Where has all the CO2 gone? WUWT fails arithmetic & science, so cries pHraud!

Update: I've added some older papers - meant to do this earlier. (Sou - a bit later)

See also a new HW article on the same topic, with some interesting bits and pieces about pH data. (Sou - 2 January 2015)

---

In two very, very dumb articles at WUWT, one of which is a mainly a copy of a CFACT monstrosity elsewhere - there are foolish accusations of fraud about ocean acidification.

Now anyone who is taken in by this nonsense should go stand in the corner and put on a dunce cap. Then they ought to enrol in a remedial arithmetic class.

Thing is, experts have calculated how much extra CO2 humans have put in the atmosphere. It comes from burning fossil fuel, from land use changes, particularly deforestation, and from the making of cement. Only around half of what humans have emitted has stayed in the atmosphere. The rest is absorbed in the oceans and on land - with plants absorbing something like 30% of the extra and the oceans absorbing around 25%.

If you look at it from another perspective, you'll see that the oceans must be absorbing more CO2. That other perspective is that the increase in atmospheric CO2 means an increase in the partial pressure of CO2. When partial pressure of a gas in contact with a solution rises, the solution dissolves more of the gas. If temperature increases, then all else being equal, the solution will give up the gas. However right now, even though the temperature is rising, the increase in partial pressure outstrips this rise - so the oceans are taking CO2 from the air.

Two very foolish articles at WUWT

About that foolish article - actually there are two of them at WUWT (archived here and here). The first one seems to have started at CFACT and went all around the deniosphere but I doubt that anyone of any brains took any notice. Still, I'll write about it because it's another instance of disinformers shrieking "fraud" so as to pander to the scientifically illiterate deniers. It's appalling the way these US lobby groups will defame scientists. It's so easy for them to do so. They just write a stupid unscientific article and say scientists are committing fraud. They bypass saying that a scientist made a mistake (which in this case they didn't). They don't bother with facts. They ignore all other evidence and jump straight to an accusation of fraud. Why? To appease their paymasters, most likely.

Deniers don't understand the most basic (sic) science

The scientists who are defamed at WUWT and by CFACT and in various parts of the conspiracy theorising world of deniers are Dr Richard Feely and Dr Christopher Sabine.  It's not the first time that Anthony Watts has shown how dumb he is by posting a silly article about Dr Feely. Back in 2012 there was a rather dumb email sent to Dr Feely that Anthony wasn't ashamed to publish (archived here). In it, the author got very confused about pH and what it is. His main argument can be summarised in this excerpt:

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

But as you know, the equation for the pH of an aqueous solution is logarithmic and defined as pH = -log[ H+ ] . As you also know, there are 14 orders of magnitude that define the pH scale from zero to fourteen units as per this equation. So a movement of .1 units towards acidity cannot equal a 30% increase in acidity as claimed in this article. It is actually .1/14 or only 7/10ths of 1%. ...

Wrong! Here is a link to a primer on ocean acidification, with an explanation of pH and percentage change in acidity. A drop of 0.1 from a pH of 8.2 to 8.1 represents an increase in acidity of 26%. There were some WUWT commenters who tried to set the author straight, though many who commented didn't have the first clue.

Richard Feely and Christopher Sabine are two of the world's leading experts on ocean acidification. That's probably why disinformers decided to target them. It's the Serengeti Strategy with a twist. Usually the strategy is to target only one person at at time. Almost any scientist who studies ocean chemistry will tell you that all the evidence shows that pH of the ocean is dropping.

Enter the denier hydrologist - Mike Wallace

What got the disinformers going was that some denier or other named Mike Wallace decided that the all the world's experts were wrong about ocean acidification. Now Mike Wallace isn't studying ocean acidification, he's got a list of various AGU posters and a some papers on hydrology under his "Professional Biographic information" on his "professional" website - of Mike Wallace & Associates. (I expect his associates are called Mike Wallace and Mike Wallace).  Nevertheless, he was sufficiently bold to correspond with Drs Sabine and Feely "over a period of several months". (The good professors must have the patience of saints.)  Mike was apparently seeking robust measurements of ocean pH for the entire 20th century. Good luck with that!

