Some people claim, that there's a human to blame …

Re Ferdinand Engelbeen, 7/1/10 at 8:08 am & 7/2/10 at 4:53:
Your new explanation doesn’t help. I don’t understand what you mean equating sums to averages. What we’re discussing here are all time averages over the same interval of time, are they not? IPCC says the data are monthly averages (of what, mol/m/sec?), but the numbers are in mol/m^2/yr. AR4, Figure 7.8, p. 523. You seem to have a rationale that supports both the Takahashi diagram and the +90/-92 GtC/yr total ocean fluxes. This might be understandable on examination of the data. Can you provide a link to the data that supports the total ocean fluxes of 90 and 92?
The link to … fig03.jpg is no help. It’s a washed out version of one figure from the link I gave you on 6/28 at 8:56, … air_sea_flux_1995.html. If any reader is interested in more information, my link is included in a more comprehensive link at http://www.ldeo.columbia.edu/res/pi/CO2/carbondioxide/pages/air_sea_flux_2000.html
You provide a link to … ZeebeWolfEnclp07.pdf. You again repeat the identical link I provided to you on 6/27/10 at 7:56. I don’t think you are following this dialog at all, repeating references and putting words in my mouth.
You refer me to Figure 1 for the Bjerrum plot “that I don’t like”. You put words in my mouth (YPWIMM). Bjerrum has been discussed extensively here, but I said nothing to indicate that I don’t like it. IPCC relied on it but failed to cite it. When you and others who have been fooled by IPCC apply the Bjerrum plot, you fail to apply the applicable constraints.
Every scientific hypothesis, theory or law has a domain of validity. You misapply Bjerrum. It requires thermodynamic equilibrium. IPCC says only equilibrium. You incorrectly call for dynamic equilibrium, putting words in the mouths of IPCC and Zeebe & Wolf-Gladrow, too. You even use dynamic equilibrium incorrectly where it might have applied. You admitted this was true when on 6/26/10 you wrote,
>>Climate never is in dynamic equilibrium… .
The Bjerrum solution to the stoichiometric chemical equations for CO2 show that adding CO2 would increase acidity, and by derivation, that the ocean would create a bottleneck to absorbing CO2 (IPCC and Revelle limit this to ACO2, which is compounding the nonsense). Those effects are true only in transitions between thermodynamic equilibrium states, which exist nowhere on Earth.
Your references to the Wattenberg measurements and Meteor cruises were useless. Regrettably, I don’t read German. They appear to be irrelevant, if for no other reason than the fact that IPCC did not rely on them.
You wrote,
>>The definition pCO2 as described here has nothing to do with a novel model of Henry’s Law, it is based on Henry’s Law.
I didn’t say what you protest. YPWIMM. Further, you are wrong that the definition of pCO2 is based on Henry’s Law.
You asked,
>>Do you agree that if the pCO2 of seawater, as defined here, is higher than the real atmospheric pCO2 above it, that the seawater will release CO2 and reverse?

Set this up as an isothermal experiment, constant salinity, constant isotopic mix of CO2, and the answer is yes. That is Henry’s Law, extended beyond thermodynamic equilibrium by experimental Henry’s constants.
You say incorrectly,
>>The water in the cell absorbs instantaneously for the skin of the surface, not the whole 100-200 m depth of the cell.
If this were true, a can of pop would go stale instantaneously. If this were true, the wind speed would have no effect, contradicting the science behind Takahashi’s model. Dissolution is a mechanical and statistical process, so the process is not instantaneous. It continues until the probability of a molecule entering the water is the same as the probability of one leaving it.
A superior model to yours is that the surface layer entrains air in bubbles, in an amount and to a depth that increases with increasing wind. The effective skin depth for dissolution is the total area of the ragged interface plus the surface of all the bubbles.
The skin model works as the water approaches a stagnant pond.
You say,
>>That is where dpCO2, wind speed and diffusion speed (which is very low) are involved. The uptake/release rate for a given wind speed and dpCO2 needs about one year to get in full equilibrium for the full depth, thus in the mid-latitudes is never reached as the seasons change the same cells from emitters to absorbers and reverse within a year.
