Touchy Feely Science – one chart suggests there's a 'pHraud' in omitting Ocean Acidification data in Congressional testimony

“…startling data omission that he told me: “eclipses even the so-called climategate event.””

Willis Eschenbach tips me to a story by Marita Noon, titled:

What if Obama’s climate change policies are based on pHraud?

I’ve reproduced portions of it here, with a link to the full article. The graph with ALL the data is compelling.


 

“Ocean acidification” (OA) is receiving growing attention. While someone who doesn’t follow climate change science might think OA is a stomach condition resulting from eating bad seafood, OA is claimed to be a phenomenon that will destroy ocean life—all due to mankind’s use of fossil fuels. It is a foundational theory upon which the global warming/climate change narrative is built.

The science and engineering website Quest, recently posted: “Since the Industrial Revolution in the late 1700s, we have been mining and burning coal, oil and natural gas for energy and transportation. These processes release carbon dioxide (CO2) into the atmosphere. It is well established that the rising level of CO2 in our atmosphere is a major cause of global warming. However, the increase in CO2 is also causing changes to the chemistry of the ocean. The ocean absorbs some of the excess atmospheric CO2, which causes what scientists call ocean acidification. And ocean acidification could have major impacts on marine life.”

Within the Quest text is a link to a chart by Dr. Richard A. Feely, who is a senior scientist with the Pacific Marine Environmental Laboratory (PMEL)—which is part of the National Oceanic and Atmospheric Administration (NOAA). Feely’s climate-crisis views are widely used to support the narrative.

hitimeseries2_med

Feely’s four-page report: Carbon Dioxide and Our Ocean Legacy, offered on the NOAA website, contains a similar chart. This chart, titled “Historical & Projected pH & Dissolved Co2,” begins at 1850. Feely testified before Congress in 2010—using the same data that shows a decline in seawater pH (making it more acidic) that appears to coincide with increasing atmospheric carbon dioxide.

The December edition of the scientific journal Nature Climate Change features commentary titled: “Lessons learned from ocean acidification research.”

However, an inquisitive graduate student presented me with a very different “lesson” on OA research.

Mike Wallace is a hydrologist with nearly 30 years’ experience, who is now working on his Ph.D. in nanogeosciences at the University of New Mexico. In the course of his studies, he uncovered a startling data omission that he told me: “eclipses even the so-called climategate event.” Feely’s work is based on computer models that don’t line up with real-world data—which Feely acknowledged in email communications with Wallace (which I have read). And, as Wallace determined, there is real world data. Feely, and his coauthor Dr. Christopher L. Sabine, PMEL Director, omitted 80 years of data, which incorporate more than 2 million records of ocean pH levels.

Feely’s chart, first mentioned, begins in 1988—which is surprising as instrumental ocean pH data has been measured for more than 100 years since the invention of the glass electrode pH (GEPH) meter. As a hydrologist, Wallace was aware of GEPH’s history and found it odd that the Feely/Sabine work omitted it. He went to the source. The NOAA paper with the chart beginning in 1850 lists Dave Bard, with Pew Charitable Trust, as the contact.

Wallace sent Bard an email: “I’m looking in fact for the source references for the red curve in their plot which was labeled ‘Historical & Projected pH & Dissolved Co2.’ This plot is at the top of the second page. It covers the period of my interest.” Bard responded and suggested that Wallace communicate with Feely and Sabine—which he did over a period of several months. Wallace asked again for the “time series data (NOT MODELING) of ocean pH for 20th century.” 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.” He then included a few links to websites that Wallace, after spending hours reviewing them, called “blind alleys.”  Sabine concludes the email with: “I hope you will refrain from contacting me again.” But communications did continue for several more exchanges.

In an effort to obtain access to the records Feely/Sabine didn’t want to provide, Wallace filed a Freedom of Information Act (FOIA) request.

In a May 25, 2013 email, Wallace offers some statements, which he asks Feely/Sabine to confirm:

“…it is possible that Dr. Sabine WAS partially responsive to my request. That could only be possible however, if only data from 1989 and later was used to develop the 20th century portion of the subject curve.

“…it’s possible that Dr. Feely also WAS partially responsive to my request. Yet again, this could not be possible unless the measurement data used to define 20th century ocean pH for their curve, came exclusively from 1989 and later (thereby omitting 80 previous years of ocean pH 20th century measurement data, which is the very data I’m hoping to find).

Sabine writes: “Your statements in italics are essentially correct.” He adds: “The rest of the curve you are trying to reproduce is from a modeling study that Dr. Feely has already provided and referenced in the publication.”

In his last email exchange, Wallace offers to close out the FOIA because the email string “clarified that your subject paper (and especially the ‘History’ segment of the associated time series pH curve) did not rely upon either data or other contemporary representations for global ocean pH over the period of time between the first decade of 1900 (when the pH metric was first devised, and ocean pH values likely were first instrumentally measured and recorded) through and up to just before 1988.” Wallace received no reply, but the FOIA was closed in July 2013 with a “no document found” response.

Interestingly, in this same general timeframe, NOAA reissued its World Ocean Database. Wallace was then able to extract the instrumental records he sought and turned the GEPH data into a meaningful time series chart, which reveals that the oceans are not acidifying. (For another day, Wallace found that the levels coincide with the Pacific Decadal Oscillation.) As Wallace emphasized: “there is no global acidification trend.”

MWAcompilationOfGlobalOcean_pHJan82014

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?”


Full story here: http://www.cfact.org/2014/12/22/what-if-obamas-climate-change-policies-are-based-on-phraud/

There’s a petition: http://www.ipetitions.com/petition/restore-the-worlds-ocean-ph-measurements

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Admad

I had long wondered why previous geological instances of much higher atmospheric CO2 concentrations had not extinguished all sea life, as the present AGW meme would suggest should happen.

Ding!

Robert W Turner

They treat the oceans as if they were a beaker in a laboratory with their “modeled” pH change. There is essentially a limitless amount of salts to resist pH change from a minor increase in dissolved CO2. Now there is evidence that the claim is entirely fraudulent and I’m not surprised.

Robert W Turner

Those of you who have not read the original article might find it interesting that Feely was awarded $100,000 from the Heinz Foundation (Founded by John Kerry’s wife) for the research in question. Things that make you go hmmm.

For more graphs and gridded confirmation see:
ferdberple January 2, 2015 at 8:44 am (near end)

PiperPaul

Because it was the wrong type of CO2, obviously…

SanityP

Pointing out the obvious here, only man made CO2 emissions will cause unspeakable climate rapture sometime in the near, never approaching future …

Alx

Well yes now there is good CO2 and bad CO2. Climate science has gone biblical.

hobgoblin2

There are differences of course and the increase in one over the other as measured is a keystone of the AGW issue. Although there is now some doubt as to the original basis for this claim.

Because it’s Rotten CO2, just like there’s Rotten Snow.

jorgekafkazar

Because CO2-god, him not plenty-plenty angry.

BallBounces

Like cholesterol, there is good CO2 and bad CO2?

Ball Bounces – apparently: C14/O16; C14/O18; C15/O16;C15O18 …. 15 isotopes of C, three main isotopes of O, variations in fractionation, plant type preferences, more O18 at the equator, less at the poles …
The more we know, the more we know we don’t know.

JJM Gommers

There is natural CO2 which is optical left turning and anthropogene CO2 optical right turning, hahahaha

pesadia

Actually, there is no bad cholesterol.
See “the oiling of america” on utube
It’s mind blowing

pesadia

Actually, there is no bad cholesterol.
See “the oiling of america” on utube.
It’s mind blowing

John Francis

How can these farauds live with themselves? Astounding revelation.

John Francis

Man, I hate typing on an iPad!

Gerry, England

Counting the grant cheque dollars keeps their minds of it.

NancyG22

@ pesadia
Wow, thanks. 49 minutes in and the Cholesterol Consensus Conference sounds a lot like the Climate Consensus Crap.

Dr A. Cannara

Well Admad, maybe study some basic chemistry — for instance fluid temp vs dissolved gas equilibrium with gas above? Perhaps the far higher Devonian CO2 content of air without far lower ocean pH can be explained by study, of water temperature? Whddya think, Admad?
;]

BillD

By now I guess that everyone knows that there was no phraud, just a misinterpretation of the data. This is all clarified on Skeptical Science. This is why real scientists look at peer reviewed studies, not work by graduate students that is unreviewed and also outside of the student’s field of expertise. Did someone already point out that the original publication and testimony is still correct? I did not go through the 400+ comments.

ozspeaksup

“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?”
err?
pharma GMO and climate pseudo sciences for a start,I’m sure theres more.

mark

Nutrition is hugely corrupt.

Polar bear science, as recently as last month (Southern Beaufort Sea population estimates, which simply left off two-three years of available date to generate an anomalously low population estimate and an exaggerated declining trend – discussed here http://polarbearscience.com/2014/12/17/recent-s-beaufort-polar-bear-count-was-a-cherry-picked-result-new-evidence/ )

John F. Hultquist

Yes, John – the link I provided is an update to that WUWT story. It shows that the study was not just terminated prematurely, as first appeared to be the case, but rather, the authors left out the data for 2011 and 2012 which was available to them. Mark-recapture data collection continued until 2013 in the Southern Beaufort – they reported data up to 2010 only. That makes it relevant to this “acidification” story.
And Merry Christmas to you all.
Susan

I really enjoyed and was saddened by your recent post:
http://polarbearscience.com/2014/12/18/polar-bear-biologists-miss-the-mark-in-new-study-on-invasive-mark-recapture-effects/
Sad photo but unsurprising result, frequently seen in collared animals. One of those unmentioned side effects. Some studies actually document mortality caused by collaring (wolf studies in particular). Of course that would not look good in Polar Bear studies.
Which prompts me to ask how this picture even was released and by whom?
Keep up the good work.
Have a Merry Christmas and all the best for 2015.

“Wallace was then able to extract the instrumental records he sought and turned the GEPH data into a meaningful time series chart, which reveals that the oceans are not acidifying.”
There must be something wrong with that data. Otherwise, it is not just omission, but deliberate misrepresentation’ proclaiming the opposite of what the data shows.
Better adjust the data as soon as possible.

Denis Ables

And you guys haven’t yet gotten around to our cosmologists who have built numerous bunny trails (dark matter, dark energy, dark flow, etc. etc.) all baseless, in their attempt to keep their “big bang” alive. They refuse to acknowledge the electric universe. Redshift measurements across our universe donot imply the same as from the local cop’s radar detector. (Some of those far out galaxies are now moving faster than the speed of light. Any real scientists would consider that sufficient to begin re-examining the basic premises.)

noloctd

Bwahahaha.

