frequencies, a Moving Window average technique can alias up to 20% of the underlying noise into the lower frequencies, greatly distorting the resulting signal. It’d be better to use something that aliases less than 1%. That would require a properly designed Hamming, Kaiser, or other phase-linear filter.

      Since we don’t have the source code and data we can’t tell if it’s a processing problem or a real physical phenomena. I’m continually frustrated on not seeing the data and the source. Amazon gives away storage for Free. DropBox gives away storage for free. GitHub is free. There’s really no excuse for not posting all the data and the code for any analysis somewhere for free.

      • Peter are you referring to my plots? The data sources are provided. Also I have used a dropbox account to provide supporting information. Feel free to process the data to your whim if you choose to access the WOD yourself, as I did.

  7. Hmmm…so real ocean pH oscillates over a 60 year period! Who would have thought that? How about the chemical basis for this?

    http://chemwiki.ucdavis.edu/Physical_Chemistry/Acids_and_Bases/Aqueous_Solutions/The_pH_Scale/Temperature_Dependent_of_the_pH_of_pure_Water

    “According to Le Châtelier’s Principle, if you make a change to the conditions of a reaction in dynamic equilibrium, the position of equilibrium moves to counter the change you have made. Hence, if you increase the temperature of the water, the equilibrium will move to lower the temperature again. It will do that by absorbing the extra heat. That means that the forward reaction will be favored, and more hydrogen ions and hydroxide ions will be formed.”

    This is for pure water, though. The table given for fresh water shows heating from 0 to100C changes the pH from 7.47 to 6.14, very substantial!

    • I speculate that the big dip in the chart during the Great War might be due to a pause/hiatus/whatever in global sampling. Perhaps the samplers were limited to certain areas with normally lower pH? A pity that Michael Wallace didn’t comment on that in this or his previous blog post. I’m too lazy to look at the data myself.

  8. For ocean water, one should look at the effect of CO2+H2O=> H^(+) +HCO3^(-), etc. and see which way these reactions are forced with temperature. I would have used SST as one of the predictors, although I guess PDO, ENSO gets part of this.

  9. Once again, if this were a private sector for profit business engaged in a hoax like this, if true, there would be people in jail. There’s too much money in government funded research.

  10. Never mind the hoax. Consider what the real data shows us.

    It appears to show that warming and more atmospheric CO2 are both associated with more alkaline oceans rather than more acidic oceans.

    That ought to cause a stir.

  11. Lewis. When the veil is first lifted the reaction is sometimes …

    Incredulity. A feeling of unreality. “We are through the looking glass, people … ”

    What follows reveals personal, internal processes. To ignore? To believe? To dis-believe? To trust? Distrust? To enquire further?

    Dig deeper than the citations?

  12. “This occurrence of a model-replacing-data-without-disclosure has few publicized precedents of this scale.”

    Yes, and it is especially unusual in the “climate science” field where the norm is model-replacing-data-with-disclosure.

    /grin

  13. 1. The data was replaced without disclosure, by a model hind cast.
    2. The substituted history, known as the FEEL2899 report was itself used as the technical basis for testimony to the US Congress.
    3. In turn, OA mitigation research funding was augmented,
    4. and the regulation of anthropogenic greenhouse gas (GHG) emissions was strengthened and deepened.

    1. Failure to disclose.
    2. Presented knowingly bogus (ie, false) testimony.
    3. Secured pecuniary advantage.
    4. Impacted / influenced national legislation.

    Where’s the NY Times editorial? Where’s the outrage from UK Guardian? Why are multiple ‘Green’ NGO’s silent? Meanwhile these people just walk out free as a bird without criticism from their peers or being held to account by the authorities? Astounding.

    • the scientists are simply following orders.

      Your boss asks you to write a report showing oceans are becoming acidic with increasing CO2. You:

      1. Disobey, which is insubordination and grounds for dismissal.
      2. Obey, write the report and get a raise.

      Those that choose 1 are quickly weeded out of the system, leaving those that chose 2 free to write whatever they are ordered to write. Courts have generally held that scientists acting under point 2 would not be criminally liable, as they were not involved in formulating the orders.

      • 100 government scientists are ordered to write a report showing “up equals down”. an independent scientist writes a report on WUWT showing “up not equal down”. Which report will be shown to Congress and the Press? Of course “up equals down”. 100 scientists say so. the debate is over. the 1% that say otherwise, they are deniers, paid by big oil and should be thrown in jail.

      • Government funded science has been on a …. 35 years long opulent “Gravy Train” ride that will be nigh onto impossible of being “derailed” anytime in the near future.

      • It’s alright, they covered themselves. Endnote 1 to the brief:

        Organizational affiliation is provided for reference only.The findings and conclusions in this science brief are those of the authors and do not necessarily represent the views of the National Oceanic and Atmospheric
        Administration or the California State University.

        Footnote to the brief:

        This science brief was made possible with funding from The Pew Charitable Trusts. The opinions expressed in this report are those of the authors and do not necessarily reflect the views of The Pew Charitable Trusts.

        What is NOAA doing taking money from the Pew Charitable Trusts? The ‘brief’ is the worst form of grey literature.

  14. If GEpH measurments are inadequate for measuring ocean pH, I assert that the temperature measurements behind GISS, CET, etc are equally bad, or worse. Those measurements are taken by non scientists reading thermometers with data reported to one degree. By this logic they could not be useful for measuring the 0.7 C° of warming in the last century.

    They too should be replaced with a model.

    • Yes that seems about right. The same might be said about sea level changes of 3 mm/year. Ha ha.. what calipers do they use to make those measurements?

  15. A good resume of the insane approach to pH measurements. It is beyond any common knowledge to prefer a SP based assay above a good calibrated GEpH measuring device. In any laboratory on this planet, the GEpH method is used with the most diverse spectrum of solutions to standarize the pH of any solution. Imagine that in a biology lab, a chemical lab the GEpH should be replaced with a spectrophotometer based assay. I think one would be surprised to see the many instances in which a SP based method would be completely off due to other reactions with the indicator dyes. Redox reactions come to mind. Apart from this, the extra work and chemicals, expensive equipment, calibration procedures will add to the cost and time that is required for a SP based assay compared to the ease of use, stability and cost of the GEpH method. More than 100 years of use of the GEpH is not easily relaced with a new method that has to show its robustness under so diverse circumstances.

    • Moreover, it appears that the validity of SP based pH measurements is only supported when those measurements are backed up by, of all things, GEpH meter readings.

