Guest Post by Willis Eschenbach
A recent post by Anthony Watts highlighted a curious fact. This is that records of some two and a half million oceanic pH samples existed, but weren’t used in testimony before Congress about ocean pH. The post was accompanied by a graph which purported to show a historical variation in ocean pH.
I was unimpressed by the graph in that post, which seemed simplistic and, well, in a word, wrong. But on the other hand, I certainly found it bizarre and most interesting that someone would throw out that huge amount of scientific data. That was the reason I forwarded it to Anthony, in the hope of unraveling the actual truth of the matter.
So … as is my wont, I’ve now taken a look at the data myself, albeit at the moment a very preliminary look. The data was conveniently provided by a WUWT commenter in .csv format here, my compliments to him for the collation. He also has a good explanation of the process, along with R code. Note that there has been no quality control on the data. About 2% of the surface pH values are well outside the range of oceanic pH, and I removed them before looking further at the data.
Now, the first question I asked was, where were the samples taken? The problem with the graph in the recent post linked to above is that it lumps together samples taken in various parts of the planet. And unless the sampling is uniform in time and space, this is a Very Bad Idea™.
So I made a map that shows where each surface sample was taken. For simplicity, and because this was my first cut, I restricted myself to those samples with a depth of 0 (right at the surface), which are a bit less than a tenth of the total samples. Here are two different views of the same location data.
Figures 1a and 1b. Two views of the location of the surface samples of the global pH dataset, centered on the Pacific and the Atlantic. In some regions you can see the tracks of the oceanographic expedition vessels quite clearly.
Now, I must confess that this was a surprise to me. I hadn’t expected the concentration of samples around Japan, it appears the Japanese oceanographers mush have been quite busy. And I also hadn’t expected the high sample density in the Baltic Sea and the other enclosed seas (the Black Sea between Turkey and Russia, and the Caspian Sea to its right).
Finally, here are the average pH values by gridcell, for the entire period of record
Figure 2. Average values of pH by gridcell in the record.
Now, you can see from these maps that we cannot simply put all of that data into a single box and extract a timeline from it.
So … was there “pHraud” in not utilizing this data? I say no, there was no fraud. I say this in part because it’s so difficult to infer intent. Because I have been falsely accused of having bad intent a number of times, I’m sensitive on the subject. I dislike accusations without evidence, and I see no evidence of fraud in this case.
However, it is a huge scientific resource, two million plus pH samples taken by oceanographers over decades, and not using it without some solid scientific reason for ignoring it just doesn’t work for me. What I suspect has happened is that the mass and complexity of the data was too overwhelming, and so the investigators simply put it into the “Too Hard” pile. But that’s just speculation, the real reason may be entirely different. Regardless of the reason, I do think that the authors should have explained their omission.
In any case, that’s the story so far. It certainly appears to me that there is plenty of data there for meaningful time series extractions in some areas. There are, for example, about 400 1°x1° gridcells that have more than a hundred observations per gridcell, and groups of nearby gridcell cells combined have much more data. The North Atlantic and the oceanic area off of Japan seem like they would have more than adequate data for time series extraction.
I may or may not do any followup on this dataset, but I invite readers to use the data for their own analyses.
Regards to all,
w.
ADDENDUM: As usual, I request that if you disagree with someone, please have the courtesy to QUOTE THEIR EXACT WORDS THAT YOU DISAGREE WITH, so that we can all understand the exact nature of your objections.
OK, an engineer’s question about the scale of all this. Atmospheric mass is ~5.15×10^18 kg. The mass of all of the CO2 currently in our atmosphere is around 2.0×10^15 kg. Mass of the oceans is somewhere around 1.4×10^21 kg. If we dissolve every single bit of atmospheric CO2 into the oceans that’s a change of a little over 1.4 ppm. Chemists, how acidic would 1.4 milligrams dissolved CO2 make one liter of sea water? (or 1 mole of CO2 in 32,428 liters of water.)
Am I missing something here besides the buffering?
If we dissolved every bit of atmospheric CO2 into the oceans, we would all, every living creature on the planet, be dead, extinct.
But there hides the Warmistas’ biggest lie – more CO2 is beneficial.
Yea, that was my point… considering that we’ve only got about 140 ppmv “extra” CO2 in the atmosphere before we hit that point below which plants start suffering.
If you consider the fact that greenhouse operators add CO2 to the interior atmosphere now, then it is highly likely that plants are already suffering. When you consider the amount of primary productivity that dinosaurs required, and that the planet currently could not support a population dinosaurs comparable to the Jurassic or Cretaceous, it seems pretty certain. My favorite speculation is that the similarity between the present and the late Permian might mean the same termination. Since the end of the Permian was cold (like now in fact) and CO2 was very low (not quite as low as the present), there seems to a reasonable possibility that inadequate primary production ended the Paleozoic and ushered in the Mesozoic. So, we are experiencing a “wave of extinctions” they say. What comes after Cenozoic, and is human CO2 output slowing the onset?
Duster, If I remember correctly the O2 levels rose throughout the Mesozoic as well. All that evil plant life gorging itself on that excess planet killing CO2. Dinosaur’s size increased along that same time line. Simple correlations but does certainly suggest that CO2 is good for life and not bad. Wonder why the Climateers can’t get their heads around that concept?
“Chemists, how acidic would 1.4 milligrams dissolved CO2 make one liter of sea water? (or 1 mole of CO2 in 32,428 liters of water.)”
That amounts to an increase in dissolved inorganic carbon (DIC) of about 0.031 mmol/kg, which would lower the pH by about 0.06 pH units.