I'm having trouble trying to figure out just what the point of the article is. There is reference to a brochure, and 2010 testimony and to an omission of "80 years of data" but where it's omitted from isn't specified. When referring to "Feely's chart", the author might mean this one, in which the pH observations do start in the late 1980s, which would be about right.

 The chart came from the BAMS State of the Climate in 2007 report, and the pH and pCO2 data came from the Hawaiian Ocean Time Series. Here is the image from the BAMS report:

Fig. 3.26. Time series of atmospheric CO2 at Mauna Loa (ppmv) and surface ocean pH and pCO2 (μatm) at Ocean Station Aloha in the subtropical North Pacific Ocean. Note that the increase in oceanic CO2 over the last 17 yr is consistent with the atmospheric increase within the statistical limits of the measurements. [Mauna Loa data: Dr. Pieter Tans, NOAA/ESRL, www.esrl.noaa.gov/gmd/ccgg/trends; HOTS/Aloha data: Dr. David Karl, University of Hawaii, http://hahana.soest.hawaii.edu.]
Source: BAMS State of the Climate in 2007

Whatever, the article doesn't just allege that Drs Feely and Sabine have it wrong, CFACT (and WUWT) is accusing them of fraud. That's a big call. So what is this accusation based upon?

The data isn't missing - it's just not good enough

Well, it seems that these scoundrels think that there must be another "80 years of data, which incorporate more than 2 million records of ocean pH levels". The article goes on to say that NODC/NOAA has all these data. Thing is, that it seems to me that Mike whatshisname can't tell good data from patchy, poor data.

For a comprehensive article on ocean acidification, you could do worse than this one by Scott C. Doney, Victoria J. Fabry, Richard A. Feely, and Joan A. Kleypas: "Ocean Acidification: The Other CO2 Problem", which was published in Annual Reviews in 2009. As the article says (and which the disinformers avoid telling you) - my emphasis:

Ocean acidification is a predictable consequence of rising atmospheric CO2 and does not suffer from uncertainties associated with climate change forecasts. Absorption of anthropogenic CO2, reduced pH, and lower calcium carbonate (CaCO3) saturation in surface waters, where the bulk of oceanic production occurs, are well verified from models, hydrographic surveys, and time series data (Caldeira & Wickett 2003, 2005; Feely et al. 2004, 2008; Orr et al. 2005; Solomon et al. 2007). At the Hawaii Ocean Time-Series (HOT) station ALOHA the growth rates of surface water pCO2 and atmospheric CO2 agree well (Takahashi et al. 2006) (Figure 1), indicating uptake of anthropogenic CO2 as the major cause for long-term increases in dissolved inorganic carbon (DIC) and decreases in CaCO3 saturation state. Correspondingly, since the 1980s average pH measurements at HOT, the Bermuda Atlantic Time-Series Study, and European Station for Time-Series in the Ocean in the eastern Atlantic have decreased approximately 0.02 units per decade (Solomon et al. 2007). Since preindustrial times, the average ocean surface water pH has fallen by approximately 0.1 units, from approximately 8.21 to 8.10 (Royal Society 2005), and is expected to decrease a further 0.3–0.4 pH units (Orr et al. 2005) if atmospheric CO2 concentrations reach 800 ppmv [the projected end-of-century concentration according to the Intergovernmental Panel on Climate Change (IPCC) business-as-usual emission scenario]. 

It's basic chemistry and physics. If, as Mike whatsit claims, the oceans aren't absorbing all that CO2, then he has to explain the following:

• Where has one third of the CO2 disappeared to?
• Why have gases and solutions started to behave so unnaturally. In other words, why haven't the oceans absorbed the CO2? What is different that causes it to stop behaving as a solution under pressure from a gas.

Mike claims to be a hydrologist. I don't suppose that means he has to have any understanding of chemistry, but he does say that he graduated in science, so you'd have thought some of what he was taught would have sunk in. Apparently not.