ConfusedPhoton

There are three kinds of lies: lies, damn lies and climate science
What would these people do without their games (ops sorry models)

Designator

At least they didn’t “adjust” the data.. hehe

mike

I don’t know if anyone else caught it, but a certain blogger-dude who goes by the “anonymous-coward” (a term once applied to me by one of ATTP’s regular denizens (but on another blog, I note)) pseudonym, “ATTP” (aka “wotts”, aka “Anders”, aka “Mr Wishy-Washy, Passive-Agressive, Milquetoast, Milk-sop, Hamlet-Wannabe, To-Blog-Or-Not-To-Blog?-That-Is-The-Question, Oh-Please-Do-Keep-On-Blogging-Anders-Cuz-We-All-Just-Luv-U-and-Need-U!, Pardonnez-Moi-While-I-BARF!!!, A-Worse-Fusspot-Than-HotWhopper Mouth-Off”), has “dissed” this blog (see ATTP’s “AWOL” post) by calling WUWT “an anti-science, hate site”! . CAN YOU BELIEVE IT?!!!
Well, in the interest of “building bridges” , I would like to reach out to “Anders” (or “wotts” or “ATTP” or “MWWPAMMHWTBONTBTISQOPDKOBACWAJLUANUPMWIBAWFPTHMO” or whatever that needy, little drama-green has taken to calling himself, lately) with a settled-science, huggle-buggles, luvie-duvie comment, of my own (on-topic, I might add):.
Great post, above, but what does anyone expect (though it’s always fun catching the hive out doing violence to the norms (sentimental, bourgeois, defeatist-wrecker, class-enemy “norms”, to be sure) of the scientific method, if that’s, indeed, what we have here)? I mean, like, attempting to question the work of a “climate scientist” (a de-oxy oxymoron) is the equivalent of questioning the aeronautical engineering theories of some cargo-cult shaman makin’ a scare-booger cowrie-shell or two off the fortuitous flight-path of some DC-3. I mean, like, make any effort to inquire into the work of these tenured parasites and they will, of course, immediately understand that you’re potentially messin’ with their sell-out, Lysenkoist scams; hustles; rip-offs; flim-flam; “BIG LIES”; self-serving, brazen-hypocrite double-standards; “cull” immunities; and their dork-avenger (kids can be so cruel!), ivory-tower, snooty disdain for the contemptible, hoi-polloi philistines who think that goof-off, lazy-bum lefty-leeches should get their weenie-butts a real job, just like everyone else.
I mean, like, it’s all really just about these hive-bozo tools smoochin’ the “right rumps” and producing the “right answers”, which, in turn, scores them their slops-and-swill ration-cards–good for some one or another of the hive’s toady-grade, snout-ready troughs, generously provided by their careerist-hack, flunky-minder hive-betters. And that’s why they never reduce their own carbon foot-print by video-conferencing their obscene, CO2-spew, party-time eco-confabs–or to put it in other words, that’s why the ATTP creep-outs never SET THE INSPIRING PERSONAL EXAMPLE, THEMSELVES, AND NEVER EXERCISE LEADERSHIP FROM THE FRONT, WHEN IT COMES TO ZERO-TOLERANCE FOR CARBON-PIGGERY!!! AND THAT’S WHY THEY DON’T PRACTICE WHAT THEY PREACH!!!
I do hope ATTP gets a chance to read this comment (perhaps VV will re-produce it at his blog)–see, guy, this blog is not about “hate” at all. Rather, it’s really just all about callin’ out Gaia’s little-sneak agit-proppers and their fun-and-games B. S.

eyesonu

Could you condense all the horseshit. I have no idea what you were trying to say.

Brandon Gates

“I’m stoned”

David Socrates

” I’m” or is it “We’re” ??????????

Brandon Gates

I have entered the ranks of Ringo Starr and his ilk who got tired of having difficulty finding the door.

David Socrates

Mmmmm….didn’t they recently induct Ringo into the Hall of Fame?

Dale Muncie

tell us how you really feel.
well put.

Pachygrapsus

Gobachev sings. Tractors! Turnips! Buttocks!

mike

@eyesonu
Yr: “Could you condense all the horseshit…?”
Happy to oblige, eyesonu, ol’ buddy–“YO MOMMA!!!”

The oceans are buffered against ever becoming acidic.
CaCO3 (insoluble) + H2O + CO2 = Ca(HCO3)2 which is both soluble and alkaline.
The oceans below the surface layers are anyway always saturated with CO2. There is liquid CO2 lying in the deep ocean trenches. As Prof. Plimer so neatly expressed it: “The oceans can only become acidic if the earth runs out of rocks.”

Thanks. That explains why there is no acidification from acid rain in the ocean, but plenty of acidification in the Northern granite enclosed lakes.

highflight56433

Acid rain is the result of NO2, NO3, SO2 and SO3… as one learns in elementary chemistry … 🙂

tty

Not quite, all rain has always been mildly acidic (pH 5.7-6.0) due to the presence of CO2 in the atmosphere.

Now, if Acid rain can have a ph of as low as 3.5, why is that not a source of ocean acidification?

CameronH

There is no acidification problems from human activity in any freshwater lakes. thuis is more environmental pseudo science. Included in the acid rain scam was the forest dies offs which, again, time showed was nothing to do with industrial emissions. In actual fact, some studies even showed that the fertilization effect from the sulphur emissions was helping the forests. This is why we hear no more of the evil acid rain.
I do not know if our politicians are just gullible fools or whether they are just using these hysterical beat ups as deliberate excuses to increase their political power.

If my memory serves me right there was a significant trout dieoff in the Norwegian mountain lakes in the 60’s. It was caused by acid rain from England, Rhur and Saar. The same acid rain acted as a fertilizer for the lakes with limestone bottom. After scrubbers were installed, the problem went away. But- have you seen the brown cloud coming from China? It is not CO2 that makes it brown. China uses 45% of the world’s coal, much of it low grade lignite, and scrubbers cost money to operate so they are frequently down for “Maintenance’.

richardscourtney

lenbilen
You provide an important warning from the past when you relate a popular but untrue myth saying

If my memory serves me right there was a significant trout dieoff in the Norwegian mountain lakes in the 60’s. It was caused by acid rain from England, Rhur and Saar. The same acid rain acted as a fertilizer for the lakes with limestone bottom. After scrubbers were installed, the problem went away. But- have you seen the brown cloud coming from China? It is not CO2 that makes it brown. China uses 45% of the world’s coal, much of it low grade lignite, and scrubbers cost money to operate so they are frequently down for “Maintenance’.

All rain is acidic and all rain contains sulphur without which all life on land would cease. The acidity of rain corrodes stones, notably limestone. And the acidity of rain can be increased by anthropogenic emissions (i.e. emissions from human activities) with resulting enhanced corrosion and harmful health effects near the emissions.
The Acid Rain scare in Europe was typical of ‘green’ scares in that it took some true facts and exaggerated those facts to create an untrue scare.
The Acid Rain scare said that emissions of the oxides of sulphur and nitrogen (SOx and NOx) from German and UK coal-fired power stations were enhancing the acidity of rain with resulting ‘waldsterben’ (i.e. forest death) of northern European forests. There was much activity to find “evidence” to support the scare, and changes to Scandinavian lakes were assumed to be such evidence.
This scare was promoted because France had adopted nuclear power for its electricity generation. Costs of German and UK electricity would increase if their coal-fired power stations had to remove SOx from flue gases by use of ‘scrubbers’ (i.e. flue gas desulphurisation; FGD). FGD adds ~20% to the capital cost and ~10% to the operating costs of a coal-fired power station. The increase to German and UK energy supplies would increase the economic competitiveness of France relative to its nearest economic competitors.
At the UK’s Coal Research Establishment (CRE) we conducted research on all matters pertaining to the Acid Rain scare, including trials of liming Scandinavian lakes to ‘correct’ their pH.
I observed that the spatial distribution of the acidity of rain over Northern Europe was not consistent with the scare.
SOx is very water soluble: indeed, ‘scrubbers’ wash SOx from flue gases by passing the gases through a water shower. And the highest concentrations of the emitted SOx were near to the power stations. So, severest effects of the enhanced acidity of rain should be near the power stations, but there were no such effects near the power stations. This was a puzzle.
The highest acidity of rain was measured to be over regions of the North Sea near to river estuaries. SOx and NOx from the German and UK power stations would need to cross regions of high rain acidity if the SOx and NOx were to reach Scandinavian forests said to be suffering ‘waldsterben’. This, too, was a puzzle.
I suggested that there was an alternative hypothesis to explain enhanced acidity of rain over Northern Europe. Phytoplankton emit DMS (dimethyl sulphide and related sulphur compounds) from the sea and this provides the sulphur required by living things on land. If the plankton had increased their activity then increased acidity of rain would result. And the plankton had increased their activity such that they were forming toxic algal blooms which were problematic at the time because they were washing up on North Sea shores. Also, I suggested the high acidity of rain near river estuaries could be an indication that the plankton were being fertilised by outputs from the rivers. Agriculture had increased use of fertilisers following WW2 and the plankton may be being fertilised by excess agricultural fertiliser running off the land and being transported to the North Sea by rivers.
Many investigations ensued and the suggestions turned out to be true.
This finding ended the Acid Rain scare. Agriculture was a major French industry and farmers had political clout in France so France stopped promoting the scare.
Subsequently, it was determined that there had been no ‘waldsterben’: on the contrary, forests in Northern Europe had grown throughout the period of the Acid Rain scare. Also, Scandinavian lakes had been affected by natural variability and by altered run-off from land resulting from changed forestry practices.
However, the Acid Rain scare had caused the European Union (EU) to create the Large Combustion Plant Directive (LCPD). The bureaucrats who operate the LCPD need to justify their jobs so they keep pointlessly tightening the SOx and NOx emission limits with a result that UK power stations are now being shut and this threatens UK power supplies.
I keep asserting that this is a warning from history. The global warming scare was killed in Copenhagen in December 2009 but – like the LCPD – effects of the scare are likely to be imposed by bureaucracies long after the scare is forgotten. Priority now needs to be constraint of the bureaucracies.
May the Peace of Christmas be with you and all those you love throughout Christmas.
Richard

Richardscourtney
Thanks for the essay on acid rain.
In this Christmas season you may enjoy my essay on the “sin of the world” and “the lie.”
Believe it or not it deals with phytoplankton
http://lenbilen.com/2014/12/22/on-the-sin-of-the-world-and-the-lie-what-does-that-mean/
Merry Christmas:

Latimer Alder

Liquid CO2 lying in the deep ocean trenches?
Really?
How do you know?

Steve Case

Exactly what I was going to ask. (-:

LeeHarvey

Maybe it’s not exactly lying about, but it’s there. It tends to stick to glass, as I recall.
http://www.sciencedaily.com/releases/2005/01/050104114942.htm

AnonyMoose

Liquid CO2 on the ocean floor, due to volcanic emissions. It’s a localized phenomenon, and is not due to any general saturation.
http://www.livescience.com/23387-mariana-trench.html

highflight56433

…last time I checked, CO2 does not exist in liquid form at deep ocean temperatures of 0 to 3 C….or any other temperature. The freezing temperature of pure carbon dioxide at one atmosphere of pressure is -78.5 C (-109.3 F), else it is a gas. 🙂 Cheers!

tty

“…last time I checked, CO2 does not exist in liquid form at deep ocean temperatures of 0 to 3 C….or any other temperature.”
It most certainly does. At temperatures around 0-3 degrees Celsius, CO2 is a liquid at pressures above c 35 atmospheres (= 350 meter depth).

Highflight – it’s not liquified by temperature, but by pressure.
CO2 can be liquified at any temperature of 303K (30 deg C) or lower by applying enough pressure. At 31 deg the required pressure is about 74 Bar, which is roughly equivalent to a depth of 740 metres in seawater.
Explanation available here:
http://www1.chem.leeds.ac.uk//People/CMR/whatarescf.html
and a better labelled phase diagram here:
http://en.wikipedia.org/wiki/File:Carbon_dioxide_pressure-temperature_phase_diagram.svg
So, yes, CO2 can easily be liquid at the bottom of the ocean!

Mike McMillan

Liquid CO2 is denser than water, so it will head for the bottom, and since it’s a non-polar molecule it won’t mix with the seawater. So if you get enough of it together, it should indeed form puddles.

highflight56433

Joe, that is interesting about CO2. However, in the real world I am not to sure that there are any “pools” of CO2 that have been discovered. Soluble chemicals in solution tend to disperse evenly. Additionally, the oceans are well mixed due to tidal and Coriolis currents. The oceans at the poles absorb CO2 from the atmosphere where the water is cool enough for the CO2 to stay in solution, then the cool water returns the CO2 rising at the equatorial warmer waters where the CO2 is then released. Everybody know that. Cheers!

mpainter

High flight
If you check around, you can find a video of blobs of liquid CO2; this taken from a deep submersible.