What you are missing is that the oceans mix very slowly, so the emitted CO2 that has dissolved in the ocean is mostly in a very small fraction of the ocean volume. The estimated change in mixed layer DIC since pre-industrial times is 0.056 mmol/kg, producing a calculated pH change of 0.11 pH unit. Double CO2 would increase DIC by a further 0.064 mmol/kg and triple CO2 would add 0.054 mmol/kg beyond that. The corresponding pH increments are 0.14 and 0.15 pH unit. With triple CO2, carbonate in the mixed layer would be just over half its pre-industrial concentration.
At some point, cranking up CO2 will be a problem. Personally, I am skeptical about that happening soon.
My source for the numbers is:
Kleypas, J.A., R.A. Feely, V.J. Fabry, C. Langdon, C.L. Sabine, and L.L. Robbins, 2006. Impacts of Ocean Acid- ification on Coral Reefs and Other Marine Calcifiers: A Guide for Future Research, report of a workshop held 18–20 April 2005, St. Petersburg, FL, sponsored by NSF, NOAA, and the U.S. Geological Survey, 88 pp.
Although I downloaded it from the web some years ago, I no longer have the link.
OK, so starting with a clean “back of the envelope” and looking at the whole of man’s contribution to CO2 instantly dissolved in the mixed layer the numbers are close to the same. Consider mixed layer average of 150m (throwing out the < 50m warm shallows and the 1000m deep near freezing polar zones) that’s 5.415×10^19 kg for water mass. Man’s contribution to atmospheric CO2 is 9.05×10^13 kg (with proper mass fraction values, my previous math was based on volume fraction… oops.) That’s still only 1.67 mg/kg CO2 in sea water or 0.038 mmol/kg. (I also used 1kg/l so I’m ignoring everything else in sea water mass wise.)
That still doesn’t make for a pH change that gets outside the real working differences of current pH meters and standard calibration solutions. And I’m assuming all the CO2 goes in at once and is 100% mixed. I’m not real worried about this.
I would like to suggest that the greater the potential change in the PH of the upper 200 meters manifests, the stronger the buffering influence of lower depths. of oceans would occur. In other words, I do not think the buffering affect of the lower depths is linear, just as the greater the increase of surface T manifests, the more lower upwelling of un-warmed water would counter the T increase
Not a matter of quantities, a matter of pressure differences and equilibria:
– a 30% CO2 increase in the atmosphere for a certain water temperature gives a 30% increase of free CO2 (gas) in the oceans surface (Henry’s law).
– a 30% increase of free CO2 in the ocean surface gives a 3% increase in total carbon (DIC) in the ocean’s surface (chemical equilibria).
– a 3% increase in DIC gives a pH drop of 0.1 unit in the ocean surface.
Change is mostly in the surface (0-200 m) as the deeper oceans show much less exchange…
Very nice, but one question; with a ~30% supposed increase in CO2 in-atmosphere yielding a ~3% increase in DIC, what is the calculated increase in Biomass? Oh, you don’t have that? So much for organic equilibrium.
CO2 was as high as 7,069 ppm 520 Mya and 12,000 ppm at 635 Mya.
That is 253% and 428% higher than the pre-industrial equilibrium.
So your math Ferdinand, provides for ocean pH’s of 5.4 and 3.4 respectively for the periods just when complex life was evolving.
On the other hand, many life-forms have pH’s in that range.
I think we need a new formula. Those numbers do not sound right.
Sorry, I did the math wrong. Obviously, with CO2 that high, pH goes below Zero making the ocean the most acidic substance in the universe at those periods.
New formula time.
James,
The 30% increase of CO2 in the atmosphere has some influence: the earth is greening with 1 GtC/year or 10% of the human emissions, as CO2 is one of the limiting factors for land plant growth.
The 3% increase in DIC in the ocean surface has hardly any influence on bio-life in the oceans as CO2 (as bicarbonate) is not the limiting factor for algae growth. The summer/winter difference at Bermuda is not more than 2,5% of DIC. Trace elements like iron are the main limiting factors…
Bill Illis, you forget that Ca and Mg were also far more abundant in the oceans… Meanwhile lots of the combination can be found as carbonates in the white cliffs of Dover (UK), the Dolomites (Italy), the karst landscapes of Ireland, the caves of Carlsbad (USA) and many other places…
But there are several web sites where you can calculate the (theoretical) pH and other ocean related data for any more recent period on earth, including ice ages:
http://biocycle.atmos.colostate.edu/shiny/carbonate/
Ferdinand Engelbeen December 31, 2014 at 7:03 am Edit
Thanks, Ferdinand. While you are correct as far as that goes, it’s somewhat more complex than that, as you’ve assumed that both total alkalinity and salinity are constant … which is generally not true.
w.
Ferdinand, as a real-world example, consider the Hawaii HOT time series of surface measurements of seawater from 1988 to 2012. During that time, CO2 rose by 12.1%. From your rules above, we’d expect a change in DIC of 1.2% … but in fact over the same period the DIC rose almost twice that amount, 2.2%.
Regards,
w.
Willis,
For the ocean as a whole, alkalinity and salinity are essentially constant on a time scale of centuries. There may well be small local variations. I plan to have some fun looking at the data you provided.
Bill Illis,
On geological time scales, alkalinity (and perhaps also salinity) will not be constant. Alkalinity is the total capacity of a solution to neutralize acid. For the oceans, that means that
alkalinity = [HCO3-] + 2*[CO3=] + minor bases (such as borate and phosphate)
A more acidic ocean will cause sediments, especially CaCO3, to dissolve. More CO2 in the air means more acidic rain which would increase the weathering of rocks. On geological times scales, that will raise the alkalinity and counteract the effect of higher CO2 partial pressure on the pH of the ocean.