      You have this backwards, the more precise SP method is used to calibrate the GE meters.
      See for example: http://pubs.acs.org/doi/ipdf/10.1021/es300491s

      “Measurements of seawater pH are currently obtained both potentiometrically and spectrophotometrically. Spectrophotometric pH measurements are much more precise (±0.0004) than potentiometric measurements (±0.003) and are increasingly preferred for direct ocean monitoring, but potentiometric measurements are advantageous for many types of studies for which less precise measurements are adequate. As such, use of glass electrodes and other potentiometric pH devices is likely to continue as a very common practice in laboratory and field investigations.
      Although the accuracy of both potentiometric and spectrophotometric measurements is intimately related to calibration protocols, calibration procedures for the two methodologies are distinct in one critical aspect. Modern spectrophotometric pH measurements, which involve the use of indicator absorbance ratios and characterizations of the intrinsic molecular properties of purified substances, do not require periodic calibration. In contrast, pH measurements with glass electrodes require frequent conjugate measurements in standard solutions in order to ensure consistent measurement accuracy”.

      • Phil,

        Let’s see.

        4 decimal places (nearest 1 ten thousandth) vs. three decimal places (nearest 1 thousandth).

        Is that really necessary or relevant with regards to what is being evaluated here?

      • You seem to be pretty ignorant in regards to measurement science. The accuracy of any of these instruments is swamped by measurement uncertainty. Shoot the stability of a samples pH alone is not sufficient to support the validity of measurements tighter then +- 0.005 at 7.0. And that’s not even getting into the human error inherent in titration!

        Speaking of accuracy, your little post is lacking. I wont say that what you pasted in is a lie, but it is deliberately misleading.

      • The problem is not one of precision, but calibration. Spectrophotometric methods are extremely precise, but all the ones I have ever used (in many areas of biology) require calibration because the instrument is subject to many different fluctuating variables. Consequently, the accuracy is really only as good as your calibration method – which in this case is provided by solutions of known pH from a gravimetric process (addition of solid compounds to water to provide a reference pH sample). These reference camples are probably checked by the potentiometric (glass electrode) equipment so you really only have the accuracy of that method to go on.

      • Desertyote, which part of the Royal Chem Soc report do you find misleading?

        Rob, is your experience with using SP methods generally or their specific use for measuring pH? Have you read the report to see how the calibration is actually done?

    • I haven’t. I did reach out to both of my NM Senators but they didn’t take an interest. I hope Senator Inhofe does take an interest and I’ll look into finding out if he is aware of this concern.

  16. Where’s the NY Times editorial? Where’s the outrage from UK Guardian? Why are multiple ‘Green’ NGO’s silent? Meanwhile these people just walk out free as a bird without criticism from their peers or being held to account by the authorities? Astounding.

    All the noise comes from the original purveyors of the great warming lie, it is they who chanted, “the sky is falling in!”…… and still make all the noise and the noisier and ever more shrill it gets as, one by one their computer generated fantasies are skewered and buried by reality – factual observations.

    But we know from what provenance where the alarmist lunatics who promulgate the global warming scare reside. Indeed – they all inhabit a strange world – on the extreme left of a parallel universe – somewhere beyond our ken – probably somewhere in the foetid nightmare realms of James Cameron-la-la-land/Hollywood.
    The left wing still parade their soiled wares and still they tell us, “next time it will be different!”………

    Pol Pot, Mao, Stalin, Chavez, Castro, even if the last two didn’t indulge in genocide – their countries ended up as backwater economic disaster zones.

    Agenda 21 is world Socialism: dressed up as global charity – a redistribution of wealth from north to south. The result is not in doubt – disaster awaits the western world and more particularly Britain and the EU – where the latest Communist Empire enters it’s death rattle – brought on by the green agenda and yet the left still insist on returning to groundhog day – or as Pol Pot described it – year ZERO.

  17. Harrytwinotter: went to your blog and it seems that you are comfortable using three sites to extrapolate a global ocean ph profile. Am I right?? By the way; why are you so contemtuous of “deniers”???

    • You have lost me there – I do not have a blog. What “three sites” are you referring to?

  18. Many believe pH sampling and measurements to an accuracy of 0.01 is easy. It is not – especially the ionic soup we call seawater. GK

    • No doubt. But scientists and/or trained technicians took the measurements recorded in the WOD. I’m happy to give them the benefit of the doubt that they did their jobs with professional skill.

      • Measurement uncertainty is measurement uncertainty, regardless of the skill of the technicians and/or trained scientists. I have taken countess pH measurements in a former career, and as part of personal research. I would never claim an accuracy greater then +/- 0.005!

  19. Layman question again: why should more sunlight drive CO2 out of the oceans? Couldn’t it be more sunlight reduces ocean absorbance from the atmosphere? Could it be both? Either way, it looks like more sunlight results in increased CO2 in the atmosphere.

    • Possibly sunlight warming oceans………or that part of the ocean that sunlight reaches/warms.
      Higher temperature – lower CO2 solubility
      Increasing salinity also reduces CO2 solubility…….but the effect is variable. depending on what salts are present.

    • The solar shortwave photons that penetrate the first 200 metres or so hit water molecules and warm the water up on a molecule by molecule basis. C02 is then released in gaseous form and moves up through the water column to the surface.

      The beauty of that description is that the outgassing process does not first require the huge increase in temperature of the ocean bulk which others have assumed might be necessary.

      And we see that the oceans become more alkaline not more acidic as the CO2 is driven off into the atmosphere.

      It becomes inappropriate to rely on Henry’s Law applied globally because the effect of injecting solar shortwave locally and regionally simply alters the balance of flows from ocean to air and air to ocean in different locations such that one gets a ‘backup’ of CO2 building up in the atmosphere whereby it comes out in one location faster than it can be reabsorbed in another location.

      The process being reversible when global cloudiness increases again.

      As for the matter of the isotope ratio it must be the case that isotope assumptions about the CO2 released from the oceans are incorrect. I suspect that the ocean biosphere is responsible.

      • The solar shortwave photons that penetrate the first 200 metres or so hit water molecules and warm the water up on a molecule by molecule basis. C02 is then released in gaseous form and moves up through the water column to the surface.

        This is incorrect, if a single photon hits a water molecule it will cause the H-O bonds of the molecule to increase its vibration/rotation. That molecule will experience multiple collisions per picosecond with its neighbors and extremely rapidly share that energy throughout the solution. There will be no release of CO2 in the manner you describe.

      • No you said that the heating by SW heated locally to cause CO2 come out of solution locally and be released at the surface without the bulk temperature rising to the necessary value. This is wrong.

      • I’m quite sure he did not say “the heating by SW heated locally to cause CO2 come out of solution locally.” Is your browser set to translate into gibberish?

      • It was already gibberish, no translation necessary. [How] would you interpret this:
        “The solar shortwave photons that penetrate the first 200 metres or so hit water molecules and warm the water up on a molecule by molecule basis. C02 is then released in gaseous form and moves up through the water column to the surface.

        The beauty of that description is that the outgassing process does not first require the huge increase in temperature of the ocean bulk which others have assumed might be necessary.”