Mike

Oh Geez, I like that one: “The oceans can only become acidic if the earth runs out of rocks.”
Me, I take my rocks in the form of TUMS which reduces my stomach acidification after I gulp a CO2-laden Diet Coke (and a stomboli).

Barry

Prof. Plimer obviously didn’t understand the rates of change involved:
“The natural pH of the ocean is determined by a need to balance the deposition and burial of CaCO3 on the sea floor against the influx of Ca2+ and CO2−
3 into the ocean from dissolving rocks on land, called weathering. These processes stabilize the pH of the ocean, by a mechanism called CaCO3 compensation…The point of bringing it up again is to note that if the CO2 concentration of the atmosphere changes more slowly than this, as it always has throughout the Vostok record, the pH of the ocean will be relatively unaffected because CaCO3 compensation can keep up. The [present] fossil fuel acidification is much faster than natural changes, and so the acid spike will be more intense than the earth has seen in at least 800,000 years.”
http://en.wikipedia.org/wiki/Ocean_acidification

Robert B

You forgot that its introduced as “A review by climate scientists at the RealClimate blog….”
How do you get an acid spike when there is literally an undetectable amount of carbonic acid in the oceans?
The equilibrium is such that there 1000 times more CO2 in pure water as carbonic acid (so about 0.3ppm if it weren’t neutralised straight away). The formation of the acid is very slow compared to the very rapid formation of hydrogen carbonate upon reaction with carbonate so there is no acid.
How can there be a spike?

Latimer Alder

‘The [present] fossil fuel acidification is much faster than natural changes, and so the acid spike will be more intense than the earth has seen in at least 800,000 years.”
Beyond the usual scary handwaving about ‘faster than natural’*, is there any evidence for this statement?
* – a pretty meaningless statement (aka ‘unprecedented’) trotted out when actual evidence is lacking.

Looks like one more reason not to believe everything you read in Wikipedia then, doesn’t it?
If Wallace is correct (and Sabine’s reaction that it was ‘inappropriate for Wallace to question their “motives or quality of our science,”’ — shades of Jones’s “Why should I give you my data … ” — gives rise at least to a prima facie case that he is), then Wiki is retailing rubbish, and not for the first time where climate is concerned.
The Climateers will, of course, do everything possible to keep their narrative on track. lying included should that prove necessary for “the cause”!

Latimer Alder

@barry
‘ The [present] fossil fuel acidification is much faster than natural changes, and so the acid spike will be more intense than the earth has seen in at least 800,000 years.”
The more I think about this the more ridiculous it is – but then, nobody at ‘Real Climate’ has ever been near an experimental science like chemistry for a long long time.
The rate of the reaction depends on the availability of both reagents – CaCO3 and CO2 (in the form of carbonic acid).
CaCO3 is abundantly in contact with seawater – chalk and limestone are the two major rocks composed of it – and they can be found in outcrops all over the world. For the purposes of the chemistry we can assume an infinite supply. The limiting factor has been the availability of CO2. More CO2 will cause more reaction. The chalk or limestone cliffs will dissolve a little more rapidly, but the overall pH of the seawater solution won’t change until all of the cliffs have gone.
This is not difficult to show experimentally with a piece of chalk and some acid.
Yet again the meme ‘faster than before’ or ‘unprecedented’ are shown to be scaremongering, not science. What a surprise (not).

Don

Don’t give them any ideas. LOL
I can see it now, man made rock shortage will doom us all if we don’t stop whatever it is we are doing. And give trillions of dollars to third word countries through the U.N.
The I.P.R.S. — Intergovernmental Panel on Rock Shortage

Wow. I actually thought the oceans were acidifying a little.
This reminds me of when I asked the head of one of the world’s largest merchant fleets when he planned to start using the ice free NW passage.
He laughed and replied “I think I’ll leave that question for Al Gore to answer”
My point is, even what we think of as facts, often turn out to be insubstantial alarmist nonsense which has slipped below the radar of our skepticism.

John F. Hultquist

acidifying a little
terminology adjustment needed, perhaps

In my Chemistry course, acidifying meant reducing the PH of the solution – even if the solution remained alkaline at the end of that step.

John F. Hultquist

My blueberries, respectfully, disagree.

Willis Eschenbach

Eric Worrall December 23, 2014 at 11:34 am

In my Chemistry course, acidifying meant reducing the PH of the solution – even if the solution remained alkaline at the end of that step.

In my chem course, we used titration to determine the pH of a solution. Adding acid to an alkaline solution was called “neutralization”, and not ever “acidification”.
w.

I have been arguing this on forums for years. If you have a glass of water that is very salty, and you add a grain of sugar, you haven’t damn well sweetened it! It REALLY gets my goat.

ghl

Eric
i prefer “neutralising”

Robert W Turner

In my chemistry, we referred to it as neutralizing. Acid and bases have very different properties and neutralizing a base does not give it any more acidic properties than it had before.

Robert B

pH 8 means about 100 times more caustic soda* than acid.
*Excuse the alarmist speak.

Don K

“Wow. I actually thought the oceans were acidifying a little.”
With data like that, how the heck could anyone tell? Maybe if we had five or ten centuries worth, a valid signal could be extracted.
“This reminds me of when I asked the head of one of the world’s largest merchant fleets when he planned to start using the ice free NW passage.”
Tangential, but I suspect that even if Arctic ice declines later in the century, the decision of running ships through the Arctic will be made by marine insurers, not shippers. And I expect they are going to want way less than 15% ice cover, reinforced hulls, and reduced speeds before they will offer acceptable rates.

Gunga Din

As to your point, that remind me of something I saw on the History Channel (a few years ago) about the Bermuda Triangle. The hype presents it as a “dangerous area”. The fact I recalled is that Lloyds of London which insures much if not most ocean vessels does not charge a premium for sailing through the area. There is no increased risk. Only the impression of it.

John Peter

I wonder if any of the American readers with professional qualifications would care to draw this to the attention of senator Inhofe so that he could hold another Senate enquiry into this sorrowful affair.

milodonharlani

IMO our blog host is familiar with Sen. Inhofe.

CodeTech

I’m also certain that Sen. Inhofe is familiar with WUWT

eyesonu

There are very many with professional qualifications who are reading WUWT.

Lawrie Ayres

A few years back I, a very humble Australian, wrote to Senator Inhofe to thank him for his efforts to have the truth about the AGW scam publicised. He very generously and graciously wrote a lengthy and thought provoking reply. He is a real American hero and should be admired as such. You would be better off writing to some of those scientifically illiterate Democrats.

Lawrie Ayres,
Sen. Inhofe is a true gentleman; very different from the average senator. He knows his science, too. Other [liberal] senators do not dare to debate him on any science subject, including MMGW.

David Socrates

“Sen. Inhofe is a true gentleman;”
..
http://www.avweb.com/avwebflash/news/inhofe_senator_closed_runway_texas_faa_investigate_203537-1.html

And a very poor pilot

David Socrates

A “gentleman” would not vote against disaster relief for hurricane Sandy, and vote for disaster relief for Oklahoma tornado victims.

Sandy was not a hurricane when it made landfall, so voting against aid to fish is hardly comparable and your equivalency is proven false

mpainter

Socks rats
You have a vertible arsenal of alarmist narrative and abuse. How many are there of you? How are you funded?

Mac the Knife

We need criminal negligence charges brought against these pHrauds. Is there any viable way to directly bring them directly to justice?

knr

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.”
That is a rather big red flag they put up and right in line wuth Jones ‘why I should I send you the data you only want to find something wrong with”
Its amazing how mush this ‘settled ‘ science which reports to be the most important thing and where there is no time to lose , so easily resorts to apporachs which very much worked against theses claims given little trust is put in place of those that employ smoke and mirrors .

Harold

Right. Unless there are a few iterations in the dialog that are missing, that has mens rea written all over it.

Yes, that’s what I thought. If the pursuit of science is towards transparency and accuracy, then why the resistance from Sabine? That’s a moot question– we all know why he was so resistant: funding.

daveandrews723

There is a certain President who claimed his administration would be “the most open and transparent” in history. We all know what that has gotten us. NOAA/NCDC and the rest of the CAGW cabal have learned at the foot of the master… or maybe he learned from them.

Pamela Gray

“you will not last long in your career.” This seems either a threat or a lament, or both! Either one speaks volumes of the still rancid climate research environment. Scientists the world over need hang their head in shame for allowing such an environment to exist. Silence is culpable. Culpable!

gaelansclark

Respectfully, silence is an indictment….to fraud, misconduct, collusion, ignorance, and any other general act of deception designed to make a result.

Mike Smith

Congratulations Mr Wallace on your development of a very nice litmus test for ocean acidification.

LeeHarvey

I see what you did there.

Mike –
Does that make Wallace’s work a litmus paper?
Just wonderin’.

John F. Hultquist

If you are looking for a color change —
http://hydrangeashydrangeas.com/colorchange.html

Aphan

+10

Feely of PMEL was also senior author on the Whiskey Creek oyster hatchery abomination, which constitutes ‘knew or should have known’ academic misconduct. See essay Shell Games in Blowing Smoke: essays on energy and climate. The oyster portion only was a guest post of the same title at Judith Curry’s. Not surprising he also violated FOI and hid the instrumental ocean pH record.
[Typos corrected. -w.]

Designator
R2Dtoo

Does anyone know if the oyster study also was funded by Heinz?

DrTorch

Why do a linear plot of the 10 year moving average? Why not just a linear plot of the annual values?
Frankly, the persistence of sub 8 pH values is eye catching. Is there meaning to this?

My impression is that Wallace lumped all known data together: measurements at very different (including coastal upwelling?) places during different seasons.
I would like to see the spread of the data within each year that was plotted. That will give some idea of the variability in measurements from instruments, place and seasonal variability over the years. I suspect that the spread is enormous compared to the 0.1 pH unit/century where we are looking for…

See my comment below, you can easily extract what you need and graph it.

Walt Allensworth

The heavy dark blue straight line is incorrectly annotated in Wallace’s figure.
Probably a simple annotation error.
This dark blue line is clearly a linear curve fit to the entire data set since 1910.
It is also clear from the chart that the measured pH has been decreasing over the last 20+ years. (the light blue 10-year moving average).
It’s also somewhat clear that this is probably just measurement variability. If we had 1,000 years of data that issue would be oh so clear.
Ain’t it always the way?

LeeHarvey

I’d say that the heavy dark blue straight line is the linear trend of the ten-year moving average line. You’d have to ask the chart’s creator why they gave that linearization instead of the linear trend of the raw data…

Why use a linear trend as a function of time at all?
Maybe it has political meaning, but it is physical nonsense.
It has the meaning of a cartoon; entertainment disconnected from reality.

The chart’s creator is the author of this post

or, more correctly, the creator is Mr Wallace.

Barry

Since the chemistry of carbonate systems is well known, can anyone provide a physical explanation of why ocean pH would NOT be decreasing? Thanks.

Latimer Alder

Buffering. The White Cliffs of Dover are still there and still abutted by the ocean last time I looked.

M Courtney

Yes, that is using the well known chemistry of carbonate systems.
But it is more complicated than chemistry. There are biological systems that react to changes too.
Increased CO2 will aid photosynthesis by phytoplankton and so change ocean chemistry. Increased emissions of dimethylsulphate (DMS) caused by the beneficial effects of increasing CO2 levels may well cause some ocean acidification.
Apparently is doesn’t, but it always seemed reasonable to me.

milodonharlani

Phytoplankton get their CO2 from seawater, not the air. There may be exceptions of course.