Past episodes of high CO2 occurred slowly compared to what we are doing. I would not be surprised if raising CO2 30 times in a million years would have less effect on ocean pH than raising CO2 by a factor of 3 in 100 years.
Willis, the real uptake depends of temperature and Revelle (buffer) factor, the increase over the past decades at several places can be seen at:
http://www.tos.org/oceanography/archive/27-1_bates.pdf
Fig. 3 and Table 2 show the trends and figures.
Willis,
You will notice that in the data set there is a column labelled DIC and another labelled nDIC. The latter has some sort of salinity correction. The P_CO2 values in the file change by 13% and the nDIC changes by 1.3%, right in line with Ferdinand’s numbers.
Salinity and alkalinity have a slight upward trends, I don’t know why. The salinity corrected alkalinity, nTA, is almost perfectly constant.
I found it interesting that the file has two independent determinations of pH: a direct measurement and indirect from bicarbonate and carbonate. The r.m.s. difference is 0.007 pH unit, so if the two methods are equally accurate, the standard deviation of each is 0.005 pH unit. Impressive.
“Salinity and alkalinity have a slight upward trends, I don’t know why. ”
Surface salinity varies from place to place in the ocean depending on the balance between evaporation and precipitation; excess evaporation leads to higher salinity, excess precipitation leads to lower salinity. If a given location in the ocean has a trend in the relative amount of precipitation and evaporation (whatever the cause of climate change), there will be a trend in surface salinity.
The ratio between alkalinity and salinity stays constant, since all salts are affected equally by dilution. So the trend in DIC has two components, one due to a trend in alkalinity linked to the salinity trend and one due to increased CO2. The variable nDIC has the first contribution removed.
The data selection is a major part of the story. What is as important, is Sabine’s reaction to questions put to him through FOI and the answers he gave. They appear to suggest they knew they were cherry picking data, but didn’t think they would get caught.
FOI? Did Sabine provide documents under FOI?
Tim, if you have sparse data, scattered in place and seasons over the years with an accuracy of 0.1 pH unit, how do you find a trend of 0.05 pH unit over the period 1850-1984?
It’s a lot more than a single tree to fabricate a hockey stick for the IPCC.
Why did they not reply to the FOI request and give snarkey replies if they had a good scientific basis?
If the accuracy of 0.1 pH is a random error, large data set averages are more accurate. This is exactly the same issue as thermometer reading, where plus or minus 1 degree readings (and even large offsets due to urban heating or poor placement) were used to generate a data set claimed accurate to 0.05 C or so, with a total rise in 150 years of 0.75 C. Unless there is a shifting bias in the readings that is not corrected for, your argument falls on its face.
Leonard, agreed, but Berényi Péter has gridded the pH data in 5×5 degree boxes and he finds an essentially zero trend with an error margin over 30 years of ~0.02 unit/decade.
The measured (and theoretical) trend at a few places with modern equipment is around -0.015 unit/decade, thus not measurable with the pH glass electrode pH measurements.
The measurements in earlier decades were even more scarce and the trend smaller (CO2 increase 1850-1984 was about the same as 1984-current).
“However, it is a huge scientific resource, two million plus pH samples taken by oceanographers over decades,”
I remain puzzled how a mere 2 million bits of data cannot be analyzed in a short space of time by any of the groups with big computers.The new supercomputers in England could knock it over in 2 minutes, Mosher and Zeke 1/2 an hour, Nick Stokes or McIntyre perhaps a week.
Heck it could be a class project at any US university course on climate change.
Data entry….
Analysis by computer is a snap, you try entering 2 million results with coordinates.
They are already available with dates, depth and coordinates. Or did you think Willy keyed in 200,000 datapoints by hand the last few days?
Willis, regarding sampling density, I enquire as to why folks were measuring ocean Ph. I figure that there was local concern about the effects of industrial pollution on the oceans, thus programs to monitor closely the Ph were part of other environmental monitoring projects.
Japan, Baltic, Caspian and Black Sea?
Scientific curiosity to start with [why did Darwin look at finches ?], because you can and because it’s a feature of water that can measured easily.
http://en.wikipedia.org/wiki/Challenger_expedition
Oceanography is important to Japanese that get a lot of their food from the sea. The Baltic, the Black and the Caspian seas are special cases which have aberrant and very variable conditions, hence interesting to study. The Baltic is brackish to almost fresh and very influenced by river runoff and occasional injections of salty water from the North Sea. The Black sea is unique (in the present) by being anoxic at depth while the Caspian is essentially a big salt lake. Incidentally, even in the deep anoxic part of the Black Sea, with a high concentration of H2S the pH does not go lower than 7.6.
Just saw Fabien Cousteau diving around the Great Barrier Reef off of NE Australia. He and Philippe Cousteau keep talking about the acidification of Great Barrier Reef etc. Looking at the average values of pH taken around that area Fig 2), it looks like it is among the most alkaline (pH 8.25). I wonder if those values were taken closer to 1910 or 2013? What are the pH values there now? Has it moved closer to pH 8.19 or 8.13 (or lower) now – that info should be available? Without time of measurements it’s hard to tell what’s going on between 1910 and now.
Probably not. The symbiotic algae in corals “eat” a lot of CO2 and keep the pH high. It can touch 9.0 in late afternoon over a coral reef. Lower in the morning of course, since photosynthesis stops but respiration continues in darkness.
There is no such thing as ‘an’ ocean pH. It varies diurnally, seasonally, and by ‘ocean ecosystem’ of which there are 8 in the Pacific. Swings are 1 to 1.5 annually, far more than theoretical possible AGW changes. Driven by biology, not climate. Essay Shell Games in ebook Blowing Smoke has referenced details. That is why we exist on a blue planet suffused by oxygen.