      • How else would it be interpreted. Stephen was obviously keeping it as lay as possible but the solubility of CO2 decreases with increased temperature, you have a problem with that fact?

    • Hi Richard111
      Try incorporating some biology into your thinking.
      Q: What biological precess utilizes sunlight to fix CO2 and produce sugar?
      Hint: Things that are green ( and I dont mean NGOs)
      More sunlight increases photosynthesis provided there is abundant CO2.
      Phytoplankton do this in the oceans.

  20. Great work by Michael Wallace

    The NKVD-like pernicious political micro-management of ocean “acidification” “research” points to the total and egregious fraud that the whole thing is from start to finish. Those perpetrating it should end up in prison.

    How many times does one have to repeat,
    Calcified multicellular organisms evolved in the Cambrian with atmospheric CO2 20x higher than today.

    And no, you can’t hide behind deep time like a creationist, chemistry doesn’t change with time, even where CO2 is involved.

    Harry, whoever you are, please report to your nearest police station.

  21. The quote –

    “Currently the major obstacle to rapid correction appears to be a consensus among those in power, that ocean pH cannot (and could never) be instrumentally measured using any conceivable means for any conceivable ocean purpose by any conceivable scientist.”

    My thoughts on that thought. If you can NOT instrumentally measure something in any conceivable way, HOW in hell do you “model” it?

    The obvious answer is you can’t model something you don’t know – sort of like trying to model climate since we have no true idea what are the driving forces behind climate change or we would be able to define exactly why ice ages happen, and why there is a difference between the lengths of time between them, as well as lengths of them. And without good data, there is nothing to even form a “best guess” on in the first place. Might as well get out the crystal ball if you are going to “model” something your can’t define.

  22. When I studied physical chemistry a many decades ago, the accuracy of pH meters was limited by the glass electrode and determined to be ± 0.1 pH units. This is a physical limitation and while there were many electronic meters that would give a reading to 2 or 3 decimal places it did not alter the inherent limitation of ± 0.1 of the glass electrode. A further factor was that pH measurement with a glass electrode became increasingly unreliable as the concentration of NaCl approached 0.1 mol/l As sea water salt concentration is greater than this then accurate measurement of pH with glass electrode are always going to be questionable. However, if the salinity remains constant then the error will presumably remain constant also in terms of getting relative readings .

    The spectrophotometric method assumes that nothing else other than water is reacting with the dye. Given the microbial activity and algal photosynthetic activity all exchange hydrogen ions, as does the CO2 / bicarbonate / carbonate equilibrium, not to mention anything else that may be dissolved, then the pH value produced by this method would be highly suspect. In addition the amount of dye used is extremely small so as not to influence the pH itself (they are of course weak acids or bases) but therein lies another inaccuracy in that it takes very little activity by the factors mentioned above to change the proportion of the acidic to ionic form of the dye.

    • Peter Foster March 31, 2015 at 8:52 am
      The spectrophotometric method assumes that nothing else other than water is reacting with the dye.

      No it doesn’t, it measures the position of the following equilibrium:
      HIn+H2O↔H3O+ +In-
      The equilibrium coefficient of which is given by:
      Ka =[H3O+][In−]/[HIn]
      which gives:
      pH = pKa + log([In-]/[HIn])

      pKa is known for the indicator used and [In-]/[HIn] can be determined spectrophotometrically.

      The source of the H3O+ doesn’t matter.

      • Do it at a different ionic strength/temperature and you will get a different result. Salinity values are a must for sea water.

      • Phil.
        March 31, 2015 at 12:49 pm said ithe spectrophotometric method “measures the position of the following equilibrium HIn+H2O↔H3O+ +In-”

        No it does not. The spectrophotometer measures the proportion or amounts of [HIn] and [In-]:
        It does not know or care who is the donor or receiver of the H+ ion. Therefore if an acid other than H3O+ is the donor, or a base other than H2O is the acceptor then it the method will not measure pH.
        pH = -log{H3O+] the spectrophotometer cannot measure [H3O+]

    • “Does this mean all of the thousands of pH readings I took in the lab before 1988 were wrong?”

      The only way to know for sure is to develop a model and hind cast all your work.

  23. This would seem to have all the elements [as] a mainstream, eminently peer-reviewable, article. No

    [Use a valid email address please. .mod]

    • Nor was the Feel2899.pdf product peer reviewed by any journal. But if that was good enough for Congress, I suppose this blog post suffices for the rest of us, for now.

  24. I have a question. Recall Royer et al

    http://dx.doi.org/10.1130%2F1052-5173%282004%29014%3C4%3ACAAPDO%3E2.0.CO%3B2

    adjusted Veizer’s temperature record

    To this crazy sloping temperature record,

    http://en.wikipedia.org/wiki/File:All_palaeotemps.png#cite_note-2

    In which Royer would have you believe that the period Veizer marked as glacial around 450 million years ago was now hotter than today. The reasoning for such adjustment was pH adjustments.

    My question: was this pHraudulent pH data used to change the temperature record?

  25. An excellent article. Thank you, Michael Wallace. Yet another dataset that has been rigged to fit the political agenda and suppress any real understanding of the climate science.

    Two things spoil the otherwise excellent presentation. Damned running means and the lack of any DATA.

    The odd flat top ( slight dip ) around 1975-80 is an obvious distortion artefact. Get yourself a real filter and you will find that there is a peak there which will likely be close to the trough in SST at about the same time. There will likely be other aberations caused by the crappy filter.

    The resemblance to inverted SST is obvious and merits a closer look, which brings us to defect no. 2:

    which I later downloaded.

    Where ?? Please. You got it , you think it’s a scandal yet you don’t make it available.
    Where’s the beef?

  26. It has already been shown by several authors that the short term ( circa 3y ) variability of atmospheric CO2 is mainly a function of SST: d/dt(CO2) correlating with SST.

    This data seems to show the integration of that relationship, with the long term ( inter-decadal) levels of CO2 correlating with SST.

    I can see why they would wish to “disappear” the data.

    • That the integral , rather than the rate of change appears to correlate on the inter-decadal scale suggests that the system reaches a new dynamic equilibrium within that time span.

      This is why it is important to have access to the data, without the distortion of the 10y running mean.

      One of the first things I would do is examine whether there is still a significant lag between pH and SST having passed a non distorting 6y low pass filter. The 10y.

      That would give a means of estimating the primary time constant of the reaction. Comparison to variations in atm CO2 should be informative.

      Of course the fact that evidence was given to Congress on the basis of a flawed model not observations is a scandal. But sadly, there’s nothing new about that.