Ocean pH varies greatly day to day. Monterey Bay aquarium used to have a daily plot of pH on their water intake that showed daily and seasonal variations. Now they seem to have bought into “Acidification Alarmism” and the graph has disappeared from view. Maybe it is buried there somewhere still, but it used to be easy to find. No longer. All you get now is all their research on Ocean Acidification. What a change over a few short years.
Nevertheless, you can find a few morsels here and there. This is from Scripps:
“They found that in some places, such as Antarctica and the Line Islands of the south Pacific, the range of pH variance is much more limited than in areas of the California coast subject to large vertical movements of water known as upwellings. In some of their study areas, they found that the decrease in seawater pH being caused by greenhouse gas emissions is still within the bounds of natural pH fluctuation. Some areas already experience daily acidity levels that scientists had expected would only be reached at the end of the 21st Century.
Read more at: http://phys.org/news/2011-12-comprehensive-key-ocean-ph-variations.html#jCp
Oh yeah: CONCLUSION – more study is needed. 🙂

tty

As a matter of fact practically all seabottom rocks are alkaline (limestone, basalt…). As an oceanographaer once said “the oceans consist of an alkaline liquid in an alkaline container”.

Barry

Latimer, there is buffering but the real issue is the rate of change:
“The natural pH of the ocean is determined by a need to balance the deposition and burial of CaCO
3 on the sea floor against the influx of Ca2+ and CO2−3 into the ocean from dissolving rocks on land, called weathering. These processes stabilize the pH of the ocean, by a mechanism called CaCO3 compensation…The point of bringing it up again is to note that if the CO2 concentration of the atmosphere changes more slowly than this, as it always has throughout the Vostok record, the pH of the ocean will be relatively unaffected because CaCO3 compensation can keep up. The [present] fossil fuel acidification is much faster than natural changes, and so the acid spike will be more intense than the earth has seen in at least 800,000 years.”
http://en.wikipedia.org/wiki/Ocean_acidification

mpainter

Barry:
” the need to stabilize the pH of the ocean”
Barry, do not swallow the horsegrunt of the alarmists. Ocean pH varies from under 7.5 to over 8.1_naturally_, so stabilize where?
I suggest that you work on stabilizing your sphincters.

Dr K.A. Rodgers

Have a read of the first chapters of Krauskopf’s “Introduction to Geochemistry”. You’ll need first year undergrad chemistry to follow it.

Dr Rodgers thanks for your several helpful comments on this thread. When I was looking at the carbon cycle in the oceans recently, I got the understanding that CO2 doesn’t exist as a pure gas in the oceans. It becomes a carbonate, but distinguishable from the other carbonates produced by the action of seawater on the rocky seabed. Can you straighten me out please?
And if warming oceans are supposed to be nett outgassing carbon dioxide, how do they absorb more and become less alkaline?

ferd berple

ocean pH varies by depth. change the vertical circulation via long term ocean oscillations and you change the pH. depending where you are in the ocean cycle, pH will either be increasing or decreasing.

Barry, the pH of the ocean surface is indeed decreasing over the past decades, as measured by a few longer time series like Hawaii (since 1989) and Bermuda (since 1985), buoys and regular research ship cruises. See:
http://www.epa.gov/climatechange/science/indicators/oceans/acidity.html
and http://hahana.soest.hawaii.edu/hot/trends/trends.html
The decrease of pH is accompanied with an increase in DIC (total inorganic carbon) and pCO2,
This shows that the CO2 is coming out of the atmosphere into the oceans, not the other way out.
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 (some were accurate to +/- 150 ppmv…), 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 biolife…. 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…

I have never trusted the OA claims. Indeed as Wallace found changes in pH correlate with upwelling which increases during the negative Pacific Decadal Oscillation. The fact is pH changes rapidly with depth and there would be considerable uncertainty depending how a 200 meter average was derived. As the graphs in my presentation show pH varies dramatically depending on location, and on a a daily, seasonal and decadal basis starting around 2:50 https://www.youtube.com/watch?v=ooaZLoJXhu4

Joseph Murphy

I have somewhat trusted the claims, they make ‘first glance’ logical sense. What never sat well with me is the absolutely minute changes we are dealing with causing any sort of issue. Nature just ain’t that sensitive.

Latimer Alder

‘ Nature just ain’t that sensitive.’
Sure. Any organism that was really badly affected by tiny changes in pH would not have survived long. We know that pH naturally varies a lot on daily, monthly annual and decadal tiimescales.
Nor any that found a less than 1 degree change in ‘average temperature’ (even if that is a meaningful calculation) beyond its capabilities.

Bill_W

Barry, the ocean has many other ions in it plus the insoluble forms with various counterions (rocks, crystals, etc.). Many of these ions are themselves weak acids and bases. So it is a complex equilibria with dozens of different species and buffers, not just carbonic acid (in case you are not a chemist this is CO2 + H2O). In addition, there are thousands (or millions?) of different species of coral and shellfish which use carbonate in its various forms to make their shells. Some may use carbonate, some bicarbonate, and some CO2 directly in their various membrane transporters so they can also affect the equilibria of the various forms of carbonate. In addition, the photosynthetic organisms will use the CO2 to fix carbon to make glucose. Some of them will use CO2 directly; others may pull in bicarbonate instead. So you have hundreds of different inter-related equilibria going on. So, just as with so many other issues in the climate area, it is enormously complicated. But these problems can be oversimplified down to just a few species or processes and politicized. Those that do this over-simplification are known as simpletons.

ferd berple

the most plentiful organizm on earth is algae. It consumes more CO2 than any other organism. algae produce about 330 billion tons of oxygen each year, which represents 500 billion tons of CO2. In comparison, humans produce 6 billion tons of CO2. but we rule the planet. just ask anyone.

The net result of all sea life is an estimated drop out of ~6 GtC/year form the ocean surface into the deep oceans. That is based on continuous sampling of dropping organics and inorganics at the same places as the continuous pH, DIC, etc. measurements. The difference in CO2 uptake is returned as CO2 in the same ocean surface layer by the whole chain of phytoplankton eaters and their predators…

Barry

Well, when I read the following, in the context of your “complicated processes”, I’m not convinced that all those other equilibria will compensate:
http://en.wikipedia.org/wiki/Ocean_acidification

Michael 2

You pay your money and you take your chances.
http://idioms.thefreedictionary.com/You+pays+your+money
Or “YMMV” – your mileage obviously varies!

Eliza

The Ocean is actually quite alkaline not acidic. Our blood pH is 7.4 slightly alkaline. pH 7 = Neutral

TRM

I once thought ocean acidification was a problem just like I once thought CO2 was going to cause Earth to overheat. I’m so glad I read both sides and judge from that standpoint. This site is very good for getting the details out. These days the first question I ask is “Is that a model output or real world data?”.
Kudos to Wallace for not backing down in the face of threats. How completely dogmatic and unscientific their response to him was.

Tom

These shysters have a very slack attitude to the meaning of words, unlike real scientists. Something that becomes very slightly less alkaline does not mean it becomes very slightly more acidic. The 2 states are different. It’s like saying someone who becomes less obese becomes more anorexic, which is daft.

Nigel Harris

No, it’s exactly like saying someone who becomes less obese is slimming.

Alx

Obese, fat, slim are all relative terms, Acidic and alkaline are specific terms related to specific ranges. An alkaline solution can never become more acidic and an acidic solution can never become more alkaline. They can only be various levels of one or the other. That the term acidic is used so loosely by the media means they are ignorant, that the term is used so loosely by scientists means they are dishonest.

RH

Yes, but less alkaline, or more neutral, isn’t very scary. Acid burns and is very scary. All those poor sea creatures swimming around in burning acid. What kind of monsters are we? Where can I buy my carbon credits?

ossqss

How the heck do these type of folks get away with this type of fallacy. Where is the due dilligence and verification process in congress?
This type of garbage sets policy based upon fantasy. I mean really, if this was type of thing was done in any other facet of our lives, there would be jail time involved for the perpetrator.
To heck with the FOIA, there should be a class action law suit for damages rendered!
Let the discovery process commence!

“…if this was type of thing was done in any other facet of our lives, there would be jail time involved…”
Oh…you mean like all of those bankers that are in jail?
Oh…wait…

Latimer Alder

Great argument.
‘Look – other fraudsters over there! Leave OUR fraudsters alone.’
Unconvincing.

Eliza

In fact Ammonia NH3 which exists at high pH values (alkaline) is very toxic to fish because it is lipid soluble, enters cells, and many basic enzymes don’t work anymore. NH3 is converted to NH4 in a more acidic environment and is NON-toxic because it is not lipid soluble.

Jeff Alberts

Methinks that having a single trend line for PH of ALL the oceans is like having a single global temperature trend line. Physically meaningless.

Dr K.A. Rodgers

Yup … even of one ocean.

michael hart

Exactly. And pH is harder to actually measure . Like ‘warming’, there is a high probability of it being net beneficial (if anyone was ever able to measure that).
Alarmists like “acidification” because they think it is a nice simple way to scare the horses. They assume that most people’s understanding of chemistry is at least as bad as their own.

Latimer Alder

There is a perfectly good chemical term – neutralisation – that is both technically accurate for the processes involved and does not hold the connotations that ‘acidification’ does for the general public.
That supposed ‘scientists’ continue to use the latter, though aware of the possibility of general misunderstanding, suggests to me that their motives aren’t totally those of objectively seeking the truth. That they strenuously argue for its retention is further evidence of this

tadchem

The pH range 7.9 to 8.2 is in the range of the bicarbonate buffer system. At this pH range the concentration of CO2 (as carbonic acid – H2CO3, or CO2 hydrate) is 1.5 to two orders of magnitude *lower* than the concentration of bicarbonate ion HCO3-. Bicarbonate is the form plankton, corals, and other shell-forming sea creatures need to use to make their shells, including coral reefs.

Several experimental data-sets do show (moderate) acidification over time – see e.g. figure 7 in this report:
http://tos.org/oceanography/archive/27-1_bates.html

schitzree

Ruth – the time lines for the pH measurements in the paper you linked to are all in the 15 to 30 year length. They would take us back to the mid 80’s at best, or to the highest point on M Wallace’s graph.
Anytime you see a Climate Alarmist who thinks the world started sometime after 1972 then you can bet the measurements from before then will disprove their theory.

Thanks Ruth for the link! Mine of Bermuda was gone…
schitzree, the problem with many of the historical measurements are accuracy, place and time of measurement. Few series were repeated over time at the same places in the same seasons, which make it very difficult to know the overall trend of pH.

RobW

Can someone post a link to an article a couple years back that demonstrated the ocean around San Francisco fluxuated a full pH unit daily. Thanks

Rob there was a paper High-Frequency Dynamics of Ocean pH: A Multi-
Ecosystem Comparison http://www.plosone.org/article/info%3Adoi%2F10.1371%2Fjournal.pone.0028983
that has this graph http://landscapesandcycles.net/image/97416191.png
and discusses daily changes in Elkhorn Slough and Monterrey just south of SF, among other changes at other sites.

Willis Eschenbach

RobW December 23, 2014 at 8:09 am

Can someone post a link to an article a couple years back that demonstrated the ocean around San Francisco fluxuated a full pH unit daily. Thanks

In addition to Jim Steele’s excellent link, you might be referring to my post called “The Electric Oceanic Acid Test“, which contains the following graph:

w.

RH

Warmer temps equal higher ph. So the answer to “ocean acidification” is global warming?

Tom T

” 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.”
A rather Gavinesque ‘how dare you accuse me of fraud’ response.

ferd berple

“you will not last long in your career.”
==========
clearly a threat .

RH

I hate to be wet blanket, but these noaa directors are pretty skittish when dealing with the public. I’d like to see the actual email exchange before concluding that a threat was issued.

PiperPaul

pHraud from Ph(D)rauds?