Can I assume then that you also don’t think there is such a thing as a global temperature? Temperatures also vary diurnally, seasonally, by latitude, by altitude, and for all sorts of other reasons. Perhaps you should let climate scientists know about the futility of their efforts before they make a fool of themselves. 🙂
Of course there is no such thing as a global temperature. Temperature is an intensive property. Climate scientists have repeatedly shown themselves to be fools (or they have an agenda).
Ditto
Count The Git as a sceptic here, too. He also notes that the calculated global temperature has fallen somewhat over the decades…
Friends:
I, too, support phillipbratby when he writes
For those who have not read it, Appendix B of this discusses the various possibilities of what so-called ‘average global temperature’ may be and the implications of those possibilities.
Richard
Would the term “convenient incompetence” be appropriate?
Willis wrote: “What I suspect has happened is that the mass and complexity of the data was too overwhelming, and so the investigators simply put it into the “Too Hard” pile. But that’s just speculation, the real reason may be entirely different.”
My guess is that the real reason includes issues with the accuracy and quality control of the data. Glass electrode data are usually not much better than +/-0.1 pH unit, and can easily be much worse if proper procedures were not followed. So one has to sort through the two million data points to try to figure out which are really reliable, and most will likely end up in the “don’t know” pile. So I think it is likely to be “too hard” combined with “too little chance of ending up with something useful”.
Actually no pH measurements are ever much better than +/-0.1 pH units since they all ultimately refer to calibrations with a chemical standard calibration fluid. These are claimed by manufacturer to be exact to 0.01, but they aren’t. Even the best brands often vary by +/-0.05.
Thanks All for continuing to follow up and develop the WOD information.
I haven’t been able to post because of a technical problem. Also I haven’t wished to interfere, but at this point it seems there are many speculations that don’t match with the work I’ve produced on this nor do they match with the full history of my communications with the two PMEL authors.
Anthony Watts now has a copy of my transcript of PMEL communicaitons. Stephen McIntyre was given that transcript over a year ago if I’m not mistaken. Perhaps one of them will post. I don’t want that on my own site. Also all readers and writers may wish to examine the 11 posts regarding my own preliminary data extractions at
http://www.abeqas.com/category/ocean-ph/
Also it might be of interest to know that I covered these same concerns via several comments I posted at RealClimate last January (17?).. about a year ago. For some reason, there was no followup interest from anyone, but the comments are for the most part still there. Michael Mann was the guest host for that piece titled “if you see something, say something”. I’m grateful that they did not remove those comments but I hope they will sign the petition.
Also please note that the petition I produced was in response to indifference from every single subject matter expert and Senator that I took this up with discretely over many months. The petition only asks that NOAA do its job and develop this data properly. This way people like myself, Willils, and others, don’t need to take time out of our priorities to do their job for them.
Also, the petition doesn’t accuse anyone of fraud. If the PMEL authors of note were to sign the petition, that would be a good start towards reducing the heat on this topic and moving towards reform. Again the petitiion is at:
http://www.ipetitions.com/petition/restore-the-worlds-ocean-ph-measurements
“Willis Eschenbach tips me to a story by Marita Noon, titled:
What if Obama’s climate change policies are based on pHraud?”
So now, a week later, not a fraud? If anyone is a fraud, I’m suggesting a particular grad student and his mentor both whom don’t vet their work before accusing people of fraud.
I told Anthony about the story, not because I thought it indicated fraud, but because I found it quite bizarre that a pile of data that big, 2.5 million observations made by professional oceanographers over decades, would just be ignored.
Note that the accusation of fraud came from Marita Noon, not from me. As I said above, I’m reluctant to ascribe motives. Heck, half the time I’m not sure what my own motives are until after the fact, and perhaps not even then.
w.
What part of “Willis Eschenbach tips me” are you try to evade?
trafamadore December 30, 2014 at 9:09 pm
What part of me saying immediately above that “I told Anthony about the story” are you try [sic] to evade?
w.
Do you have a problem with reading and comprehension ? Look at the comment from Mike Wallace at 7:46 pm … the very one prior to and, yeah, 10 minutes before your diatribe.
Streetcred December 31, 2014 at 12:45 am Edit
Streetcred, it’s totally unclear who the “you” in your comment is referring to. I suspect it’s trafamadore, but large oaks of contention grow from such small acorns of misunderstanding.
In any case, it’s very common for someone not to see a comment made ten minutes before theirs. Suppose I pull up the thread at say 9 pm. I then start reading it. At 9:15, I come across a comment I want to respond to. I spend another fifteen minutes answering it, including looking up references and getting a new cup of coffee. My response goes up at 9:30.
Meanwhile, there are an entire half hour (gasp!) of comments I haven’t seen that have been added to the thread.
So sue me …
w.
Follow the indentations, Willis. Had Trafamadore taken 30 minutes to compose and publish that rubbish then he/she/it definitely has an issue with reading and comprehension, so your explanation is in his/her/its case is weak. If Trafamadore had done any research into sourcing the original article alerting the pH issue then he/she/it would be fully aware that the author has been 100% ethical in how he has prosecuted his business. It is appalling that Trafamadore should accuse Mike Wallace “and his mentor both whom don’t vet their work before accusing people of fraud” … what does he think that they are, CAGW warmista?
Willis … “So sue me …” What an outrageous statement, are you serious or is it just the New Year cheer?
Streetcred December 31, 2014 at 4:57 pm
Thanks, Streetcred. I don’t trust the indentations in the slightest, as they are difficult to follow. I and many others often reply at the wrong indentation level … heck, it’s not uncommon for people to post on an entirely incorrect thread.