      • Mike, the “model” in this case is a quite direct physical-chemical model of ocean chemistry. The solubility of CO2 in seawater is known for every combination of salt, temperature, DIC (dissolved inorganic carbon), pH, alkalinity…
        The model is validated by the data collected at a few fixed stations over the past decades and repeated research trips over the same tracks. All what one can say is that the researchers didn’t warn that the pre-1980 trend was from a model, as the pre-1980 data weren’t reliable…

    • Mike,

      Short term variability of the CO2 rate of change is from the influence of temperature (and precipitation) on (tropical) forests. The long term trend is NOT from the biosphere and the overall long term influence is not more than 8 ppmv/K over the past 800,000 years. Near all CO2 increase over the past 160 years is from human emissions, maximum 6 ppmv from temperature…

  27. Sorry, but I don’t understand the purpose of this article. It is simply a repeat of an earlier presentation mostly from the same author of where there were 484 responses, including several of mine… Here a repeat of my comment:

    I have the impression that this is the same kind of discussion as for the pre-Mauna Loa CO2 data compiled by the late Ernst Beck: non-accurate instruments (…), wrong places where was measured and data for the same year all over the scale…

    Further the influence of CO2 on pH is very small: In Hawaii a drop of 0.05 pH unit with a (mainly seasonal) variability of 0.05 pH unit for an increase of 45 ppmv CO2 in the atmosphere (Bermuda has a double seasonal amplitude). That is about 40% of the total CO2 increase since the start of the industrial revolution.

    The next problem I see is that the pH is variable from place to place, even in the open oceans far away from the coasts, depending of uptake and release of CO2, downwelling and upwelling, temperature and bio-life…. There is a 0.5 pH unit difference (and more), depending where you measure and in what season.

    Thus I don’t think that he historical data have much value, as one need a series of data with very high accuracy (better than 0.01 pH unit) at the same place at high (at least monthly) frequency over many years to have a clear picture of any pH trends…

    The latter is the case for a few places in the oceans:
    http://www.tos.org/oceanography/archive/27-1_bates.pdf

    I like to see the spread of the historical measurements and the geographical distribution of the measurements in Wallace’s figure 1-a. I am pretty sure that the average geographical distribution of the measurements changed from year to year, making the whole exercise without any value about the possible influence of the increasing CO2 in the atmosphere on the pH of the ocean surface.

    It is like taking the temperature of Oslo a few years long and then the temperature of Rome for a the next few years and then back to Oslo. With as conclusion that there is an oscillatory trend in temperature…

    • While your points are reasonable, it seems improbable that the sampling errors should follow changes in average SST anomalies that well.

      Again, I’d like to see that without the distortions of the 10y running mean to see how similar they are.

      • The problem is less the sampling errors than the distribution of sampling over time. There are large differences in pH between polar and equatorial waters and even larger at upwelling places. If there was more sampling at/near upwelling places, then ENSO will have a huge influence both on the “global” pH as on rainfall in the tropics, as ENSO highly influences upwelling…

      • That is precisely what I meant by sampling errors. I did not say measurement errors.

        It may be possible to evoke uncertainty or bias is the sampling over time but when it starts to look like the changes in gobally averaged SST, it becomes hard to suggest that sampling bias would, coincidentally, be responsible without a fairly solid argument as to why sampling practice would follow SST.

      • I can agree mostly with Ferdinand on this one. The concept of a global ocean pH is even less meaningful than that of a single global temperature.

    • Ferdinand the posts at my blog site detail the sampling locations for most years and I’ve also posted a giant location file set at the dropbox site I’ve referenced. The WOD itself can be reviewed by you as well if you are seriously interested in the question of sample locations. For my part, I worked from an educated guess that a 10 year average might be a good place to start for a globally circulating water mass, and given the interesting parallels to other ocean drivers, I think I will be proven right. Perhaps some day a magic stationary sampling location, or a magic sampling trajectory will lead one to the most optimal fidelity of sampling to reality on all of the scales and modalities of interest. In the meantime, I hope that future comments this time can focus on the actual topic of this post regarding pH measurement accuracy, regardless of where the measurements were taken. I’m looking forward however to perhaps new posts on the location issue as well as the modeling issues, whether I write those or someone beats me to it.

      • Mike,
        The main problem with the “global” pH as you have compiled is that it is not global, as the sampling places were changing in all years and decades.
        No matter if you make 10 year averages or not, the sampling was one decade mostly in summer (1920’s) or more evenly distributed (1980’s-1990’s) which already gives a difference of 0.1 pH unit. Some decades the samples are mainly in the North Atlantic tropics and other decades mainly in the Southern Pacific, away from the tropics. In all cases the Southern Ocean is undersampled.
        The pH of the oceans is not the same everywhere and is heavily influenced by temperature and bio-life. The “globally circulating water mass” needs decades to circulate from one side of the globe to the other side and centuries for the part that circulates through the deep oceans, which has a huge influence on the pH of the upwelling places.
        Thus your compilation doesn’t say anything about the “global” ocean pH changes, as the sampling point error is many times larger than even the measurement error and than the theoretical drop in pH since 1850 (only around 0.1 pH unit).

        Further, the ocean carbon chemistry “model” used by Feely was validated at several fixed sampling stations (and more repeated sampling at the same transects). Here for 6 stations distributed over the oceans (mainly the Atlantic):
        http://www.tos.org/oceanography/archive/27-1_bates.pdf

  28. How much buffering capacity is there in the ocean relative to the amount of CO2 we could ever possibly release from fossil fuels?

    With 68% of the global benthic sediment comprised of mostly calcium carbonate there is a good bet that there is unlimited buffering capacity from the sediments alone.

    http://geology.uprm.edu/Morelock/dpseabiogenic.htm

    CaCO3-rich sediment weighs about 1g/cm^3 so a 1 m thick layer of the global carbonate sediments weighs approximately 3.5 * 10^17 g, or about 3.5 * 10^15 mols of CaCO3 in just the top m of the worlds carbonate marine sediment. According to Hansen, if we were to burn every possible fossil fuel we could it would release 1.25 * 10^16 g or 2.84 * 10^14 mols of CO2 into the atmosphere. So there you have it, there is an order of magnitude more mols of CaCO3 sediment in the top m of global carbonate sediments then there is in the total gross amount of CO2 fossil fuels could ever possibly produce. Subtract the annually sequestered CO2 from natural sinks and the amount that would stay in the atmosphere to get the net CO2 absorbed into the oceans and it’s clear that the available buffering capacity of CaCO3 sediments is far greater than the possible CO2 that humans could add to seawater through fossil fuels.