Like the narrative for “hottest year” (by 0.02 immeasurable degrees), there is something fundamentally hinky about 400 ppm CO₂ being capable of acidifying, in any measure, the volume of the oceans. And “oh, but it’s just surface acidification” doesn’t count. The oceans mix. Sorry. And for someone to fuel (and shield) the narrative by stonewalling a sceptical review of their work, is, in a word, corrupt. The mass balance, as mentioned at the outset, is insignificant. Only exists in a modelled state. These people just need to go away.

Mike, the few hundred meter surface layer of the oceans is in direct contact with the atmosphere. Exchanges with the atmosphere are very fast: 1-3 years half life time.
There is hardly any exchange between ocean surface and deep oceans, only via (polar) sinks and upwelling places. That gives an exchange of ~40 GtC/year as CO2 between the atmosphere and the deep oceans, or ~0.1% of total C in the deep oceans…

Just want to reemphasize that it is Richard A. Feeley and NOAA that is responsible for this intentionally misleading chart.
There will be an accounting someday and it is good to have a list of the perps.

I have added Feeley to my growing list of perps . Wallace asks “is it acceptable to omit the majority of the data ” But it seems to be a pervasive tactic accepted by peer reviewed climate “science”
http://landscapesandcycles.net/American_Meterological_Society_half-truth.html

David Socrates

If data begins at 1850, why has Wallace omitted the data from 1850-1910 in his chart?

Roy Hartwell

Do keep up !!! The glass membrane pH electrode was not invented until 1909. Before that time , pH was measured by indirect means such as titration against an indicator. Any scientist knows you cannot reliably compare data sets obtained by such widely different methods unless you have a reliable means of validating them.

Yeah…just ask Mann!
/sarc off

David Socrates

The definition of pH does not depend on how it is measured.
..
I guess Wallace is just cherry picking the data.

mpainter

socks: give your opinion, please, of scientists who behave in the manner documented in this post. Thanking you in advance.

To have some idea about the change in pH of the oceans, the accuracy of the measurements would need to be better than 0.01 pH unit. Someone who has an idea of the accuracy of the first glass electrodes of that time? My last pH titration was some 40 years ago…

The accuracy does depend on the measurement. What a fish!

David Socrates

OK mpainter.

Wallace should include the data from 1850, instead of dropping 60 years of it. He’s doing the same thing Feely is doing.

mpainter

It seems that you are putting Wallace on the same level as Feeley, regarding their respective behavior in this affair.

David Socrates

Yup….seems like both of them qualify as “cherry pickers”

tty

The pH scale wasn’t invented until 1909.

Bill Illis

David Socrates reminds me of Dana Nuccitelli.

Hey, maybe he is Dana Nazicelli   ☺ 

Lots of young folks here? Used to do pH titrations in the lab 50 years ago. OK, maybe not as “good” as the new electronic methods (calibration) but why not show the whole record with error bars?? Titration may be 0.05 to 0.2 units depending on procedures, high end spectrography may be 0.02, others less accurate.
http://news-oceanacidification-icc.org/2014/05/27/precision-and-accuracy-of-spectrophotometric-ph-measurements-at-environmental-conditions-in-the-baltic-sea/
So, why not show the whole record? Or does it show that there is nothing to see? Roy?

Thanks Wayne, I was looking for the accuracy of the early glass electrodes…
If we put the ancient electrodes and procedures at 0.1 units (best result) and the pH drop at a fixed place in the oceans with a growth of 40% CO2 is not more than 0.1 pH units over 100 years, what then is the value of the historical data, taken at a lot of different places in different seasons? Or shall we conclude that near all pre-1985 data are within the error band of the measurements?

tty

Remember that no measurement is better than its calibration. Modern pH-meters certainly measures to bettter than 0.01 units, but they really can’t be calibrated to nearly that precision. pH is basically chemical, so ultimately all instruments must be calibrated against a standard solution with known pH. Those are not exact to 0.01.

Fortunately, one can (theoretically) calculate the pH from other observations in the oceans, as they have done for Bermuda and Hawaii, including some overlap of the two methods. If that is better than 0.01 pH unit still is questionable, but anyway easier to obtain than direct pH measurements. Although colorimetric analyses seems quite promising and not labor intensive, so that such automated equipment can be installed maintenance free in merchant ships. Automated pCO2 measurements are already installed in commercial ships…

mpainter

Ferdinand
You never before admitted that the Bermuda and Hawaii pH figures were theoretically derived. These are your touchstons for ocean pH increase and now it comes out that these are not direct measurements, if I understand you correctly.

mpainter, they performed both direct pH measurements and calculated ones. The calculated ones are far easier to obtain and more reliable than the direct pH measurements, but both (partial) series overlap each other.
See: http://hahana.soest.hawaii.edu/hot/trends/trends.html and look at the pH comparison…

Roy Hartwell

The one clear thing there is to see on the data presented is that choosing the downward slope of the trend curve obviously shows a decrease in pH. But that’s just a snapshot in time. If I quoted the trend for 1950 to say 1970 it would quite clearly show an increase in pH with time. Other points could/would indicate no change with time ( 1970 to 1990 ?). You pays your money you takes your choice.
The bottom line is anyone REALLY cherry picking data (say to fit a preconceived hypothesis-surely not !!) could easily do so with a naturally fluctuating system.
Does the pre-1910 data show any difference ? I don’t know but I might wager a small amount of pension that it would also show a natural cycle.
But hey, I’m just a newcomer on the comments here.
( ps. Wayne, I can only claim 43 years in the lab 😀 )

Roy, I doubt that the pre-1985 data have any value if they were taken with glass electrodes (+/-0.1 pH unit), different places and different seasons. We are searching for a (theoretical) trend of about -0.1 pH unit over the first 100 years of human emissions…

Gary Hladik

David Socrates, can you point us to the “omitted” data 1850-1910?

David Socrates
sleepingbear dunes

As a chemistry illiterate, why are the annual amounts around 1920 and 1960 be so much below the general trend? If no error in capturing the data, what possible real life situation would cause what appears as a significant statistical outlier.

Pat Frank

Those offsets are probably just due to regional outliers, sbdunes. None of the points in the trend line represent the global ocean. All of them are probably complied from regional maritime series where pH happened to be measured during some study. So, depending on what regional excursions enter into the record average, the supposed global pH average can wander about.

Alx

Sabine warns Wallace to not question their “motives or quality of our science”, I am sure Wallace did no such thing, but Sabine bringing it up means he is aware of his ulterior motives and it’s influence on his work.
It’s like when a cop asks the question, “Did you take John Smiths cash and checkbook from under his mattress?” and the suspect responds, “No I didn’t, John Smith is lying, there was no checkbook under the mattress.”

Harold

More like:
Cop: Can I see what’s in your glove compartment?
Perp: There’s no cocaine in there.

mpainter

Except Wallace was no cop, but a colleague.

Alan Watt, Climate Denialist Level 7

The original article also states:

In 2010, Feely received the $100,000 cash prize from the Heinz Family Foundation awards (established by Teresa Heinz, wife of Secretary of State John Kerry). The Heinz award site touts Feely’s work: “Ocean acidity is now considered global warming’s ‘evil twin,’ thanks in large measure to Dr. Feely’s seminal research on the changing ocean chemistry and its impact on marine ecosystems.”

That’s a significant motivation not to respond to inquiries like those of Mike Wallace.
I would be interested to hear the scientific justification for building a model to produce time series output and then not checking that against empirical data of the same type one already has. Really, I would.

Alx

Well mathematically $100,000 is more money than $0. Scientifically this leads to an irreversible upward trend in Mr. Feelys ability to buy more stuff. Morally and ethically totally bankrupt.

Robert W Turner

Wow, I just read this in the original article as well and can’t believe it was omitted here. How convenient for him that scientactivists are now being paid to manufacture results. I always had a feeling that finger pointing at skeptics claiming they were all being paid by the fossil fuel industry was simply a projection of guilt, not I’m quite certain. Feely’s connection to this foundation and award money need to be investigated.

CaligulaJones

Shorter answer: we need more $cience…

mpainter

Now it will be all over the State Department how the wife of John Kerry, Sec. State, US, got took by a dubious scientist for $100 grand.
And next the world.
Pass the ketchup, please.
These frauds never believe that they will be sniffed out.

Jeff Alberts

Dick Feely and seminal research. There’s a puerile joke in there, I’m sure.

sailboarder

Omitting data, thus lying to Congress is an is a criminal offense, is it not?

Joseph Murphy

Contempt of congress or purgery is against the law. It is up to congress to enforce it however.

Alan Watt, Climate Denialist Level 7

I believe that only applies if a witness is put under oath. Most people who appear before congressional committees are invited by whichever political faction believes the presentation will further their policy goals, and are not put under oath. Unlike some professions which require a professional license and civil liability insurance, climate scientists (and scientists in general) are not legally held to any specific standard of performance. So even if he did give testimony under oath, I really doubt Feely could be charged with perjury or held in contempt of Congress unless he were specifically asked whether the historical pH data were measured or modelled and gave a false answer. If you have access to a transcript of his testimony, it might be interesting to research, but I would not hold out much hope you would find anything incriminating.
Basically, if you are an impartial jurist, how can you hold it a crime to repeat before Congress what a witness has already published in a (drum roll, please) peer-reviewed journal? Thus the corruption of peer-review has ripple effects in other venues.
Eventually this will get sorted out as it has in other professions. We don’t allow bankers, stock brokers, or realtors to regulate themselves by their own standards (although they all claim the ability to do so). Eventually the body politic will figure out that as a group scientists have ceased to be disinterested seekers of truth and joined the throngs of other self-interested parties, and must be externally monitored and regulated as such. The more climate science tarnishes the common view of science, the sooner that reckoning will come.
Or possibly our civilization will collapse first from the cumulative corruption and stupidity of the people we have unwisely elevated to public office — it’s a tough call.

eyesonu

Unfortunately, I must agree with you.

David S

So who was measuring the Ph of the oceans to a depth of 200 meters back in 1910? For that matter who was measuring it in the years since?

MikeN

I’m seeing a large drop in pH since 1985 or so. This looks like the equivalent of arguing there is no pause in temperatures because the 30 year trend is one of increase.

Russ R.

Mike Wallace would do better publishing his findings than touting them on blogs.

You are unfamiliar with electronic publishing?

Alx

Hard to publish a study, when the authors of the study you are researching are running for the hills. I think you knew that or maybe not.

mark d

The moving 10 year trend does show a decline in PH. Am I missing something?
PS… I want to say thanks for exposing this (sadly unsurprising) cover up. A scientist, more than any other professional, should be most forthcoming with their information. They should be interested in the truth, and welcome critique.

The whole POINT of sharing data is so that other scientists can eliminate observer bias (motivation) as a source of error in the analysis.
I want you to question my motives. I need you to question my motives. I give you my data and and my code to aid you in the destruction of my claims. If I give you my data and I give you my code and you cannot find any effect due to choices I made in analyzing that data, then you are rationally obligated to accept my results.

Steve Oregon

Unfortunately The Team has made the whole POINT of sharing data selective and obstructionist to limit the ability of other scientists to eliminate observer bias (motivation) as a source of error in the analysis.
The Team has been hypersensitive and condemning of anyone who would seek to challenge their motives. When faced with opportunities to defend their motives by sharing their data and code they often refused in order to prevent any destruction of their claims.
Their lack of confidence in their own work prevented them from exposing their data & code to reviews which would critique their choices made in analyzing that data.

Pat Frank

It’s not their lack of confidence, Steve. It’s that they know what isn’t tendentious (forced into predecided conclusions) is outright lies. To be charitable, a fair bit of the former rests on incompetence.