That’s why I ask people to quote the words they object to, so we can have clarity about who and what they are disagreeing with.
Thirty minutes was just an example, Street. In fact, all trafamadore needed was to take more than ten minutes to answer, and he’d have missed the new post … and I often go get a coffee or otherwise consider my answer, taking up ten minutes easy. Heck, I’ll often go off and read a few more comments, then come back to answer the earlier comments. So no, it’s not “weak” to think trafamadore might have taken ten minutes to answer … we’re not all as swift as you consider yourself to be, I guess.
So sue us all, I guess …
w.
“So sue us all, I guess … ”
That is so immature … on what grounds do you suggest that this might be possible ?
Streetcred December 31, 2014 at 5:04 pm Edit
Streetcred January 1, 2015 at 10:08 pm
On the grounds of humor … I picked up the phrase from when I was a musician backing up an amateur production of Guys and Dolls, but since then it’s gained its modern meaning, viz:
Best regards,
w.
An excellent post ten minutes before yours, directly above yours, and you poison the well with this “acidic” comment?
Yes well. Readers shouldn’t HAVE to trawl through data to construct time series where prima facie an interesting scientific truth emerged from recent analysis showing a rising pH.
We spend literally $trillions. And if ocean acidification is disproven, that may be one of the most valuable discoveries in history.
What are you thinking? It’s simple physical and general chemistry. The partial pressure of CO2 goes up in the air (physical chemistry), more CO2 goes into the H2O (physical chemistry), the pH falls (general chemistry). Lot’s of details, like the temp of the water and the buffering in the water (both general chemistry) and where the water comes from (history, just kidding, Ill go with physics), but in the end it’s simple physical and general chemistry.
@trafamadore
You’re right – up to a point. You’ve written the first chapter of the story
If you did the experiment in the lab with pure water and CO2, you’d get the results you describe. That’s about as far as the theories of physical and general chemistry will take you.
But the oceans ain’t the lab and sea water ain’t pure.
The challenge for the experimentalists/observationalists is to show whether the expected effect actually happens in practice in the oceans where a whole host of other factors are in play (some of which you have mentioned).
The discussion to date show that they are nowhere near having enough usable real world data to adjudicate one way or another on the issue. Looks like they won’t have for a very long time either.
And even if there were shown to be a real world change in pH, it would be necessary to show that this actually mattered to anything we care about.
Personally I find it hard to believe that many organism couldn’t withstand a pH change of about 0.1 units. Any more than there are many which can’t cope with the temperature changes between winter and summer or between a week of low relative humidity and a week of high. Anything so highly adapted to a very narrow environmental range is unlikely to be widespread nor long lived (in evolutionary terms).
Andrew, there was no rising pH. The pH “trend” in the compilation of Wallace is the result of scarce data taken at different places and seasons over the years…
Strange, with all the talk of ocean acidity destroying coral reefs, no samples taken on the lower half of The Great Barrier Reef where all the fertiliser from agriculture and where the coal exporting ports are located, and very few from Mackay upwards, the same for Ningaloo Reef. it is almost like they were trying to hide something.
‘For the period from 1940 to 2009, corals from
both inner as well as mid-shelf sites exhibit the same overall decrease in δ11B carb of 0.086 ±0.033‰ per decade, equivalent to a decline in seawater pH (pHsw) of ∼0.017 ±0.007pH units per decade. This decline is consistent with the long-term effects of ocean acidification based on estimates of CO2 uptake by surface waters due to rising atmospheric levels. We also find that compared to the mid-shelf corals, the δ11B carb
compositions for inner shelf corals subject to river discharge events, have higher and more variable values and hence higher inferred pHsw values. These higher δ11B carb values for inner-shelf corals are particularly evident during wet years, despite river waters having lower pH. The main effect of river discharge on reef-water carbonate chemistry thus appears to be from higher nutrients driving increased phytoplankton productivity, resulting in the drawdown of pCO2 and increase in pH sw.
Coral records of reef-water pH across the central Great Barrier Reef, Australia: assessing the influence of river runoff on inshore reefs
http://www.biogeosciences-discuss.net/11/11443/2014/bgd-11-11443-2014-print.pdf
Does this help?
Willis: My Brother teaches “medical chemistry” at a community college in a large metro area.
Unlike my ERA when even at the University, you might have 2 to 6 students sharing ONE already 20 year old pH meter, at his school there is a pH meter for every student in the class, he intentionally gives the students one meter per 2, to enforce “teamwork”. None the less, he typically has 15 pH meters lined up, in FRESH 7.0, commercially made…buffer at the beginning of each pH usage type class. He looked at the previous measurements and comments and asked, “Who are these IDIOTS, and what experience do they have with instrumentation???”
He explained: 15 current (within 5 years) vintage, digital, self compensating (for temperature) pH meters, in commercial buffer solution. Line them all up, look at them 7.00 pH +/- 0.1 pH units. ALL THE TIME. Strangely (NOT!) you average them all and the number will be 7.0 +/- 0.07 or so pH units. It is NOT a self corrector type of error. (I.e., the central mean theory DOES NOT SEEM TO HOLD for this sort of measurement.
When he say claims to .03 or .01 pH unit accuracy by averages he SNORTED. “Meaningless”. I would tend to agree.
I doubt it is the meter that is the issue. More likely it is the glass electrodes. If you use cheap electrodes or if they have been mishandled (banged around, allowed to dry out) it will not matter how good your meter is.
It IS possible for careful, knowledgeable workers to get precision of 0.01 pH unit with NIST primary standard buffers: R.P. Buck et al., Pure Appl. Chem., Vol. 74, No. 11, pp. 2169–2200, 2002. But it is not easy.