Diffusion speed has nothing to do with dissolution, assuming you mean vertical diffusion within the ocean. It would, of course, if we were considering transitions between states of thermodynamic equilibrium. But the surface layer is churning, and is in disequilibrium. It never achieves “full equilibrium”, especially in recognition of the fact that partial equilibrium is not defined. The surface layer absorbs as much CO2 as necessary to satisfy Henry’s Law for the appropriate Henry’s constant at the local temperature.
The conditions in the layer do not satisfy the Bjerrum plot. The surface layer supports dissociation of CO2(aq) into its various ions, and those support the biological pumps, fed by contact and diffusion, at their respective speeds and independent of the air-surface flux.
The surface layer takes about a year to get fully charged with CO2, because that is approximately the amount of time it takes to cool to ice water. It is the time it takes to travel from the tropics to the poles.
You say,
>>- Henry’s Law works bidirectional.
It’s bidirectional in the sense that one may either load or unload a 10-ton truck. Henry’s Law provides the carrying capacity. It’s in gms CO2/100 gms H2O, not grams per unit time.
>> – … which by Henry’s Law is directly proportional to [CO2] in the seawater of interest.
Henry’s Law does not depend on the concentration of CO2 in the water. It depends on the temperature and salinity of the seawater, and no other characteristic of any known significance of the solvent.
>>- besides temperature and salinity, pH and DIC play a huge role in the changes of free CO2 (denoted as [CO2]) in seawater.

(a) you’ve got it quite backwards, and (b) the reverse relationship only applies under thermodynamic equilibrium, which doesn’t exist.
>>- the consequence is that an increase of 100% in atmospheric pCO2 results in a 100% increase of oceanic pCO2, when in dynamic equilibrium, but only 10% increase of total CO2 in seawater, due to the change in pH as result of increased CO2.

Dynamic equilibrium is your personal invention, not physics. The second part would be true passing between states of thermodynamic equilibrium, where the stoichiometric equilibrium constants apply.
>>- the 90/92 GtC as described in the literature (and adopted by the IPCC) is the sum of all monthly CO2 fluxes out of all cells separately the sum of all monthly CO2 fluxes into all cells, not the sum of yearly averages of the +/- cells, with or without a factor.

Incomprehensible. Please demonstrate with data or even algebra.
>>- the deep ocean – atmospheric CO2 exchanges are far less than the 90/92 GtC, as most exchanges are within a year in cells of the mid-latitudes which are emitters in summer and absorbers in winter.

(a) Incomprehensible and (b) the deep ocean does not react with the atmosphere, if that is what you mean. Similarly and equally wrong, IPCC shows the intermediate and deep ocean layers exchanging CO2(g) with the atmosphere (AR4, Figure 7.10, p. 530), and support it with the CO2 Response Function, an equation, (AR4, Table 2.14, p. 213, fn. a).
>>The residuals can be seen in Fig. 2 … .
No, they can’t. Residuals are the instantaneous differences between two functions of time, data points and smoothed, fitted curves, each in ppm. The residuals then are also functions of time and in units of ppm. Figure 2 is in dimensionless slopes of residuals in ppm/ppm for CO2, and in meg/meg for O2/N2.
>>If you call a variability of less than 2% of the absolute value “not well-mixed”, including seasonal variability and NH-SH gradients, what in heaven (or earth) is then well-mixed?
I said no such thing. YPWIMM. IPCC used the term well-mixed, and that is for their purpose of claiming MLO data is global, when it is local. That it does to match the rise in CO2 to the rise in temperature, to frighten the gullible, to dislodge public funds, and to receive academic fame and recognition.
IPCC uses the assumption of well-mixed to calibrate all CO2 stations so that the various CO2 concentration record overlap. That is what you see as less than 2% variability. This is done in part by its application of a “linear gain factor” to CO2 readings at stations other than MLO. When you use the calibrated result to prove the assumption, you have lifted yourself by your own bootstraps.