    It’s disturbing when looking through the literature on this subject. The research seems solid up until about 1988ish, then all of a sudden there becomes a litany of research involving CAGW pseudoscience filled with unsubstantiated claims with no citations to back them or citations leading to highly questionable model based or poorly designed experimental research. One such unsubstantiated claim is that carbonate sediment reaction to increased pCO2 operates on timescales of a 5,000-6,000 years and that this mechanism can only neutralize 60-70% of CO2 despite a much higher budget of CaCO3, and of course it was software models that came to these conclusions, much like throwing chicken bones except the bones lie less often:

    http://onlinelibrary.wiley.com/doi/10.1029/98GB00744/abstract

    I can only shake my head at such asinine claims. They simply ignore the ample research showing that these mechanisms operate essentially instantaneous on a geologic timescale, with empirical evidence showing these reactions take place on annual, seasonal, and diurnal timescales:

    http://www.sciencedirect.com/science/article/pii/S0016703706019983
    http://www.osti.gov/scitech/biblio/6768316
    http://www.jstor.org/discover/10.2307/30063990?sid=21106307848193&uid=2&uid=4&uid=3739672&uid=3739256
    http://archives.datapages.com/data/sepm/journals/v75/data/075/075003/454_gsjsedres750454.htm
    http://link.springer.com/article/10.1007/BF02784696
    http://tube.aslo.net/lo/toc/vol_58/issue_1/0131.pdf

    • RWTurner, you forget that there is only a fast mixing between ocean surface and the atmospheric CO2 for the upper few hundred meters. The mixing (and uptake) of CO2 by the deep oceans is much slower: there is hardly any exchange between the deep oceans and the surface, most deep ocean – atmosphere exchanges are via the polar deep water formation and the coastal upwellings…

      • It doesn’t matter how fast ocean currents mix CO2 within the deep and shallow seawater. Shallow ocean’s biologic pump and pCO2 in the atmosphere are intertwined which is then intertwined with the deep oceans via marine snow and various biologic activity. Not to mention that there is ample carbonate sediment in the shallow water mixed zone to actively keep equilibrium with pCO2.

        There is currently a net flux of carbonate sedimentation on the sea floor (0.9-2.2 * 10^14 g/year) and I’m not aware of any time during the Phanerozoic where there has been net global dissolution, even for 2,000+ ppm CO2 in the atmosphere. If mixing were so limited that excess CO2 could build up in shallow sea water and the ocean was no longer saturated with respect to CaCO3 then the geologic record would be quite different. CO2 may not have much to do with overall seawater chemistry at all:

        http://www.biogeosciences.net/7/2795/2010/bg-7-2795-2010.pdf

      • It should make people wonder how Trenberth can get his heat mixed at depth but that the water doesn’t take any CO2 with it. :)

      • Ok, I had to dig a little through the literature to find out where the meme of it taking thousands of years for CaCO3 sediments to neutralize pCO2. After finding several citations to literature that didn’t make the claim at all or to citations to literature that cited that meme from other literature itself, I finally found out where that claim stems from. It is from an Archer paper (go figure) from 1998 that coupled two models together. Somehow I’m not surprised at all that the entire meme is model based, and using 1998 computational power at that.

        http://geosci.uchicago.edu/~archer/reprints/archer.1998.neut_long.pdf

        And yes Michael, it’s funny how a simple stoichiometric reaction is claimed to take thousands of years to operate yet heat somehow distributed to the deep ocean in 40 years, 40 times faster than complete ocean circulation itself! It all makes sense if you drink enough Fool-Aid.

    • I am not sure what your point is. It sounds like you could be unhappy about the semantics. The semantics are not all that important. The process of the lowering of the pH of seawater is call “ocean acidification”.

    • Ian L. McQueen,

      I have a question for you:

      When you comment here, you appear to be a sceptic. Personally, I don’t care if you’re sceptic or alarmist. But on another blog you wrote:

      My posting to “…..the ever-ridiculous WUWT” (which is very much correct):

      Why would you say that?

  29. Michael Wallace,

    Sorry, but after reading the rebuttal of your article at:
    https://quantpalaeo.wordpress.com/2014/12/26/not-phraud-but-phoolishness/
    I only can agree with the rebuttal.

    Not only does the distribution of the sampling changes enormous from decade to decade (even more per year), the seasonal distribution changed too. in 1920’s over 60% of the samples were taken in summer, in the 1980’s and 1990’s the seasonal mix was better distributed, but fall and winter were still undersampled.

    In summer, the pH is lowest at all places of the oceans…

    • Ferdinand, after your statement that you agree with the rebuttal, are you also suggesting that modeled hind cast data to make proclamations of ocean pH trends is okay or valid? Hope not.

      My take…

      There seems to be enough for me to say that the historical data have sampling problems that cause some apples to oranges issues, and I believe that the exercise of creating an “average ocean pH” is fraught with major problems.

      So, instead, what has happened is that people with what seems to be a government-funded bias just make sh!t up, don’t tell anyone, then proclaim that the sky is falling? How/when did models with no accepted validation technique and without source code disclosure become reality? This is the major reason for the lack of credibility in my mind of those who claim that the models tell us accurately where we’re going. I work with and use models (validated with real-world observations) all the time in my job.

      Bottom line: it seems to me that trends in ocean pH are unknown at this time. Maybe this is unsatisfying, but it appears to me to be true.

      Bruce

      • I agree Bruce. Also, there are likely areas where the sampling was applicable in both location and season to get an idea of how the models do vs. actual measurements. (Why was this not done?)

      • Boulder Skeptic,

        Besides measurements, the pH of seawater is quite fixed when two of four parameters are known: ocean carbon chemistry is well known as that are equilibrium reactions which were established already 70 years ago… See:
        http://www.moyhu.blogspot.com.au/2013/09/active-ocean-acidification-calculator.html
        The “model” that Feely used thus is proven chemistry and validated at several fixed sampling places over the past decades:
        http://www.tos.org/oceanography/archive/27-1_bates.pdf

        The only point that one can blame Feely e.a. is that they didn’t make it clear to congress that the data before 1980 were based on a model, not the sampled data, as the latter are too inaccurate and too sparse to detect a change of 0.05 pH unit over the course of 130 years (pre-1980).

  30. The oceans dissolve CO2 (as well as outgass) with only 1000nth of it converting to carbonic acid:

    “Although the concentration of CO2(aq) far exceeds that of dissolved H2CO3 (in the order of 10³) we denote the concentration of all dissolved CO2 by [H2CO3].” – from section 9.2 of “CHEMISTRY OF CARBONIC ACID IN WATER” at http://www-naweb.iaea.org/napc/ih/documents/global_cycle/vol%20I/cht_i_09.pdf

    Thus, all the charts in all of the chemistry texts look similar to Fig. 9.6 of the IAEA text, however, their graphs frequently omit the proper labels noting that the two of the species are combined into one, as in (a) below:

    “Here we will use the symbols:

    a = [H2CO3] + [CO2aq] b = [HCO3] c = [CO3²]”

    The intent of these chemistry texts on the carbon dioxide species in sea water is to provide equilibria for varying pH and other variables such as temperature (e.g,, not to be used as a predictor for pH given total dissolved CO2):

    “Unfortunately, as noted by Dickson (1984), the field of pH scales and the study of acid-base reactions in seawater is one of the more confused areas of marine chemistry. The primary intent of measuring pH is to use it together with appropriated acid-dissociation constants (and other information – see section 1.2.5 above) to calculate the speciation of the various acid-base systems in seawater.” – from section 1.3.1 of “Part 1: Seawater carbonate chemistry” at http://www.epoca-project.eu/index.php/restricted-area/documents/doc_download/268-oa-guide-ch1-2010.html by Andrew G. Dickson.