The problem is that it is really easy for people to think they are getting that kind of precision when they are not even close. Which is why the historical data is likely to be pretty much useless.
Max,
Many thanks.
I think your post – with many others on this thread (and many others on this excellent site) – does indicate that the science is – actually – not settled.
There is a substantial (huge?) amount we simply do not know.
The oceans are huge.
A one degree by one degree grid square is – on the equator – 3600 square (nautical) miles in extent – that is 4 767.456 016 8 square statute miles – per http://www.onlineconversion.com/area.htm (bigger than Delaware or Rhode Island, and about 85% of Connecticut, or more than half the size of New Jersey; bigger than Cyprus, and about one third the size of Belgium).
And, forgive me, most of the non-empty grid-cells have one reading for pH, during 1910 to 2013.
Well, I guess we are a bit data-deficient.
Happy New Year to All.
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took a quick look at the data:
1. most of the data is to 2 decimal places. I find it hard to believe that scientists would record pH to 2 decimal places unless they felt their equipment had that sort of accuracy.
2. I removed the outliers (ph 9), then plotted the average pH for zero depth by year, with no correction for lat long or season or girding, under the assumption that these are basically random noise by year and will cancel out.
graph is here
http://i57.tinypic.com/2wlyhs2.png
ferd, what exact year is the outlier of just over 7.0?
At first glance I thought it might by 1998 which would make it both an outlier and a remarkable coincidence, but upon closer inspection it looks more like 1996 or 1997?
correction. outliers pH LT 6 or GT 9 removed
http://tinypic.com/r/2dm9vk6/8
correction for outliers here:
http://oi60.tinypic.com/2dm9vk6.jpg
the first graph didn’t have the outliers removed. the second does.
here is the SQL I used. LT and GT replaced for HTML.
SELECT OSD_All.[Year], Avg(OSD_All.[pH]) AS AvgOfpH
FROM OSD_All
WHERE ((((OSD_All.[pH])) LT 7 And ((OSD_All.[pH])) GT 9) AND ((OSD_All.Depth)=0))
GROUP BY OSD_All.[Year], OSD_All.Depth
ORDER BY OSD_All.[Year];
[See correction below. .mod]
it late, corrected sql here
SELECT OSD_All.[Year], Avg(OSD_All.[pH]) AS AvgOfpH
FROM OSD_All
WHERE ((((OSD_All.[pH])) GT 7 And ((OSD_All.[pH])) LT 9)
AND ((OSD_All.Depth)=0))
GROUP BY OSD_All.[Year], OSD_All.Depth
ORDER BY OSD_All.[Year];
Unweighted averaging just gives you an average of a smallish region, heavily representing, say, the area around Japan. To give an idea of the poor spatial spread of this data, I counted for each year the number of 5×5° cells that had any data in each year. There are probably 1500 or so such cells covering eligible ocean (not ice, land).
In a good year, that is just 1/3 of cells. In, say, 1997, it could be about 3% coverage. And to give an idea how lopsided the data is within cells, here is, in descending order, the numbers for 1989:
That is, just 14 cells had half the data points. That’s what you get with a simple average.
I find it hard to believe that scientists would record pH to 2 decimal places unless they felt their equipment had that sort of accuracy.
You report the reading to one more decimal place than the accuracy of the instrument. Standard lab practice.
“You report the reading to one more decimal place than the accuracy of the instrument. Standard lab practice.”
On analog instrumentation? Yes. On digital? No.
Nonsense. You usually report the reading and accuracy to the same precision. e.g 7.82 +/- 0.02
I find it hard to believe that scientists would record pH to 2 decimal places unless they felt their equipment had that sort of accuracy.
==========
it appears the instrument is indeed accurate to 2 decimal places.
see: Mark January 1, 2015 at 5:19 pm
SOP 6: Determination of the pH of seawater using a glass/reference electrode cell.
9.2.2 Precision (with care) 0.003 pH units (1 SD).
9.2.3 Bias <0.004 pH units.
“I find it hard to believe that scientists would record pH to 2 decimal places unless they felt their equipment had that sort of accuracy.”
Sadly, that is not true. Give people a digital readout with 2 decimal places and most will assume that they have 2 decimal places of accuracy. Really careful scientists won’t, but they are a minority.
Surely the raw data should be captured as displayed. If others wish to ‘adjust’ it later, then at least there’s a full audit trail back to the original.
I think some guys in Norfolk (CRU UEA) got into a bit of hot water by omitting this step and just recording what they thought the instruments should have said. Bad ‘Science’.
Looks like there are a significant number of gridcells or larger combinations of gridcells where well populated time series of Ph can be put together for that area. If a bunch of these show similar trends, that would seem to provide pretty good evidence about the global trend, and this approach would not be very difficult at all.
Trying to optimally extract the global PH moving average from the full pile of data might be “too hard,” but taking a good first look at it should not be.
you could expand the group by clause in the above sql to include location, season. this would tend to isolate the trend at each location and season, and then you could average these all together for each year. SQL NULL handling should eliminate the need for infilling as commonly required in other techniques. No need to interpolate missing data. I’ll give it a quick look in the morning to see if it makes any difference.
If you put a layer where all the tectonical plates are shown above the sample’s concentration please note two important things:
Not only on the coast of Japan the Ph-samples are sampled in areas where there are frequent high techtonic activity and/or volcanos on the bottom. The activity of techtonic plates are one main reason for the sampling.