IPCC’s CO2 records are well-calibrated. Its linear gain factors used for the calibration are secret. The burden is on IPCC and you to define well-mixed, and then to demonstrate its existence. Otherwise, you may not rely on the assumption and call the result science.
Homogenized milk is probably well-mixed under the most exacting definition.

Jeff Glassman says:
July 3, 2010 at 10:26 pm
So a first puzzler is how did Takahashi, et al. manage to measure ACO2 flux, and reject nCO2 flux?
Takahashi measured tCO2 fluxes, the 90/92 GtC from the IPCC being total fluxes and the difference is the net sink rate in the oceans. The 90/92 GtC is responsible for the residence time and only of interest for total exchanges between the atmosphere and oceans (including the fate of 14C from the atomic bomb testing). The net sink rate of around 2 GtC is of more interest as that is what the decay rate influences for any extra added CO2 (whatever the origin).
The emissions are known with reasonable accuracy, the increase in the atmosphere with quite good accuracy, the difference is what is absorbed by other reservoirs. The partitioning between oceans and vegetation as sinks can be calculated from d13C changes and oxygen use. See:
http://www.bowdoin.edu/~mbattle/papers_posters_and_talks/BenderGBC2005.pdf
That gives an alternative calculation of the ocean’s sink rate, still with wide margins of error.
———-
Wrong. IPCC’s equations 7.1 and 7.2, conveniently abbreviated by Phil, above, on 6/29/10, are stoichiometric equations. They are found online in Zeebe & Wolf Gladrow, “CO2 in Seawater: Equilibrium, Kinetics, Isotopes”, 24/06/2006, Chart 3, but including four stoichiometric equilibrium constants for the reactions. The solution to the stoichiometric equations is the Bjerrum plot, id., Chart 5.
Wrong again. As clearly indicated in Zeebe & Wolf-Gladrow, the equilibrium reaction is simply mass equilibrium for any amount of mass of the items in the equations. The reactions go both ways, whatever the concentrations or change in concentrations involved, and the results are dictated by the equilibrition constants k1 and k2. It is the equilibrium constants which are deduced from stoichiometric conditions, not the basic equilibrium reaction.
The equilibrium constants change with temperature, pressure and salt content. More with temperature than I expected, thus one need to take into account the influence of these parameters when calculating the results. Wattenberg in the 1920’s cruises did correct his findings for temperature, salt content and pressure…
As most of the reactions are very fast (less than 1 second), the reaction on any change in mass of one of the reactants (including pH) or circumstances (temperature, pressure) is almost instantly. Thus thermal equilibrium or not, for any instance or change of temperature, the results can be calculated.
———–
Wrong. CO2 is not known not to be well-mixed for a variety of reasons. One of them is the falsification of the records by IPCC to make MLO overlay both SPO and Baring Head. Another is the heavily smoothed nature of these curves. These results to not occur in nature. Another is the fact that SPO sits in a CO2 sink, while MLO sits in the plume of massive oceanic outgassing, and the records should not look alike.
I have sent the graphs of the raw, unaltered (hourly averaged) data + the smoothed curve of MLO together with these from the South Pole. These show clear differences in seasonal trend and a few ppmv difference over a year. The yearly average and trend of the smoothed data and of the raw data and independent flask data for each station are almost identical. MLO is in a “huge” plume out of the oceans, but shows less seasonal variation and similar vlaues than other NH stations. South Pole is in an ice desert, far away from the southern ocean sink and at 3,000 meter receives mainly air (and precipitation) from the whole SH oceans, up to the equator.
And have a look at the color scale of the AIRS satellite: 365-380 ppmv, or +/- 2% of the full scale for one month, where a lot of the differences can be seen. Over a year that is even less. Above Mauna Loa, the “plume” is even lower in CO2 content than at the NH mid-latitudes (flask measurements at sea level in Hawai and Mauna Loa show near identical values, while MLO is already mixed in the trade winds) and the South Pole is higher in CO2 content than most of the Southern Ocean.
Your allegations are simply without any ground.