    • The oceans dissolve CO2 (as well as outgass) with only 1000nth of it converting to carbonic acid:

      Almost all of the CO2 dissolved converts to carbonic acid, it just doesn’t stay there, it converts to bicarbonate, where most of it remains with a small amount converting to carbonate.

      • Yes, that is the generally accepted assumption by many marine biologists and climatologists, however, those you do hard science point out in my links is that what is referred to as carbonic acid in your cartoon is actually aqueous CO2 with a small bit of carbonic acid.

        If all of the C02 dissolved disassociated into carbonic acid species, then the atmosphere would have no CO2 and all of the plants would die!

      • Oh, never mind. I see that your Bjerrum chart replaces H2CO3 with CO2.

        Yes, of the portion that does not dissociate into carbonate and bicarbonate ions, about a 1000nth is actually carbonic acid at any given time, which is the point I was trying to make.

        However, marine biologists and climatologists assume that dissolved CO2 is actually carbonic acid due to graphs in chemistry texts that fail to note the distinction, without ever having actually solved the molecular equations.

        On the other hand, the authors of the chemistry texts never in their wildest dreams would have thought that their graphs would have been so abused.

      • An example of a fully dissociated acid is hydrochloric acid, which outgasses virtually no chlorine, even when NaCl is added.

        Many marine biologists and climatologists assume that CO2 and H2CO3 are one and the same.

        If that were true, all of our carbon dioxide would have been fully sequestered in the oceans.

      • jonesingforozone April 1, 2015 at 3:55 pm
        Yes, that is the generally accepted assumption by many marine biologists and climatologists, however, those you do hard science point out in my links is that what is referred to as carbonic acid in your cartoon is actually aqueous CO2 with a small bit of carbonic acid.

        As one who does ‘hard science’ I know how to read a graph, there is no reference to carbonic acid in the one I posted, in fact it’s rare to find a Bjerrum plot which does.

        If all of the C02 dissolved disassociated into carbonic acid species, then the atmosphere would have no CO2 and all of the plants would die!

        No-one said that, there’s that little word I used, “almost”, the equilibrium constant between carbonic acid and CO2(aq) is ~2×10^-3. While CO2(aq) and carbonic acid are frequently lumped together because of the relatively small amount of carbonic acid that doesn’t mean that the role of carbonic acid as a transition state between CO2(aq) and bicarbonate is not understood.

        jonesingforozone April 1, 2015 at 4:20 pm
        Oh, never mind. I see that your Bjerrum chart replaces H2CO3 with CO2.

        Thank you for your apology!

        Yes, of the portion that does not dissociate into carbonate and bicarbonate ions, about a 1000nth is actually carbonic acid at any given time, which is the point I was trying to make.

        But not what you said, carbonic acid is a transition compound to bicarbonate.

        However, marine biologists and climatologists assume that dissolved CO2 is actually carbonic acid due to graphs in chemistry texts that fail to note the distinction, without ever having actually solved the molecular equations.

        Not true.

        jonesingforozone April 1, 2015 at 5:38 pm
        An example of a fully dissociated acid is hydrochloric acid, which outgasses virtually no chlorine, even when NaCl is added.

        Indeed, but unlike carbonic acid Cl- is stable and there is no reason why anyone would expect Cl2 to outgas!
        A more relevant comparison would be sulfurous acid which is basically SO2(aq) which converts to bisulfite.

      • Still, it is the ratio of dissolved H2CO3 to CO2, which is about 1 molecule per 1000 in seawater, regardless of pH and regardless of the formation of carbonate and bicarbonate species, that defines the acid as being very weak.

        H2SO4 is another example of a even stronger acid than HCL and whose equilibrium with sulfur trioxide is undetectable.

        Were our atmosphere temporarily polluted with sulfur trioxide, all of it would end up in every nearby body of water, killing all life as we know it.

        Sulfurous acid, on the other hand, is a weak acid, though many times stronger than H2CO3. If the air were sporadically polluted by SO2, as by a copper smelting process, for example, I’m sure the residents would eventually drive the mining company out of town with pitch forks. The folk of the said town would then replace the income derived from the mining company with earnings from the drug and human trafficking trade.

        Yet, it is just as invalid to conflate SO2(aq) with H2SO3 as it is to conflate CO2(aq) with H2CO3.

      • (not conflated by you, of course, just the ocean acidification alarmists, especially in the marine biology and climatology fields)

      • From an ocean sediment proxy, the pH level of the oceans 21 million years ago was 7.4, then the pH level increased to 8.2 about 7 million years ago. See “Foraminiferal boron isotope ratios as a proxy for surface ocean pH over the past 21 Myr” at http://www.nature.com/nature/journal/v363/n6425/abs/363149a0.html

        Rather than relying on their shells to magically precipitate, sea creatures use specialized glands to produce and maintain them, so that it does not take millions of years to adjust to changing pH.

        In the 1960’s, a marine biologist experimented with shellfish, adjusting their pH down to 6.4 in a controlled environment, and concluded that shell maintenance must be the result of work on the part of the organism. (I read this this paper, not realizing that I would want later to share it, unfortunately).

        It was not a statistical study, to which ocean acidification mongers are limited.

      • jonesingforozone April 2, 2015 at 12:40 pm
        Still, it is the ratio of dissolved H2CO3 to CO2, which is about 1 molecule per 1000 in seawater, regardless of pH and regardless of the formation of carbonate and bicarbonate species, that defines the acid as being very weak.

        No it is not, it is the dissociation of the acid to produce H+ that defines the strength of the acid. This is frequently expressed as the pKa of the acid, the larger the pKa the weaker the acid.

        H2SO4 is another example of a even stronger acid than HCL and whose equilibrium with sulfur trioxide is undetectable.

        H2SO4 is a weaker acid than HCl.

      • Perhaps, but the term “weak” acid applies to H2CO3 regardless of the pH of the solution. It is considered weak because of the high ratio of aqueous CO2 to H2CO3, even though the more basic carbonate and bicarbonate species may dominate.

        H2SO4 is “stronger” than HCL in that the amount of sulfur trioxide that escapes from its solution in water is “immeasurable.” The chorine that escapes from an HCL solution is “virtually zero,” to four significant digits, which is incalculably greater than immeasurable.