In the Baltic Sea there are two main reasons for sampling forgotten and/or not intended by those who use the usually tables for Ph-valuses:
* Due to an agreement back in time which is caused due to the problem of the Baltic Sea water being more or less poisoned the last Century, reasons all from “leaking” from industries, none or bad existing watercleaning to the number of leaking warships after WWII is one reason for a large number of samples among others taken by Naturvårdsverket in Sweden
* The water in the Baltic Sea lacks continued in-trasported normal sea water which has a higher value for Oxygen (the water in the Baltic Sea is usually said to be “brackish water”. Reason for all this can be found in one geological wellknown fact: Due to landrise still much higher north a line over from Varberg (Swedish westcoast over to close to Västervik (north Kalmar) the amount of water passing from the Baltic Sea out finally in the Atlantic Ocean, is as high as 10 000 000 000 cubic meters each year due to higher landrisespeec in the northern parts of Scandinavia (including the Baltic Sea)
South the mentioned line there is a landsinking.
This causes effects on the existing polluted sludge storage which in it self is a problem for the countries around the Baltic Sea.
All in all the places where no or only a few samples been taken are the majority of places around the world’s Sea systems….
Something to be better taken into consideration, I think….
Willis writes “There are, for example, about 400 1°x1° gridcells that have more than a hundred observations per gridcell, and groups of nearby gridcell cells combined have much more data.”
Maybe there are some grid cells that are adequately covered temporally to do a trend on? It’s only a sample but that again climatology does that all the time with proxies to get their historical global temperature trends….
Let me be clear that regardless of what this data shows, I think that the ocean is gradually becoming more neutral, at about 0.01 pH units per decade, as a result of increasing atmospheric CO2. This is most clearly shown by the Hawaii HOT time series of pH measurements.
But since in geological times the creatures of the ocean went through long periods of much higher CO2 levels than at present, I also think that this slight neutralization won’t make any difference to the creatures in the ocean. In the ocean, chemistry doesn’t rule life … life rules chemistry.
w.
I’ve witnessed some diplomats bowing simultaneously and successfully to opposite directions. Scientists should also stick to their own strengths. For example, some contributors here have already convincingly demonstrated the the infinitesimally small neutralizing impact on ocean pH of all atmospheric CO2 – let alone the about 4% human portion. There is very little to add to it, but perhaps the following:
The islands of Hawaii rise up to 13,675 ft (4,168 m). Much of the Pacific Ocean surrounding the state slopes down to 20,000 ft (6,100 m) deep. It’s pretty impressive and ever on-going. It seems hasty to exclude its temporary impact on ocean alkalinity* in the region.
*Assuming that an ISO 17025 accredited laboratory is willing to declare 0.01 pH unit accuracy even for the tested samples, let alone extrapolating beyond.
Hello Willis.
My understanding in this pH thingy is that it relates more to the climate than to the impact on life.
Of course there has being going on a much hypet noise about the danger to the life, but the main point is that it is about the climate.
The pH variation in the oceans is a significant pointer to the temp variation in the oceans.
Cherry picking a point in time and showing an oceanic temp picture for that time and then trying to imply forcefully that that must have been the case for a longer time period it does inforce a false perception and a falce (manufactured fact) proof of the oceanic temp variation, which by the way is very important to understand the climate, especilly in the last 150 years (the GW era).
The oceanic temp measurements may not give a good enough picture of the oceanic temp trend during the GW era.
The pH measurements and it’s trend may assist to a better estimation towards it.
As far as I can tell, the pH drop in oceans as served by the Feely and Sabine it implies that there has being a considerable absorbtion of CO2 from the oceans during almost all the anthropogenic CO2 emission era, meaning that the oceans were in a warming trend for all that time, as expected in a AGW scenario or a human-made GW.
The period of the significant pH drop after 1988, as per Sabine’s work, is not a long enough period to support in it’s own the claim of the “acidification” of the oceans. Actually the “acidification” (as a claim forwarded) implies (rather strongly) that even before 1988 the “picture” has been the same, a supossed significant pH drop, a warming trend for the oceans….aka AGW.
20 years is a very short time, even in the case of that sharp pH drop to reach to a conclusion that anthropogenic CO2 emissions is actually causing oceans acidification, unless implying and suggesting (rather forcefully and arbitrary) that that must be the case even prior……….and that sharp drop (as cherry-picked) means that it is good only for compensating for the time period of the “bad data”. In it’s own is good for nothing else.
As already accepted, by a very “good” reason for the cherry pick of data given……..as there was not a choice but to resolve to it.
The problem generally with “cherry-picking” of this nature is not actually the act itself, or the excuse about it one may give or offer, but actually what was done with it,…… for what purpose and for what motive…. is the real problem.
Served as a fact for gonverment policy is far to wide and long reaching……….not mentioning the whole media hype and noise……….
Sorry for going so long with this, only trying to explaing my own understanding.
cheers
Hello Whiten,
If the oceans warm, they will expel CO2 and the pH will increase.
What is measured is that more CO2 is dissolved in the oceans (total carbon increases) and the pH decreases, despite the temperature increase.
So I fear that you have things somewhat in reverse…
The main problem is that the real drop in pH is only 0.04 units over the past 30 years, so you need very accurate equipment which was absent before 1980…
@willis
Ummm.. I think the best you can say is that ‘At Hawaii, the ocean is gradually becoming more neutral’.
Generalising from just one series to ‘the ocean’ is going a lot further than the available data allows.
But I agree with your general point. Any organism so specialised that it can’t withstand a pH change of 0.1 units is going to be a very short lived one in evolutionary terms
More CO2 —>more plant food—>more plants—>more organic debris—>lower pH at depth
BUT
Upwelling—>more nutrients—>proliferation of plants—>love that CO2 yum yum
win-win for the oceans
Two short statements sum up the whole matter.