Alx

And if one does not provide their data and code to aid in the investigation of their claims, what are we then rationally obligated to accept?

ferd berple

Mosh makes an excellent point.
All too often we see studies in which the results only show up when the data is tortured via convoluted mathematics. Yet which analysed by more conventional mathematics, the results disappear.
If your results are robust, they should not depend on the choices you made in analysing the data. If the results change depending on your methods, then the first thing you should suspect are your methods.
Unfortunately, all too few scientists speak out because of the “you will not last long” problem.
Silence is Golden is the rule all too often, especially among the incompetent. Don’t question my results and I won’t question yours. In that way our faulty science will remain above reproach while we collect our government grants. Should anyone ask, the dog ate the data.

John F. Hultquist

Mosh makes an excellent point.
He also mentions code, meaning equations with operators, special symbols, and constants. Mistakes are easy to make and hard to find. Especially true if you have looked at many lines of code dozens of times.

Steven Mosher on December 23, 2014 at 9:42 am

Steven Mosher,
Wonderfully put.
That kind of Feynman-like view is wisdom. An intellect should, to be in objective mode, fully aid critics to find all possible issues with one’s work.
Steve, Happy Holiday Season to you.
John

I second John’s statements. Thank you.

Steven Mosher,
Excellent! Feynman couldn’t have said it better.
Now, if you can just get Michael Mann to go along…

Bill Illis

Let’s see some breakpoint data for the BEST project Steven.
Having asked politely for this 9 times now, I’m assuming your comments above contain some qualifiers as in, some data can be released and some not.

Kasuha

The graph is lacking one important feature – error bars. I believe we can safely assume measurement error was pretty large prior to invention of modern pH measuring methods and taking that into account, all ups and downs prior to 1970 can likely safely hide into it. All that’s needed for the data to be compatible with the ocean acidification hypothesis is for any measurements prior to 1970 to have pH +/-0.1 stochastic and +0.1 systematic error. And something tells me people were not after pH 0.01 accuracy before 1970.
Now what I really want to say is that this definitely needs some attention. The data don’t say much, but the reluctance to provide them is suspicious.

ferd berple

anytime your trend depends on the choice of endpoints, you have no trend.

I believe we can safely assume measurement error was pretty large prior to invention of modern pH measuring methods
No we cannot assume that. Stoichiometry is capable of highly precise, repeatable, measurements.
It is however safe to assume that measurements of equal precision are likely cheaper today than 100 years ago.
On the other hand, systematic error might be more common today with overconfidence on a black box experiencing instrument drift.

Kasuha, I agree on that point: pH measurements with glass electrodes may have been accurate to 0.1 pH unit in the early days, while we are looking for a trend of 0.1 pH unit over (the first) 100 years of human emissions. Thus I fear that most of the 2 million historical data simply can’t show the real trend in pH of the oceans…

michael hart

And they need to be adjusted for salinity…
There is a host of variables that need to be discounted before the panicists hypothesis crosses the credibility threshold.

Windsong

Curiouser and curiouser. Craig Welch, lead reporter of The Seattle Times 2013 award winning “Sea Change” series on ocean acidification, refers to the research of Richard Feely and Christopher Sabine as sources for the content of the series.

And Welch never responded to my letter pointing out the scientific misconduct in both the corals and the oysters he used for Sea Change. No retraction, no correction, nothing. See esssay Shell Ganes for the details and references to both acidification scares. Prof. Cliff Mass in Seattle also bogged this and tried to get Seattle Times’s attention based on my guest post at Judiths. No luck either.

Windsong

A correction or two would interfere with the steady stream of awards the OA series has accumulated, like the du Pont award last week. Craig Welch and the Times have been less enamored of Dr. Mass lately due to his criticism of it. Welch’s response to Dr. Mass has citations of Feely and Sabine papers.

etudiant

Afaik, the global carbon inventories, in billions of tons, are roughly as follows:
Fossil fuels, 4000; atmospheric CO2, 700; vegetation and soil, 2000; oceans, 40,000.
So burning all the fossil fuel we can reach could increase the oceanic CO2 content by about 10%.
It is difficult to create a catastrophe from a 10% change.
That leaves the scientists working for the US in a dilemma.
Recognizing that oceanic buffering overwhelms any possible CO2 effect conflicts with their employers mandate, expressed by Interior Secretary Sally Jewell, who announced that ‘climate change deniers are not welcome in the Department of the Interior’, the umbrella agency that manages NOAA. So they either toe the official line or leave, with not many places to go.
Eisenhower, in his prescient farewell address, spoke of the dangers arising from a government monopoly on scientific research funding. Climate science today could be the poster child illustrating his fears.

Latitude

Oceans do not magically suck CO2 out of the air…
…if it did, we wouldn’t have any
Present CO2 levels are not high enough to affect ocean pH
Biological processes produce so much acid….the buffer would have to run out first….the oceans would be acid without CO2

Barry

Sorry, but Henry’s law is well known. Higher CO2 concentrations in the air means more dissolved CO2 in the water, leading to lower pH. And while there is plenty of “buffer” in the ocean, it’s a rate constant problem — the ocean can’t keep up with the increase in dissolved CO2. This page explains the biological impacts: http://www.pmel.noaa.gov/co2/story/What+is+Ocean+Acidification%3F

Latitude

Barry, you just said it’s impossible to have a fish aquarium in a closed building…
use your head and stop buying into this crap

Tom T

The inability to buffer claim is based entirely on the flawed model in question.

Barry, see the graph from Evans 2011 below. It is not a simple rate problem as you suggest. The upper ocean can deal with 3 times the current CO2 in a matter of weeks.

Barry is right in this case: any change in CO2 of the atmosphere translates to a 10% change (due to the Revelle/buffer factor) in total CO2 and a drop in pH of the upper ocean layer within 1-3 years. That is what is measured in several places over the past decades.
If that will have any impact on sea life is doubtful as the main calcifying organisms evolved at much higher CO2 levels during the Cretaceous, witnessed by the white cliffs of Dover and many such places all over the world…

Latitude

Ferd, Barry is not right…..Barry said: “Sorry, but Henry’s law is well known. Higher CO2 concentrations in the air means more dissolved CO2 in the water, leading to lower pH”
the ability of water to absord CO2 is buffer dependent…..a higher buffer can absorb more CO2 and have no change in pH
Barry said: “And while there is plenty of “buffer” in the ocean, it’s a rate constant problem”
No it is not…..since buffers can change

Latitude, seawater is a rather weak buffer: it is in equilibrium at about 10% of the change in the atmosphere. That gives that the 30% increase in the atmosphere only shows up as a 3% increase in DIC (CO2 + bicarbonate + carbonate) in the ocean surface layer, even if free CO2 in the surface layer also increased 30% per Henry’s law. But free CO2 is only 1% of total carbon in seawater…
Further the quantities are not that different in the ocean surface layer as in the atmosphere: ~1000 GtC in the “mixed” ocean layer, ~800 GtC in the atmosphere. The 30% increase in the atmosphere did increase the surface layer with only 30 GtC. Which makes that the surface layer is fast saturated (1-3 years behind the atmosphere).

Latitude

Fred, northern latitudes hold more CO2 than southern…it’s because they are higher in buffer
Henry’s law assumes there are no chemical reactions taking place….
the more buffer…the more acid you can add without affecting the pH

michael hart

Barry December 23, 2014 at 10:45 am
“…it’s a rate constant problem..”

+10 Barry.
Atmospheric CO2 not in equilibrium with the ocean.
Sources maybe removed by thousands of miles from sinks.
Sources may become sinks and vice versa, depending on season or time of day.
And the inter-conversion of free CO2 and bicarbonate is about ten million times slower than a diffusion limited reaction. That’s why every living organism utilises carbonic anhydrase to speed the reaction up.
It’s not just economists that made unworldly assumptions about equilibrium.
Henry’s Law looks pretty flaccid in face of those home truths.

highflight56433

Yep, we should be really reaalllyy reeeaaallllyyy worried! Look at how CO2 has been so deadly to planet #3:
http://wattsupwiththat.files.wordpress.com/2013/06/co2_temperature_historical.png

Latitude, CO2 in the polar seas is higher and pH lower, because the temperature is lower and therefore more CO2 is absorbed (and transported to the deep)…

Due to the ocean’s buffering capacity and the biological pump, as seen in the graph below, the upper ocean can experience upwelling that drives CO2 levels to 3 times higher than what would be expected from equilibrating with the atmosphere. Within a week, the concentration of CO2 and thus pH drops to levels that are 70% of what atmospheric equilibration would predict.
http://landscapesandcycles.net/image/98786989.png
Read Evans (2011) Seasonal cycle of surface ocean pCO2 on the Oregon shelf. JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 116

Latitude

The upper ocean can deal with 3 times the current CO2 in a matter of weeks……
It has to…..biological processes (acid) are magnitudes higher…and the carbonates are CO2

Jim, careful, pCO2 pressure is not the same as CO2 content… pCO2 is caused by the amount of free CO2, that is 1% of total inorganic carbon (CO2 + bicarbonate + carbonate) in seawater. If the pCO2 triples, free CO2 may have tripled, but the rest of the carbon may have changed just a few % to give a new equilibrium…

aGrimm

Very few have much of a clue regarding the oceans’ complex water chemistry – I don’t. However, we might be able to educate the public a little by comparing their water chemistry to a swimming pool, which may be more familiar to people. Of course a swimming pool is a closed system, but the idea and importance of buffering can be demonstrated in a properly balanced pool.
In a pool the main concern is to control the alkalinity. The ideal pH range in a pool is 7.4-7.8. (Note that the pH of the human tears is about 7.5, which is considerably more “acidic” (less alkaline) than the normal ocean alkalinity.) The chemicals added to a pool, for health reasons and prevention of algae, are typically quite acidic – in the pH of 3 range. This causes the water to become acidic and makes for uncomfortable swimming and a bunch of other problems, notably corrosion. To counter the acid, alkaline chemicals are added – typically in the forms of sodium carbonate (soda ash, pH = 11.4) and sodium bicarbonate (pH = 8.4). It takes a lot of the bicarb (pH = 8.4) to counter the low pH acids, so initially the bicarb is introduced in large quantities and this provides an alkaline base. The oceans have this same alkaline base in enormous quantities. In the pool, this alkaline base prevents large pH swings when the sanitizing acids are re-introduced/refreshed. The soda ash, with its high pH, is used in small quantities to make small adjustments to the alkalinity. If too much soda ash is used, the pH will rise to an uncomfortable level. In this case, an acid is introduced to lower the pH and what is funny is that CO2 gas is sometimes, not often, used to accomplish the desired drop in pH.
As a pool is used, there are over two hundred known chemical reactions occurring in it and quite likely twice that many unknown chemical reactions. These reactions constantly change the pool water chemistry, which requires constant oversight and testing. Lord knows how many chemical reactions are occurring in the oceans every second. The hubris of scientists, to think man is causing much to change ocean water chemistry, is astounding to me. When one considers all the effort we expend to control the water chemistry of a dinky water source like a pool, it is stupid to think we can influence and “control” the oceans’ water chemistry.

Barry

Oh yes, it’s so complicated that no one can know anything. Let’s just throw up our hands and keep polluting the planet. See previous comment explaining that it’s a rate constant problem, not an equilibrium one.

No one suggests we keep polluting the planet. That is a red herring. CO2 is not a pollutant but plant and plankton food.

ferd berple

Algae consume 500 billion tons of CO2 each year. The atmosphere holds 700 billion tons of CO2. We better hope something keeps eating the algae or we are in deep do-do.

Willis Eschenbach

Barry December 23, 2014 at 10:47 am Edit

Oh yes, it’s so complicated that no one can know anything.

Thanks, Barry, but I fear you have the problem backwards. It’s not that “no one can know anything”, nobody’s saying that but you.
The problem is that the natural world is indeed amazingly complicated, but despite that, people keep claiming that they know everything, and that “the science is settled”.
w.