        Sulfurous acid, on the other hand, is “a relatively strong member of the class of weak acids,” according to Chemical Demonstrations: A Handbook for Teachers of Chemistry, Volume 3 edited by Bassam Z. Shakhashiri, ISBN 0-299-12860-1. It has medicinal uses and can be mildly corrosive.

      • jonesingforozone April 2, 2015 at 10:27 pm
        Perhaps, but the term “weak” acid applies to H2CO3 regardless of the pH of the solution. It is considered weak because of the high ratio of aqueous CO2 to H2CO3, even though the more basic carbonate and bicarbonate species may dominate.

        No it is not as stated above, the term weak acid refers to the ability to produce protons and has nothing to do with the formation of the acid by the hydration of a gas.

        H2SO4 is “stronger” than HCL in that the amount of sulfur trioxide that escapes from its solution in water is “immeasurable.” The chorine that escapes from an HCL solution is “virtually zero,” to four significant digits, which is incalculably greater than immeasurable.

        Again this is not relevant to the strength of the acid, SO3 outgases from pure H2SO4 at temperatures above 300ºC due to decomposition, at more normal temperatures the amount of SO3 that escapes is ‘immeasurably’ small! Based on the true measure of the strength of an acid, pKa, HCl is a stronger acid than H2SO4.

        Sulfurous acid, on the other hand, is “a relatively strong member of the class of weak acids,” according to Chemical Demonstrations: A Handbook for Teachers of Chemistry, Volume 3 edited by Bassam Z. Shakhashiri, ISBN 0-299-12860-1. It has medicinal uses and can be mildly corrosive.

        Indeed, however according to your definition: It is considered weak because of the high ratio of aqueous SO2 to H2SO3, sulfurous acid would be much weaker than carbonic acid because that ratio is essentially infinite!

        Please stop spouting nonsense about a subject you don’t understand.

  31. The six most abundant ions of seawater are chloride (Cl−), sodium (Na+), sulfate (SO24−), magnesium (Mg2+), calcium (Ca2+), and potassium (K+). By weight these ions make up about 99 percent of all sea salts. The amount of these salts in a volume of seawater varies because of the addition or removal of water locally (e.g., through precipitation and evaporation). The salt content in seawater is indicated by salinity (S), which is defined as the amount of salt in grams dissolved in one kilogram of seawater and expressed in parts per thousand. Salinities in the open ocean have been observed to range from about 34 to 37 parts per thousand (0/00 or ppt), which may also be expressed as 34 to 37 practical salinity units (psu).

  32. While the author probably has a good point about throwing away pH data and using modeled data instead, his own modeling and reporting on it is seriously lacking, because there’s no way to reproduce the author’s analysis. There’s no code and no data made easily available.

    I introduce:

    A Rigorous Climate Modeling Discussion Checklist:

    All articles or large comments in climate modeling or data analysis should adhere to this checklist so that others may verify correctness and so the article or comment is understandable.

    “If falsification isn’t made as easy as possible, then the hypothesis isn’t even wrong”.

    1. At least one paper, previous comment, or article citation. [check]
    2. Referenced citations have a URL to the referenced papers or articles or quote directly. [check]
    3. Uncommon terms have a URL to a definition or embed the definition [check]
    4. There should be an introductory sentence, conclusion paragraph, executive summary, or some other way of identifying the key point of the article. [check]
    5. Charts and graphs have units and marked axis. [check]
    6. All data used has a URL to the data repository so that others may replicate the analysis. [fail]
    7. All code used has a URL to the code repository so that others may replicate analysis. [fail]
    8. All code has unit tests to help eliminate GIGO issues, and it helps others replicate the analysis. [fail]

    Score: 5/8. That’d score you a D+ in academia (at least the schools I asked my family about).

    The article is good from a classic academic point (items 1-5), but hasn’t caught up with ubiquitous cheap online storage capabilities of the early 21st century (Skydrive, Amazon, Dropbox, GitHub, etc).

    I welcome additions to the checklist. Note that signal processing issues should be a separate checklist, working on that one too.

    • Item 7 is tough to solve, I have wondered about it for some time. I have no compilers or interpreters on my Windows XP based laptop, and no plot software. I suppose that just being able to examine source code might be useful, but then, how many of you speak LISP ? My first choice would be Pascal, second would be C and for certain types of data sets, maybe LISP. Now, I do see why you all are laughing me out of the comments section, but do you see the difficulties that 7 conjures up ? I am NOT saying 7 is not valid, rather, how to maximize it’s usefulness. Also, data formats, FP versus integer and file organization ?

      • Item 7 is tough to solve, I have wondered about it for some time. I have no compilers or interpreters on my Windows XP based laptop

        There’s no requirement that the reader have the necessary software and that the writer limit themselves to the most primitive tools (sorry), only the capability of a reasonably technical reader of setting up the software and running it. By “reasonably technical”, I mean you should be familiar with setting up a Linux system running open-source tools (e.g. using the apt-get package manager), or buying Microsoft Office and installing the extra analysis packs for Excel, etc.

        I think you’ve found a missing item: Another checklist item should be “all tools used must have their versions documented and preferably a URL to the website where the tool may be obtained”. That’s a common requirement in modern production software, whose practices should be followed as the code used in academia gets more complex.

        I’m also thinking you should use a revision control system such as git or at least CVS…

        I find my self setting up virtual machines (VM) and installing the software if needed (for example a Linux VM is the best way to use GNU Octave on a Mac). You can also use Amazon’s EC2 virtual machines for relatively low cost if all you have is WindowsXP and a web browser. To see plots you’d need to either install Cygwin X server on XP, or you can probably render them directly to jpeg with the toolkit on Amazon and look at them in your browser.

        Heck, given the amount of free space available these days (10Gbytes for free typically), you can just upload the entire VM image or Docker Container package with code, tools, and data on it to DropBox or Amazon and that makes it amazingly easy to reproduce the environment and analysis. That’s also becoming a common practice in the production software world, because package management really is a PITA.

    • Any one who works with scientific data can easily reproduce my original time series plot of GOPph from the WOD archives, and some have already. There was no modeling involved. I did write some routines in Matlab for some of the geospatial contours I produced in some of my site’s posts, but for the global time series, it was just boring reproducible data munging. Feel free to spot check anything via the WOD’s interface if you continue to doubt the curve.

      • Any one who works with scientific data can easily reproduce my original time series plot of GOPph from the WOD archives

        How about the courtesy of the URL, as well as instructions for menu navigation if the URL doesn’t pinpoint the actual data?

        (it’s a badly designed website if the URL doesn’t pinpoint, but alas that is rampant and you can’t control that)

      • I did write some routines in Matlab for some of the geospatial contours I produced in some of my site’s posts, but for the global time series, it was just boring reproducible data munging

        So why not post the source? you’d be surprised what can creep in from “some routines in Matlab”.