Re Phil, 7/3/10 at 2:41 pm:
First, I owe you an apology. I copy the posts into a word processor for highlighting, color coding, and footnoting to build a response. When I copied your post of 6/29/10, I lost the first two offsetting quotes and the italics. That’s why I found your marks on just the second paragraph to be strange. Anyway, you were correctly quoting me, and I apologize for criticizing you on that point.
Now it’s your turn back in the barrel, and for some wire brushing, to mix the metaphors.
You said of that same quote,
>>… I believe you used the “>>” to indicate they were quotes by Ferdinand, where he got them from I have no idea.
Believe as you wish and conjecture as you might, but I was quoting Wikipedia as I said immediately above the quotation.
You don’t know what ad hominem means. When I criticize your writing as being illogical, disconnected, and outright false, those are not ad hominems. An ad hominem is an attack on the person, not his argument. When you call me an obnoxious jerk without facts or definitions, that is an ad hominem.
When I wrote that “No theory exists to guide us in disequilibrium”, you responded
>>Rubbish, Le Chatelier’s principle and reaction kinetics do just fine.”
That is false. Le Chatelier’s principle is only a guide that an isolated system disturbed from an equilibrium state will move toward an equilibrium state. It tells us nothing about the path that might be taken, or what happens to a system that is not isolated. You provide evidence that you don’t understand what you think you know, that you are willing to misrepresent what you know to score a point in argument, or that you are a careless writer. That is an offensive insertion into the dialog.
Then you add in your latest post (op. cit.),
>>Which of course they do, they allow us to describe the transition to the equilibrium state following a perturbation, which you appear to be unaware of. Le Chatelier’s principle describes the way the equilibrium will shift given a change to a system in equilibrium. For example changing the pressure of a system of reacting gases, e.g. N2,H2 & NH3. The rate of that change is described by chemical kinetics.
Le Chatelier’s principle describes no “way”, that is, no path, no direction, no trajectory. You are correct now that the LCP applies to systems in equilibrium, before and after the disturbance or change. Your previous “rubbish” crack you supported by urging that the LCP was a model for the state of systems while in disequilibrium.
Your reference to chemical kinetics might be true, but you provide no evidence of that fact. You just name drop “chemical kinetics” as if that was enough. The reader is supposed to take what you say as evidence because Phil has a PhD topic, another naked claim gratuitously inserted.
You say,
>>Those aren’t stoichiometric equations they are chemical equilibria (which are also a thermodynamic equilibria).
Your sentence is wrong on one point and ambiguous on another. Stoichiometric equations apply in thermodynamic equilibrium, which implies chemical equilibrium. Your sentence can be read to say because the equations require chemical equilibrium, that implies thermodynamic equilibrium, which is false.
But to say they are stoichiometric equations in the first place is wrong, which is more evidence that you don’t know what you think you know. As I had to explain to Engelbeen, they certainly are stoichiometric equations. Here’s a compact quote from a professor’s online notes that might help you:
>>Stoichiometry describes the proportions in which chemical species combine.
>>CH4 + 2O2 –> CO2 + 2H2O
>>is a stoichiometric equation for the combustion of methane … . All stoichiometric equations can be represented generically as:
>>aA+bB –> cC+dD
>>The numbers which quantify the amounts (a,b,c,d, nu) are called stoichiometric coefficients.
http://www.cbu.edu/~rprice/lectures/reactive.html
Does that help? Do you see now that the equations you wrote on 6/29/10 at 9:18 pm are by definition stoichiometric equations? If you need help applying this lesson to the carbonate system, you might want to read the Zeebe and Wolf-Gladrow paper I cited above. They refer to the coefficients as “stoichiometric equilibrium constant[s]”. In their entry in the Encyclopedia of Paleoclimatology, etc., above, they also specify that thermodynamic equilibrium is required.
You criticize my explanation to you about solubility as “irrelevant crap and bad analogy”. Here’s what you had to say:
>>Strictly Henry’s Law doesn’t apply to CO2 in water because CO2 reacts with water but it’s a good approximation.
while you say
>> … without taking the chemical equilibria into account Henry’s Law is useless for seawater.