Latitude

Barry, I’m sorry…you don’t have a clue
Henry’s law assumes there are no other chemical reactions getting in the way….
…The higher the buffer, the more CO2 it can hold
That fact says it’s not a “rate constant problem”

Pat Frank

Your PMEL link, says nothing about kinetics, Barry. It’s all about local equilibrium chemistry. Your kinetics argument is your own, and it’s merely an implicit proposition that not enough carbonate or oxide solids can dissolve fast enough to buffer surface waters to an invariant pH 8.1-8.2 as atmospheric CO2 increases. But you provide no evidence that this is important, and you show no evidence of understanding that the response of organisms is driven by metabolic energy, rather than chemical equilibration.
Your PMEL link gives a good example of this lack of understanding. It shows an empty pteropod shell dissolving over 45 days in water purportedly as it would be in the year 2100; presumably pH 7.9 bicarbonate (they don’t say). This shell is supposed to represent the fate of living pteropods. But an empty shell has no biological response.
Why didn’t they try the experiment with a living pteropod? Could it be because living pteropods can adapt to environmental pH? Especially interesting in that linked study, was that the researchers added HCl to make their pH adjustments, rather than bubble excess CO2 into the water. That means the pteropods did not have the benefit of higher pCO2 when they faced the challenge of lower pH. And yet, they were able to adapt anyway.
Pteropods produce a proteinaceous coat that covers the outside of their shell. It prevents direct contact between shell carbonate and sea water. Guess what that means as regards susceptibility to a small decrease in alkalinity. But, of course, the PMEL’s empty shell can’t maintain a protein coat, if it had one at all (they don’t say).
Here is a link to ocean acidification literature collected at CO2 Science. Go ahead and read through it. You’ll discover that the future is much more interesting than you expect. Biology is clever, adaptable, and has a large evolutionary bequest. Chemistry is only a small part of that, and equilibrium chemistry an even smaller part.
Calling CO2 “pollution” as you do is just language touted by green NGOs in order to channel your thinking. If you start out believing CO2 is a pollutant, you’re immediately susceptible to accepting specious proofs that it’s a pollutant.
So, what’s it going to be, Barry? Critical thought or normative moralization?

Latitude

Your PMEL link, says…………”In areas where most life now congregates in the ocean, the seawater is supersaturated with respect to calcium carbonate minerals.”
and if someone doesn’t understand the processes that led to supersaturation….they would believe it can run out

aGrimm

Barry: my comment above is an attempt to educate the non-chemists who visit this site as to the importance of a buffered system by using an example with which they might be familiar. There are those who are taking advantage of the populace’s lack of chemistry knowledge and only education will combat their nefarious purposes. Ocean chemistry IS very complicated and wonderfully we are slowly learning more each day. To my last CO2 laden breath I will support further research. However, the reality is that we know very little at this point and have a very long ways to go. Hubris: the tendency to think we are gods. We are not.
Willis & Pat Frank: spot on.

RH

”In areas where most life now congregates in the ocean, the seawater is supersaturated with respect to calcium carbonate minerals.”
Doesn’t a solution need to be cooled to become “supersaturated”? Just askin’

Latitude

Rh, no

Barry

OK, so I will spell this out:
“The natural pH of the ocean is determined by a need to balance the deposition and burial of CaCO3 on the sea floor against the influx of Ca2+ and CO2−3 into the ocean from dissolving rocks on land, called weathering. These processes stabilize the pH of the ocean, by a mechanism called CaCO3 compensation…The point of bringing it up again is to note that if the CO2 concentration of the atmosphere changes more slowly than this, as it always has throughout the Vostok record, the pH of the ocean will be relatively unaffected because CaCO3 compensation can keep up. The [present] fossil fuel acidification is much faster than natural changes, and so the acid spike will be more intense than the earth has seen in at least 800,000 years.”
More here:
http://en.wikipedia.org/wiki/Ocean_acidification

Pat Frank

It’s not “an acid spike,” Barry. If anything, it’s an alkalinity decline. The Wiki description is itself couched in specious language.
Second, the claim that it’s the largest descent in 800,000 years is based on the assumption that ice-core CO2 accurately follows atmospheric concentrations. But the record of fossil plant stomata refutes the ice-core record, at least over the last 13,000 years.
Further, the resolution of ice-cores is determined by the time of closure of the firn (solidification time of snow into ice). That time is typically 80-120 years. During closure of the firn, ice CO2 equilibrates with atmospheric CO2, and the record smears out. That means no one knows from the ice-core record whether CO2 spiked up for several decades, or not. From the stomata record, it may have done. Notice that the stomata record is invariably higher than the ice core record, where both sets of data exist.
Your worries are misplaced, Barry. You’re not thinking critically.

Pat Frank,
Second, the claim that it’s the largest descent in 800,000 years is based on the assumption that ice-core CO2 accurately follows atmospheric concentrations.
Ice core CO2 accurately follows the CO2 in the atmosphere, be it averaged over 10 to 600 years, depending of the snow accumulation. 10 years of resolution is over the past 150 years, ~20 years over the past 1,000 years, 40 years over the past 10,000 years and 560 years over the past 800,000 years.
The current 110 ppmv spike in CO2 over the past 160 years would be detected in all ice cores, including the least resolution cores as the repeatability of CO2 measurements in ice cores is 1.2 ppmv (1 sigma), thus a spike of 100 ppmv, sustained over 10 years, would be noticed in the Dome C 800 kyear record. Or a sustained change of 2 ppmv over 560 years.
In contrast, stomata (index) data are proxies, with all the problems involved. They show the local CO2 variability of where the plants grow, where CO2 levels are changing with the CO2 uptake/release in the main wind direction. That includes huge land use changes over the centuries even changes in the main wind direction in certain periods (MWP-LIA-current).
The local bias in CO2 levels can be compensated for by calibrating the stomata data to direct measurements, firn and… ice cores over the past century. But there is no knowledge how the local bias changed over the centuries… Thus while the stomata data give a good idea of the local CO2 variability, their absolute CO2 levels should be taken with a lot of salt.
Anyway, even if there is some migration (not even measurable) in ice cores, that doesn’t change the average of the CO2 levels over the period of resolution. If the stomata data show a different CO2 level over the same period, the stomata data are certainly wrong…

Pat Frank

Ferdinand, the average firn closure time at Law Dome, Antarctica, is about 50 years. See Etheridge, et al., (1996) JGR 101, 4115-4128. Law Dome was chosen for its almost ideal characteristics. The exchange time before closing is about 10 years at depth, so that the averaging with atmospheric gases is reasonably complete over the firn closure time.
Even at Law Dome, then, “accurately” following atmospheric CO2, as you have it, does not mean accurately reproducing the absolute values of CO2. ‘Accurately following’ means no more than statistically correlated. The 110 ppmv increase in CO2 since 1850 that you mention would show up in well-behaved annually resolved ice cores, but not as a 110 ppmv rise. The apparent maximum would be reduced and the trend would be flattened.
It is true that stomata are proxies for CO2. But their population is strongly determined by ambient CO2 levels. While there are other determinants stomata are only weakly affected (pdf) by water stress or typical variations of irradiance, and so they do not suffer “all the problems” of such proxies as tree rings, corals, or spleothems.
Local winds that might change ambient CO2 levels on a daily basis will not affect stomata number, which cannot vary day-to-day, but will effect the diffusion of CO2 through a firn layer. So, the wind variable you mention will more affect ice core CO2 than it will stomata count.
The idea, in any case, that CO2 is globally well-mixed seems to have become suspect. It now seems possible that Antarctic and Arctic ice cores may under-reflect the global average atmospheric CO2, apart from the averaging effect of the firn.
Recent use of fossil stomatal index has shown large swings in CO2 concentrations during the Miocene. Your dismissal of stomata is too casual, Ferdinand. In my view, where stomatal index indicates a disparately higher level of CO2 than the contemporaneous ice core data, it’s more likely the ice core is wrong, shown here, for example in a comparison for the 13th century.

Pat Frank,
Have you read the full work of Etheridge e.a. of 1996, he explicitly refutes several of your objections. There is no influence of wind on the CO2 levels in the firn near the atmosphere: they are exactly the same as above the surface. The Law Dome ice cores have an overlap of ~20 years with the atmosphere and reflect the atmospheric CO2 levels within +/- 1.2 ppmv for the same average gas age:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/law_dome_sp_co2.jpg
The averaging makes that the ice core record lags the changes in the atmosphere and that fast peaks are suppressed, but for the Law Dome ice cores, any peak of 20 ppmv happening over only one year should be just detected or a 10-year sustained 2 ppmv increase…
The 110 ppmv increase in CO2 since 1850 that you mention would show up in well-behaved annually resolved ice cores, but not as a 110 ppmv rise.
Depends of the resolution of the ice core and the length of the maximum. If the rise has a maximum longer than the resolution, the full ppmv rise will be detectable, as is the case for the -relative- slow increases and decreases of CO2 over the past 800,000 years. But for the current rise, where the end is not in sight, the ice cores only follow the increase with a lag which depends of the resolution.
It is true that stomata are proxies for CO2. But their population is strongly determined by ambient CO2 levels.
The problems are mainly in the ambient CO2 levels. Not the daily wind variations, but the level of CO2 over months, years and centuries imported by the prevailing winds. The tall tower in Cabauw, Netherlands can detect that corn is grown in the main (SW) wind direction…
One of the best stomata data in The Netherland is a thousands of years natural oak forest in the SE. In the main wind directions: SW to NW (of today!) sea was converted to land and agriculture, heather fields to forests and since 1.5 century industrialization, increased population and transport… The local offset (~40 ppmv in Giessen, SW Germany) can be calibrated away by comparing the stomata data to direct measurements and ice cores in the previous century, but nobody knows the influence of land use changes in the main wind directions and of changes in the main wind directions themselves (MWP-LIA) in the course of the centuries.
That makes that while stomata data have a better resolution than ice cores, their variability is mainly local and their averaged CO2 levels, if they differ from the ice core data over the resolution period of the ice core, are certainly wrong. Averaging does remove peaks, but doesn’t change the average over the resolution period… See:
http://www.sciencemag.org/content/286/5446/1815.full

Pat Frank, I have looked deeper into the stomata data as proxy.
First the error estimate of stomata data even over the previous two centuries is large (+/- 67 ppmv!):
http://hol.sagepub.com/content/19/5/757.abstract
Then the problem of huge CO2 changes in short time over the past:
from http://www.sciencemag.org/content/286/5446/1815.full
the trend can be enlarged:
http://www.sciencemag.org/content/286/5446/1815/F1.expansion.html
The resolution of the Taylor Dome ice core over the Holocene is ~40 years. At 11,300 years BP (1950), the stomata data and ice core data are equal. During the period 11,250-10,600 years BP, stomata data are average 330 ppmv, ice core data at 265 ppmv. A difference of 65 ppmv sustained over 650 years (borderline the above accuracy of stomata data). The change is long enough to be fully visible in every Antarctic ice core drilled until now. But is not measured in any ice core…
The difference in CO2 levels between all ice cores drilled in Antarctica with the most extreme differences in snow accumulation and temperature is not more than 5 ppmv for the same average gas age…
Thus sorry, while stomata data give a rough idea of (local!) variability and CO2 levels, their use for absolute CO2 levels in the bulk of the atmosphere is very limited and they certainly don’t refute the ice core data for average CO2 level over the period of resolution of the ice cores…