The first WUWT article ends with some silliness and a strawman:

Regarding the chart in question, Wallace concludes: “Ocean acidification may seem like a minor issue to some, but besides being wrong, it is a crucial leg to the entire narrative of ‘human-influenced climate change.’ By urging our leaders in science and policy to finally disclose and correct these omissions, you will be helping to bring honesty, transparency, and accountability back where it is most sorely needed.”

“In whose professional world,” Wallace asks, “is it acceptable to omit the majority of the data and also to not disclose the omission to any other soul or Congressional body?”

The strawman of course, is that there was no "majority of the data" omitted from the testimony to which he refers. The testimony refers to the sources of estimates of ocean acidification, including:

Over the last three decades, NOAA, the National Science Foundation and the Department of Energy have co-sponsored repeat hydrographic and chemical surveys of the world’s oceans, documenting their response to increasing amounts of carbon dioxide being emitted to the atmosphere by human activities. These surveys have confirmed the oceans are absorbing increasing amounts of carbon dioxide. Both the hydrographic surveys and modeling studies reveal that chemical changes in seawater resulting from absorption of carbon dioxide are increasing the acidity of seawater or lowering of its pH.

Enter denier 2: Peter Gadiel

Enough of the nonsense from Mike Wallace, grade one denier. I'll move onto the second article at WUWT (archived here).  It starts with this headline and opening:

Sabine’s excuse for using modeled data over real data? – ‘earlier data is not of “sufficient quality.”‘

WUWT reader Peter Gadiel writes:
After reading of the critique of Sabine’s exclusion of the historical data on ocean acidification I emailed him. I thought his response might be of interest to you at WUWT. He says the earlier data is not of “sufficient quality.”

Now you'd expect deniers to applaud scientists for not relying on data that was not of sufficient quality.  Not Anthony. He wonders:

Who determined that the directly measured ocean pH data was not of “sufficient quality” and if it wasn’t, why then did NOAA make the data available on their website as part of other ocean data in their World Ocean Database without a caveat?

Well, I'd say it was the scientist who was doing research into ocean acidification who determined it was not of sufficient quality.  Anthony points to the NODC/NOAA website and says "My search on NOAA’s NODC database for ocean pH data showed plenty of data and no caveats on use".

Oh my. Imagine letting Anthony Watts loose on ocean pH readings with "no caveats". We'd be getting articles forever and a day on ocean UHI disease.  Anyway, this was the chart he put up, a data distribution plot of pH measurements taken over time:

Source: NODC/NOAA

It looks impressive, doesn't it. What Anthony didn't tell his readers - probably because he didn't know - is that the chart represents all data from all years in the following datasets:

The cast count is:

259325 OSD casts (Ocean station data)
0 CTD casts
0 XBT casts
0 MBT casts
0 PFL casts
0 DRB casts
0 MRB casts
0 APB casts
0 UOR casts
1 SUR cruises (surface only data)
0 GLD casts
259,326 TOTAL casts 

In case you're like me and don't know what a cast is, here's the definition from the WDO documentation:

Cast – A set of profiles (or a single profile) taken concurrently. Meteorological and ocean condition information are also included for a cast if measurements were taken concurrently with the profile(s). Observations and measurements of plankton from net-tows are included if taken concurrently or in close time proximity to profiles. If there are no profiles in close proximity, a net-tow by itself will constitute a cast. Each cast in the WOD05 is assigned a unique cast number. If the cast is subsequently replaced by higher quality data, the unique cast number remains the same. If any alteration is made to a cast, this information is noted online, referenced by the unique cast number. For surface-only data in dataset SUR, a cast is defined as a collection of concurrent profiles of surface measurements at discrete latitudes and longitudes over an entire cruise (see definition of cruise below). Profiles of latitude, longitude and Julian year-day are included with profiles of measured oceanographic variables. 