1. The glass pH electrode method has instrumental errors greater than the plausible variation in waters under test.
2. So do later methods, because of sampling problems.
Geoff, so do thermometers that read out to 1 degree C and had many bad locations, have possible errors larger than the variation. These were used over 150 years to claim a 0.75 C increase with 0.01 C accuracy. However, if the variations are random, better averages can be determined if sufficient numbers of samples are used. This applies also to the pH samples.
This declining productivity of the ocean leaves in seawater is not bound carbon dioxide, the solubility decreases to the temperature rise of the Ocean (about one degree Celsius since 1910). Excess carbon dioxide is emitted into the atmosphere and its increasing concentration in sea water results in acidification of the ocean.
Ocean productivity is decreasing due to its decreasing fertilization, ie. Decreasing supplies from the depths to the surface layer of seawater silicates, phosphates, carbonates, iron, etc. Elements determining the continuation of photosynthesis, carbon dioxide binding with seawater. Lowering the productivity of the ocean is the result of a weak fertilization. Poor content life-giving elements in surface sea water is in turn the result of cosmic processes, but let’s talk about this turn.
The ocean is a biological machine and her life depends on the mixing of water in its depths. The process is as yet poorly recognized and is now marked by a lack of knowledge about the processes of ocean water exchange. Since life in the ocean is endless, it is clear that there is a circulation of water in its volume. It is caused by the constant and variable gravitational influence of the Moon and Sun on the density of ocean waters varied. Ocean tides occur on the surface and in the depths of the sea. Dense and cold water deep sea bottom sediments containing particles (including life-giving elements and dissolved minerals), escape to the surface cooling and fertilizing it, and oxygenated water surface and sink into the depths where oxygen support biological processes. Additionally upwelling (rich in silicates, phosphates, carbonates), the surface changes its acidity by neutralizing it. Water exchange between the depths and the surface is intensified by the constant changes in the position of pole-changing inclination of the Earth’s axis. This causes a change in the centrifugal force acting on the inertial mass of water and its movement horizontally and vertically in the oceans. Changing the position of the poles are due to changes in the geographical position of the Earth’s metallic core mapped location change of the magnetic poles. The kernel of gravity moves in a fluid under the influence of external kernel variable Sun’s magnetic field. When heavy metal core inside the Earth moves the liquid outer core is a change in the position of the center of gravity of the Earth and changing the position of the axis of rotation. This results in the geographical position changes polarity and as a result takes place under the influence of a variable centrifugal force, inertial motion of ocean water and mixing them in a volume’s ocean.
Ocean acidification … the most unscientific expression used to suggest to people it is happening when it is certainly not happening at all.
Absolutely. If the consensus trend is correct, the oceans are becoming more neutral, and would have to pass through a point where the water is perfectly pure. Only after that could it be described as ‘acidic’. Currently the oceans are not acidic in any shape or form, and therefore they cannot be undergoing the process of acidification.
It seems to me that everyone is bending over not to use the word ‘fraud’. The authors decided to delete a vast amount of data, presumably without a scientific proof of this in their paper. Simply to call the data ‘unreliable’ or whatever without proof is completely unacceptable.
Of course, by cutting off the data at 1988, it is almost certain that they are giving a completely false picture. Mike Wallace’s reconstruction in the other thread shows that, despite a fall since 1988, since 1900 there is essentially no trend. ferdberple’s average from the data shown above possibly shows a positive trend over this period (becoming less ‘acidic’). It also shows a positive trend in the last few years.
If these reconstructions, however preliminary, are correct, then the result is astounding. It means that pH has been changing in a natural cycle over the last 100 years, and there is no increasing ‘acidification’ that could even remotely be linked to CO2.
It has been rightly said that ocean acidification is the last refuge of the scoundrel.
I call it more than that. I call it scientific fraud.
Chris
Fraud implies malicious intent. Based on the past performance innocence cannot be excluded.
Chris, Mike Wallace’s compilation of the data doesn’t show a global or even local pH trend. It shows the average of each year of pH measurements taken at very different places and different seasons with an equipment that can’t measure the faint change in pH caused by more CO2 in the atmosphere.
It is the same as lumping the temperature data from all station above 30N together one year and the next year mainly from stations between 30S and 30N and then conclude that the atmosphere is warming…
The modern measurements since 1984 do show a small trend of 0.04 pH units at all open ocean places and repeated ships cruises if looking at the same places and the same season over time.
You discarded 2% of readings because they were ”outside the normal pH envelop”. But those figures are an average of the pH data not a true average of the oceans as a whole. There are regions where pH is 4-4.5 but you would have discarded those perhaps. Those discarded data must be inspected for position, date, time, and depth.
What is needed is a ‘pH Explorer’ similar to the ‘KNMI Climate Explorer’.
Oh for the skills and time!!!!
Notice the sparseness of data around Antarctica.
What was that again? Increasing Antarctic ice extent because of more fresh water run off?
Any data on pH is of value. If we had only a couple of dozen samples of the ocean spread over all of them, we could at least say the ocean is a bit variable but it is around pH8. If we were sampling the ocean on Titan and we had only one site to select, could we not feel confident that it was a hydrocarbon sea and probably, because of the ‘hydrocarbonological cycle’ that the whole works was hydrocarbons?
I already see something interesting. The lower pHs around the continents and particularly in the polar regions – means something? Also pH does vary with temperature a little bit (but the reverse of what we see in polar waters -pH up with Temp). Also major rivers lower pH locally, probably why continent margins seem to have lower pH. Also, pH on the ocean surface would be affected by heavy rains. I like the 1metre samples better.
A lot of confounding complications. However, I think taking all samples in decade bins for 1910 until the present decade should give us a reliable enough trend to see if pH has been lowering over a century. By the way, what was the average? Let me guess….Hmmmm I’d say pH 8.