Pat Frank

Ferdinand, regrets for the delayed response — holiday distractions and all that. . . 🙂
I have read Etheridge 1996, and understand your point about Figure 3. However, I believe you have overlooked that the points represent the very top of the compacted ice region, where correspondence to atmospheric composition is bound to be greatest.
As a smaller point, though, Etheridge, et al., corrected their empirical CO2 measurements for gravitational diffusion. They used their empirical 15-N measurement to estimate the gravitational diffusion rate, rather than the value from the barometric equation. Reliance on the empirical value automatically corrects the 15-N for any convective mixing due to wind shear.
This means their CO2 measurements were empirically corrected both for gravitational diffusion and for convection in the firn. So, it’s not too surprising that their corrected firn and upper ice CO2 values were so close to the atmospheric measurements.
Convective mixing due to wind shear does happen in firn, see here, where this is mentioned. According to J. Turner, et al., (2001) JGR 106, 7291-7311, strong high-wind storms were recorded near Law Dome about 10 times per year between 1969-1996.
Convective mixing due to wind mixes the atmospheric gas between 2-10 meters into the firn, amounting to 2-20 years of averaging, depending on snow accumulation rates.
However, the issue about accuracy concerns the extended record, not just the most immediate compaction zone.
The major problem affecting correspondence with contemporaneous gas mixing ratios is the diffusion of gas vertically through the ice over time. Gas dissolved in ice is in equilibrium with gas in bubbles above about 500 m, and with gas in the clathrates that appear below that level.
The empirical diffusion coefficients for N2, O2, and CO2 in ice cores was reported by Bereiter, et al. (2009) GRL 36 L05703. At 220 K, a typical deep core temperature, the diffusion coefficient for CO2 is 3.1×10^-11 m^2/sec. From this, one can estimate that CO2 can diffuse at the rate of 0.076 cm per year through the ice, in each direction. Of course, only vertical diffusion, (+/-)z, is important for coherence of ice core layers.
Equilibration with bubbles and clathrates means net migration of CO2 in ice across concentration gradients. This exchange would continue until a new equilibrium is attained across the diffusion zone.
That diffusion rate means ice-core CO2 in a given layer can migrate 76 cm per 1000 years. If we assume 1 cm per year of ice, 1000 years produces approximately a 152-year average. Over a few thousand years, the bulk ice CO2 may migrate across more than a meter. The result is to smear out excursions, as ice core CO2 slowly equilibrates to produce a mean of CO2 averaged over centuries, and then millennia.
If atmospheric CO2 were varying across 250(+/-)50 ppmv over several thousand years, it would seem this variation may be quite smoothed out by diffusion, and any short-term spike would be greatly attenuated. Mostly one would see an artifactual average that would make [CO2]atm seem quite constant over intermediate-length times, apart from large ice-age shifts.
In fact, one sees this effect in Lüthi, et al, (2010), EPSL 297, 226-233. They report larger variations in measured CO2 with per-cm vertical distance in younger ice earlier in an ice core clathrate zone, and smaller variations in older ice at deeper core, consistent with increasing homogeneity with time. They ascribe this aging effect to diffusion within the ice.
Likewise, B. Stauffer, et al. (2003) (pdf) (Mem. Natl Inst. Polar Res., Spec. Issue, 57, 139–152) reported multiple CO2 measurements every ~1-cm in two Antarctic ice cores (Khonen Station and Concordia Dome). The scatter among measurements decreased with the age of the ice; (+/-)3.8 ppmv at 147.4 m (930 year ice), (+/-)2.8 ppmv at 219 m (4270 year ice) and (+/-)2 ppmv at 521.7 m (16500 year ice). This trend was apparently surprising to them. Most likely these show the smoothing out of concentration differences in ice CO2 because of diffusion.
Lüthi, et al, (2010) proposed that after long times, the mean atmospheric CO2 concentration is regained, but only if one samples >10 cm of ice. This seems to be putting a favorable light on the problem.
All of this implies that the early Law Dome results of Etheridge are uncharacteristic of CO2 behavior over long times in ice cores, and should not be relied upon to indicate long term accuracy. Also, that after ~10 thousand years, ice core CO2 will no longer show perhaps even century-scale variations, but can t best only represent a long-term mean atmospheric concentration.

Pat Frank

Ferdinand, I’ve looked at the stomata references you cited. First, Finsinger, et al., 2009 compared the stomata of plants grown in herbariums in Denmark, with the ice core CO2 index of Mauna Loa and Law Dome. That is very localized sets of plants are compared with global averages. This is a bit of apples and oranges.
It is significant that the stomatal reconstructions matched the modern Mauna Loa direct measurements but departed from the century-old Law Dome reconstructions.
As the (+/-)68 ppmv error you quoted was derived by the assumption that the Law Dome reconstructions were completely accurate representations of atmospheric CO2, one cannot use this disparity to discredit the stomata reconstruction relative to the Law Dome reconstruction. I.e., such a critical analysis is circular.
A better indication of intrinsic error in stomatal reconstructions is the (+/-)18 ppmv Finsinger, et al., give for the training period, where modern stomatal density or stomatal index is regressed against modern CO2 measurements. Likewise, Stults, et al., 2011 found a stomatal density error of (+/-)22 ppmv.
Your Science references, both of them to Indermühle, et al., 1999 merely dismisses the stomatal index CO2 reconstruction by Wagner, et al., because it disagrees from the Law Dome reconstruction. Such a dismissal is tendentious and is not a legitimate disproof of the stomatal reconstruction.
Perhaps you didn’t notice, but below Indermühle, et al., 1999, on the same page in Science, was a written rebuttal by Wagner, et al., that points out that Indermühle, et al., rested their critique on stomata measurements from “altitudinally and latitudinally contrasting growth areas,” and on stomatal density measurements rather than the more reliable normalized stomatal index.
Notice also the ice core reconstructions of Indermühle, et al., concern the Holocene centered around 11000 years BP. We know from the diffusion rate of CO2 in ice, which I noted above, that smearing is possible across (+/-)8.4 meters of core, which approximately averages 840 years of CO2 deposition.
In general, the gas inside ice core bubbles is in equilibrium with the gas dissolved in the ice. The gas dissolved in the ice diffuses about 1 mm/yr along (+/-)z. So, after every 1000 years, the ice core resolution of CO2 flux is reduced by about (+/-)100 years because of averaging.
I also looked at the four references Indermühle, et al. gave for what they call, “direct measurements on air that has been enclosed in bubbles” (Refs. 3,4,7,8). In fact, they did not measure CO2 directly in gas samples taken from inside bubbles (quite possible with modern analytical methods), but rather CO2 released from bubbly ice using a dry cold needle ice crusher. Needle crushers reduce ice core samples to mm-size bits. The gases released from the core are therefore from broken bubbles and from the ice itself, not from the interior of the bubbles alone.
Finally, in stomatal reconstructions, among other variables, one must be careful to choose plants that are known to respond well to changing [CO2]atm. D. L. Royer’s 2001 review of stomata as an indicator of atmospheric CO2 discusses this in detail, with long appendixes listing the traits of various candidate species. Some of the variability of stomatal results may be due to using poorly sensitive plant species. I haven’t looked into that aspect.
However, from all this, I remain of the conclusion that stomatal reconstructions provide a better record of paleo-excursions in atmospheric CO2 than do ice core records, including back in the Holocene, and that ice core CO2 declines in resolution with greater age.

Pat Frank

It turns out, at Law Dome, the average core length per year is ~40 cm. So, my estimate of CO2 averaging by diffusion needs to be revised.
Taking 40 cm per year of core ice as typical, two years of trapped CO2 are averaged every 400 years with a standard CO2 diffusion rate of 1 mm per year. That means the resolution per ice-core year-point is 50 years of atmospheric CO2 averaged after 10,000 years, 500 years averaged after 100,000 years, and 1000 years averaged after 400,000 years — the time-length of the Vostok core.
So, for the mid-Holocene, 5000 years before the present, each ice-core year will represent a 25-year running average of atmospheric CO2. That’s from diffusion-averaging alone.

Pat Frank

From the orginal publication of Petit, et al., 1999, it seems the Vostok glacial ice core record consists of 420,000 years recorded in 3350 meters of ice. That averages 1 year per 0.8 cm of ice.
Assuming diffusion is the rate limiting step in CO2 migration, the 1 mm per year rate implies a 2-year averaging every 8 years. So, the estimates above for 1 cm progressive loss of resolution of atmospheric CO2 are relevant to the Vostok core.
The Concordia Dome ice core turns out to average about 0.43 cm of ice per year, so the loss of resolution of atmospheric CO2 by diffusion averaging is about twice the rate of Vostok.

Peter Miller

Is there anything left in the climate alarmist armoury of scary stories/pseudo-science that has not now been totally debunked?
I found this post very disquieting as it is yet another major abuse of the scientific method by those who we should be able to trust in the ‘climate science’ fraternity.

I find this more than disquieting – and I think we all need to sign the petition – how can we allow the data record to be censored? or tolerate cherry picked model output presented to Congress?

Bob

Look at Feely’s CV. Nobel Peace Prize (co-shared with Al Gore and other members of IPCC) – 2007. Yet another one.

It’s a license to kill science.

Don B

Another Hide The Decline, this time about ocean acidification.

Neo

So, the general rule now is that when scientists start making threats, you just know there is something being hidden.

Dawtgtomis

The general rules are found in the Baloney Detector. Alarmists have trouble validating most of their assumptions when those rules are enforced.

steverichards1984

PhGate?

AcidGate?

William Astley

In private industry hiding data that disproves a hypothesis would be grounds for firing.
There is case after case where there is strong evidence that a cabal of climate change ‘scientists’ are working to push an agenda, rather than to solve scientific problems.
http://link.springer.com/article/10.1007%2Fs11191-013-9647-9
Climate Consensus and ‘Misinformation’: A Rejoinder to Agnotology, Scientific Consensus, and the Teaching and Learning of Climate Change

jorgekafkazar

As soon as I saw the blue squiggle, I knew models were involved.

Scarface

I never understood how they could sell the idea that oceans, that are supposed to be warming, would absorp CO2, which they don’t. Warming oceans release CO2, cooling oceans absorp CO2.
Manmade acidification is a h-o-a-x, as we now know for sure. It’s based on a Phraud.
I can’t wait to see these climate clowns doing a lot of time for their crimes.

The warming increases the pCO2 of the oceans with not more than ~8 μatm/K that is about 6 ppmv since the LIA. The increase is currently ~110 μatm (~ppmv) above equilibrium for the current average ocean surface temperature. Per Henry’s law the ocean surface is a net sink for atmospheric CO2…

highflight56433

…and during glaciation as the poles ice extends over more ocean area, resulting in a decrease in cold water to absorb atmospheric CO2. Probably explains the yo-yo of CO2 following the glaciation periods. Everyone knows that. 🙂

I don’t quite understand. Warming increases the pCO2 of the oceans? Could you please explain this?
And correct me if I’m wrong about warming/release and cooling/absorp?

highflight56433, the sink rate is higher in winter than in summer, as the ocean sinks are at the edge of the freezing ice. Ice formation expels most of its salts and makes the also cold waters heavier than the deep ocean waters. In summer when the ice melts there is less sink capacity…

cosmicclimate, it is as follows: warmer (ocean) water builds up CO2 pressure to escape from the solution. If the pCO2 (partial pressure of CO2) of the ocean is lower than the pCO2 from the atmosphere (~ppmv), then the direction is into the oceans, no matter its temperature. The reverse pressure difference gives a flux from the oceans into the atmosphere. If both pressures are the same, nothing happens, whatever the temperature of the oceans or atmosphere.
The pCO2 in the atmosphere is given by its volumetric CO2 content (ppmv) minus water vapor which is maximum a few % near sea level. pCO2 in water is a mix of temperature, pH, bio life and total carbon (DIC) content… In general measured by mixing seawater with air till equilibrium and measuring the CO2 level in the air.

Scarface

Thank you. It gets more and more complex, the more you learn and try to understand.