Compare the pH casts with those of temperature, which delivers the following results:

Source: NODC/NOAA

The cast count is:

2,905,115 OSD casts
926,248 CTD casts
2,247,079 XBT casts
2,425,604 MBT casts
1,281,527 PFL casts
166,140 DRB casts
1,464,497 MRB casts
1,460,344 APB casts
88,498 UOR casts
5,905 SUR cruises
508,429 GLD casts
13,479,386 TOTAL casts

You could say the oceans are supersaturated in temperature :)

Now let's look at an animation showing the pH records collected for different periods. Click to enlarge:

Source: NODC/NOAA

Look again at the data above, particularly for the period 1900 to 1929 and the period to 1949 and then ask yourself how Mike Wallace put together this chart and managed to keep a straight face.

Dumb chart from Mike Wallace.
Source: WUWT

It makes you wonder who's trying to fool who. Mike's managed to get a global average when there were almost no pH measurements at all. Heck, some years he wasn't even able to put in any number from anywhere in the ocean at all yet he still found a global trend. It reminds me of those rather awful charts of CO2 measurements that deniers try to flog on the unwary from time to time.

No thanks, Mike Wallace and Anthony Watts. I'll stick to what the experts are finding. And if you want more direct observations, say of the North Pacific Ocean - look no further.

A bonus from Dr Christopher Sabine

WUWT reader, Peter Gadiel told Anthony that his rather rude "question to him" (ie to Dr Sabine) was:

As a taxpayer who is helping to pay your salary I’d like to know why you are refusing to include all the data on ocean acidification that is available.

And he reported Dr Sabine’s curt response, which was obviously written very promptly after the query, despite it being Christmas holiday time:

12:31 AM (11 hours ago)
As a public servant that must stick to the rigor of the scientific method and only present data that is of sufficient quality to address the question, I am obliged to report the best evaluation of ocean chemistry changes available. This is what you pay me to do and I am working very hard to give you the best value for your tax dollar every day. I hope you are having a good holiday season.

Indeed. I couldn't hope for more, Dr Sabine. But are the denier "taxpayers" satisfied?

From the WUWT comments

Wow, I've just noticed that Anthony's silly article - the second one with his chart from NOAA, garnered 342 comments or, as Anthony describes them more appropriately - 342 "thoughts". It looks as if everyone made a mad dash for their computer on Boxing Day. They'd had enough of Christmas celebrations or whatever they happened to be doing the previous day.


Charles Nelson couldn't be bothered reading any paper on ocean acidification and asked:

December 26, 2014 at 12:36 am
So what did they feed into their model?

oldfossil seems to think, erroneously, that Mike "managed to make sense":

December 26, 2014 at 1:30 pm
@ferdberple, remember that 80 years ago, nobody was smart enough to read a thermometer properly. That’s why GISS has to fix the data. Likewise with glass electrode pH meters.
I took a look at Michael Wallace’s page www dot abeqas dot com. On the face of it he seems to be a sane, level-headed, industrious and professional hydroclimatologist with no ax to grind either way in the climate debate. If he managed to make sense out of the historical database, a responsible scientist should also have been able to.

Ferdinand Engelbeen retorted to ferdberple, who falsely accused the scientists of deliberate fraud:

December 27, 2014 at 3:25 am
Ferdberple,
Do you accuse Keeling of fraud, because he didn’t use any historical CO2 data before Mauna Loa was established with much better measurement methods?
Do you accuse Dr. Spencer of fraud, because he didn’t use any historical ground based temperature data when he used the more accurate satellite data?
The pre-1984 pH data from glass electrode measurements are simply worthless to show any trend at all, except if based on calculations and repeated measurements over the same track in the same seasons.

There was the expected argy bargy about the term ocean acidification, with a surprising comment from Eric Worrall

December 26, 2014 at 1:57 am
Acidification is a reasonable Chemistry term to use to describe lowering the PH of a liquid (in this case the ocean), even if the end result is still alkaline (basic). When mixing acid with a solution to neutralise it, we were always told we were acidifying the solution, even though the final PH was neutral (7) – neither acid nor alkaline.

Dave is one of many who thinks he knows better

December 26, 2014 at 2:26 am
Eric Worrell. You were taught some poor chemistry! When titrating a basic solution with acid you are neutralising a proportion of the basic solution. At no time are you acidifying the solution unless you neutralise all the basic component and move the pH to less than 7. The use of the word scidification is a simple scare term and is scientific nonsensr

JohnB takes issue with the rudeness of Peter Gadiel's question, which spawned a whole heap of random "thoughts".