        I’ve got 25 years of software development experience. There is no such thing as “boring reproducible”. Off by 1 errors can be very subtle and lead to 10 year lags in downsampled data (for example)

      • Just citing “GOPph from the WOD archives” is like citing the name of a 10,000 page book without having the ISBN, page number, revision number, etc of the reference. It’s a needle in a haystack. With a book it’s not proper citation method and it’s certainly not for the web where there are trillions of URLs…

        For example, here’s my lame attempt to find the data you used, which I believe would fully specify the data set (maybe, without your source code I wouldn’t know what your are eliding).

        Is this correct? Chances are, I’m on page 78 when I should be on page 7008…

        ———–

        Your citation: http://www.nodc.noaa.gov/OCL/

        click on “WODselect Online Data Retrieval System”, which gets you this URL http://www.nodc.noaa.gov/cgi-bin/OC5/SELECT/dbsearch.pl:

        Enter search criteria such that you get a result like this:

        COPY OF YOUR DATABASE SEARCH CRITERIA:
        Horizontal line
        DATASET: OSD,CTD,XBT,MBT,PFL,DRB,MRB,APB,UOR,SUR,GLD
        MEASURED VARIABLES (must): Temperature, pH

    • I think you’ve found a missing item: Another checklist item should be “all tools used must have their versions documented and preferably a URL to the website where the tool may be obtained”. That’s a common requirement in modern production software, whose practices should be followed as the code used in academia gets more complex.

      Yes, this should be another item.

  33. Peter, the authors answer to your post is contained in the post I think..”The ocean pH data omission was an unprecedented and disturbing incident in the history of hydrological sciences. Only NOAA can likely correct this. That’s because NOAA contains the source of the problem (the FEEL2899 pH time series product) as well as its solution (the WOD database).”
    ==================================================

  34. It is a dark day for science when a computer model is regarded as more reliable than measured data, especially in regard to chaotic-nonlinear mixing and exchange processes between atmosphere and ocean.

    The safety of such a hubris-ridden attempt can only be described by a metaphor quoted from Lister in the TV series “Red “Dwarf”:
    flopping your wedding tackle into a lion’s mouth and then flicking its love spuds with a wet towel.

  35. But can you be really really sure that nothing unexpected/unpredicted in the model might occur in the real ocean regarding mixing and pH?

    • Unexpected in general no, unpredictable yes, where there is (mostly coastal) upwelling: the amount of upwelling changes with wind speed, which makes that the pH at such places is unpredictable as that does change with the wind…

      If the more recent use of far more accurate colorimetric pH measurements are compared with the calculated ones (from total alkalinity and DIC), these show the same values and the same trends over time within the measurement error ranges. See e.g. for the Hawaii data series (HOT), Fig. 1:
      http://www.pnas.org/content/106/30/12235.full.pdf.

  36. Has somebody made a copy of the WOD Database. I expect that this hubbub will cause it to disappear, just like the pre-adjusted temperature database.

  37. A computer model more reliable than measured data!

    Surely the measured data needs suitable error bars and is then, ‘Good to go’?

    • The measured data need error bars from the floor to the ceiling in Figure 1-a. Partly because of the accuracy of the glass electrode pH measurements in seawater pre-1990, but mostly because of the random sampling when changes of 0.5 pH unit are common between poles and equator…

      If calculated from other more accurate measurements like DIC and Total Alkalinity and selected for the same smaller ocean areas away from upwelling zones and estuaries, that may give a better idea of the real pH change over time, as is the case for a few longer series at fixed places…

  38. Thanks All for comments and insights and arguments to continue to ponder. I take this opportunity to address a general question and then a specific comment by Peter Foster which was published here on March 31, 2015 at 8:52 am.
    In general, any who wish to learn more about the ocean pH data are encouraged to visit the NOAA WOD site and find the “WODselect” menu item. I see today it is at: https://www.nodc.noaa.gov/OC5/SELECT/dbsearch/dbsearch.html
    Once there, the flexible database is yours to explore in many ways. I recommend simply choosing the “Measured Variables” search criteria, and then in the window that will follow, explore the types of parameter information that interest you, including “pH”. It’s designed to be easy to use.

    Peter Foster, Thanks for your comment. I think your insights have answered many of my own questions. I want to also take advantage of that and other comments to respond and expand on my post a bit.
    I first note that many subject matter experts in fields related to hydrologic circulation in general and ocean circulation (some who have made eye opening posts here as well) appear to reinforce the conviction that essential ocean science should include the search for inflection points regarding the last century or so of global ocean pelagic pH (GOPpH).

    They might also support that a ten year moving average of the GOPpH instrumental data is much better than nothing, far better than a data devoid model, and likely better than moving averages with shorter time spans. This might be especially supported, considering the search through decadal to century scaled spans of time.

    They hopefully would agree that a massive globally circulating and state – changing medium such as H20, has challenged, and will continue to challenge scientific monitoring schemes, not only for GOPpH but every other physical, chemical, and biological parameter for years to come.

    Regarding GOPpH – purposed instrumental measurement error, Peter pointed to the possibility that in practice, something like 0.1 pH unit is not accurately measurable. Peter, you did not yet propose what precision of pH measurement you believe can be accurately determined under waters of high ionic strength. This post points to the SCOR 75 proceedings (published in 1992, and here noted as reference 10) which addressed your concerns, I think. I can add that for continental groundwater and surface water measurements, ionic strengths of some waters can easily exceed those of natural sea water, and that NIST endorsed glass electrode pH meters with a reported accuracy of 0.01 pH units, are put into use for practical effects widely and routinely.

    If you know of additional reasons to discount SCOR 75 or other findings, I’m interested to learn, but in any case I can assert that such a coarse accuracy as 0.5 pH units, or even 1 full pH unit, are perfectly fine for searching for a primary infection point within the GOPpH time series. It is an embedded principal of my post which I provided the first figure and other citations to support.
    The NOAA WOD resource indicates that recorded ocean measurements can range across about 4 full pH values, yielding five pH ‘points’ from 6 to 10. This appears to be sufficient for inflection detection because 5 points are needed at a minimum for such a purpose.

  39. It might be of interest to note the IPCC ‘take’:
    In ‘Climate Change 2007: The Physical Science Basis’ they say on p405 that ‘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′
    Calculated from an estimated uptake? – I believe the appropriate American expression is ‘yeah, right’!
    Also (on p501) we find that ‘Ocean CO2 uptake has lowered the average ocean pH (increased acidity) by approximately 0.1 since 1750′
    But (p405) we’re also told that ‘the mean pH of surface waters ranges between 7.9 and 8.3 in the open ocean.’
    Given all of this, how can any of the anthropogenic CO2 / ocean pH claims hold water (so to speak)?

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