December 26, 2014 at 12:42 am
Why be provocative? If I were a public servant nothing could get my back up faster than a missive opening with “As a taxpayer who is helping pay your salary….” Forget government employees, how would someone in a private industry respond to “As a customer who helps pay your salary….” be taken? I’d give you the most sarcastic reply I could get away with.
What’s wrong with a polite request denoting interest in the topic and asking for clarification? A simple “What was wrong with the older data? Help me to understand.”

bertief thinks wrongly that the scientists "made up" the data:

December 26, 2014 at 1:02 am
I don’t have too much trouble with the claim that the old data is probably patchy and potentially unreliable. That does not, however, excuse making up your own ‘data’ using modelling to replace it.

An awful lot of people bought the disinformer's lie that the scientists "made up" data. They didn't. See the first chart above - it's data from observations. Measurements at a particular location. Read the references listed below - they describe how estimates are made going way back in time - thousands of years back in time - based on observations. Other data is calculated from measurements of atmospheric CO2 and other information. Some estimates are made from model experiments - and the models are based on observations and known physics and chemistry.

Mike M. makes the point that WUWT deniers don't even accept temperature data, which is based on at least twice daily readings from thousands of weather stations all around the world, but they'll take as gospel some denier's claims about the validity of very sparse and at times non-existent data back to 1910. He wrote:

December 26, 2014 at 9:29 am
Once again, Ferdinand gets it right. The older data are not sufficient to show the very small expected pH trend. The errors in the data are much larger than the change that has occurred.

The accuracy pf measurements of this type depend on both the accuracy of the instruments and the representativeness of the sampling. Both are much better for temperature than for pH. Since pre-industrial times, the average pH change is calculated to be about 0.1 pH unit, similar to measurement accuracy unless great care is taken in the measurements. The temperature change has been about 0.8 K, much larger than routine instrumental accuracy. Sampling is also an issue since pH, like temperature, varies with time and place. But the temperature has been measured continuously at a very large number of locations for a long time. Such systematic measurements of pH are not available, at least not until recently. The situation for pH is much more like ocean heat content than surface temperature.

Many people commenting on this site doubt the reliability of the long term temperature trends. There is some justification for that. But the pH data are far less reliable. So why would reasonable skeptics be willing to trust that data?
Mike M.

Then, when the arguments about "made up" dried out, denier "thoughts" turned to accusations of cherry picking a start date.  To which Ferdinand Engelbeen responded:

December 26, 2014 at 10:56 am
Latitude:
..and Sabine etc. have not shown that they didn’t cherry pick a start date at an abnormal high…
They didn’t cherry pick, they started the trend when more accurate measurements were established at a few fixed stations with frequent sampling.
That is like saying that Keeling Sr. “cherry picked” his CO2 data starting in 1958, when the accurate readings at the South Pole and Mauna Loa started…
Or that Dr. Spencer “cherry picked” his temperature data when the satellites started to measure them (indirectly) in 1979…

Man Bearpig has visions of Dr Sabine out in a little boat with a pH probe, probably of the fish tank variety:

December 26, 2014 at 1:27 am
I wonder if Sabine would be so kind as to provide the calibration certificate for one or more of their pH probes ?
He may have a problem doing this, as I suspect there are none available.

Here's an article for Man BearPig, describing how some ocean pH measurements are taken. And here's a link to a presentation discussing satellite sensing of ocean pH. Deniers seem to like satellites, so maybe they'll be satisfied with that.


Phlogiston probably thinks he's being clever. He just comes across as ignorant if not stupid, someone who can't understand science so he complains about details. What he doesn't seem to realise is that these very same scientists that he can't understand do use paleo data for estimating ocean pH going back thousands of years.

December 26, 2014 at 2:43 am
AGW activists use increasingly the same tactics as 6 day creationists. One is to question all historic and especially palaeo geological data, and call it unreliable. This is the creationist argument Sabine is using.

Another is what is called the “Gish gallop” after a certain over-enthusiastic creationist, and it means the practice of trying to overwhelm a debate with a deluge of “micro-points” – numerous argument of mixed quality which the opponent has no time to refute. The famous example is “101 reasons for a young earth”.

The activist media and scientific journals are the new exponents of the Gish gallop, with the constant drumbeat of alarmist articles about one disaster after another due to global warming, amounting to “101 reasons to act now on CO2 emission”.

(FWIW I don’t consider evolution and a 13 billion year old universe incompatible with Christian faith.)

Cliff Mass is looking for papers:

December 25, 2014 at 8:34 pm
Does anyone know of ANY papers that document the observed historical changes in ph before 1980?..cliff mass 

Update: I've added a couple of references for Cliff down below, which should get him started.


Willis Eschenbach had an odd chemistry teacher.

December 24, 2014 at 9:52 am
Thanks, Phil. So your claim is that if we add a small amount of acid to an alkaline solution it’s called “acidification”, if we add a larger amount it’s called “neutralization”, and if we add even more it’s once again called “acidification”?

Makes no sense.

And it didn’t work that way in my chem class. If we only added half the amount of acid needed, we wouldn’t call that “insufficient acidification”. We’d say we had done an incomplete neutralization.

It’s simple, or at least it was in 1964. Moving towards a pH of 7.0 is neutralization. Moving away from 7.0 is either acidification or akalinization.
This is also the common usage. For example, you don’t add baking soda to the top of your car battery to “alkalinize” a battery acid spill. You add it to neutralize the acid.

So on the day that people start calling that action “alkalinizing the battery acid” I’ll believe your claims. Until then … not so much …

Best regards,
w.

I'll end on that note.

---

Levinson, David H., and Jay H. Lawrimore. "State of the climate in 2007." Bulletin of the American Meteorological Society 89, no. 7 (2008): S1-S179.  doi: http://dx.doi.org/10.1175/BAMS-89-7-StateoftheClimate (open access)

Doney, Scott C., Victoria J. Fabry, Richard A. Feely, and Joan A. Kleypas. "Ocean acidification: the other CO2 problem." Marine Science 1 (2009). DOI: 10.1146/annurev.marine.010908.163834 (open access)


Byrne, Robert H., Sabine Mecking, Richard A. Feely, and Xuewu Liu. "Direct observations of basin‐wide acidification of the North Pacific Ocean." Geophysical Research Letters 37, no. 2 (2010).. DOI: 10.1029/2009GL040999 (open access)

---

Older papers (for Cliff Mass and the curious - Dr Kilho Park was very active in this research area in the 1960s) - the bibliographies of all these papers will have more references - then there's the IPCC reports.

Park, Kilho. "Alkalinity and pH off the coast of Oregon." In Deep Sea Research and Oceanographic Abstracts, vol. 15, no. 2, pp. 171-183. Elsevier, 1968. doi:10.1016/0011-7471(68)90039-9 (subs req'd)

Park, Kilho. "Deep-sea pH." Science 154, no. 3756 (1966): 1540-1542. DOI: 10.1126/science.154.3756.1540 (should be open access)

Park, Kilho. "Surface pH of the northeastern Pacific Ocean." The Journal of the Oceanological Society of Korea Vol. 1, No.1-2, December 1966: p 260. (avail here) includes diagram of the pH measuring device and more.

Alvarez-Borrego, Saul. "Chemico-oceanographical parameters of the central North Pacific Ocean." (1970). (Thesis - available here)

Park, Kilho. "Chemical features of the Subarctic Boundary near 170 W." Journal of the Fisheries Board of Canada 24, no. 5 (1967): 899-908.  doi:10.1139/f67-080 (Subs req'd)

Mellen, Robert H., and David G. Browning. "Variability of low‐frequency sound absorption in the ocean: pH dependence." The Journal of the Acoustical Society of America 61, no. 3 (1977): 704-706. http://dx.doi.org/10.1121/1.381357 - Yes, really. (subs req'd)