Phil concludes,
>>The ‘Revelle buffer nonsense’ as you call [it] is necessary to account for the chemical composition of seawater, because the simple application of Henry’s Law is not appropriate when there is a chemical reaction between the gas and the solvent.
Therefore, Phil’s conclusion is that Henry’s Law, though a “good approximation”, is never appropriate because CO2(aq) always undergoes chemical reactions in the solvent. Utterly flummoxed and outwitted, he dismisses all explanations of his errors as “crap”.
For the sake of other readers, Phil has unwittingly contradicted himself. We know that CO2 is highly soluble in water, including seawater. The water need not be in equilibrium, and it is still highly soluble. However, Henry’s constants are only known with any precision for equilibrium. As Phil first implied, those constants are a good approximation at one atmosphere and for sea surface temperatures. We know they are good approximations, not because Phil is a PhD candidate, but because when we calculate the CO2 uptake and outgassing for the conveyor belt (aka THC, MOC), using those constants, reasonable temperatures, and reasonable estimates for the flow rate in the THC, the whole system hangs together.
At the same time, the stoichiometric equations are valid, too, in disequilibrium, and the relative ratios of reactants, the stoichiometric constants are, like Henry’s constants, only defined and known under thermodynamic equilibrium. So to say the stoichiometric equations are valid is a tautology. For the carbonate system, they express chemical reactions involving all the possible components of CO2 in molecular or other forms. However, in disequilibrium, the chemical equations are not in balance, and we have nothing to suggest what the appropriate ratios are.
One thing that is known, however, is that Henry’s Law is a “good approximation”, and that it does not depend on the pH of the water, or on its stoichiometric state of imbalance, at least down to the fourth order of significance. The science is down to its limits under the state of the art for measuring the flux of CO2 across the air-sea interface using the known parameters of the pCO2 in the air and the temperature of the water, and we might throw in salinity.
IPCC, however, has a model for the air-sea flux that makes it a bottleneck for ACO2 at about 6 GtC/yr, but not at all for nCO2 at 90 to 110 GtC/yr. The difference is political: IPCC reads its charter from WMO and the UN as charging it with finding data to demonstrate its assumption that ACO2 causes global warming – overt selecting data to fit the theory!
But the estimated emissions from fossil fuel are not large enough. So IPCC adopted the Revelle & Suess’s failed 1957 conjecture of a buffer, one that would cause only ACO2 to accumulate in the atmosphere. Within a year or so after Revelle published his grant request, now elevated in the community to a paper, Bert Bolin took up the conjecture and elaborated on it. Bolin carried that conjecture with him when he became the first Chairman of IPCC upon its founding in 1988. Since that time, IPCC has elaborated on the Revelle buffer but never validated it.
The Revelle buffer is invalid. It violates Henry’s law, and not just under the idealized state of thermodynamic equilibrium, but in the empirical world of it being a “good approximation”. Because the only known difference between ACO2 and nCO2 is the isotopic mix ratio, the Revelle buffer requires the ocean to fractionate, to discriminate between different molecular weights of the components of 12CO2, 13CO2, and 14CO2. That effect may well exist, but it is far below the state of the art in measuring. The conjecture requires different Henry’s constants for the different isotopes. Even at that, the ocean would fractionate to change the mix of CO2 in the atmosphere, an example of the Suess effect, and not just absorb the two species, ACO2 and nCO2, intact.
The Revelle buffer is a relationship between measurable components in the ocean. As a result, it always has a numerical value. But in no way does a numerical value demonstrate the conjecture of a buffer effect. IPCC reports on the successful part of evaluating the Revelle buffer over the open ocean, but intentionally deleted the part that shows the measurements strongly temperature dependent. During the drafting of its Fourth Assessment Report, one of its most respected reviewers, Nicolas Gruber said, “it is wrong to suggest that the spatial distribution of the buffer factor shown in Figure 7.3.10c is driven by temperature.” That relationship between the Revelle buffer factor and temperature was a simple mapping of Henry’s Law as it depends on temperature at a constant partial pressure in the atmosphere. What IPCC’s scientists had managed to do was measure solubility (they never mention Henry’s Law), and instead of finding that the Revelle buffer was a simple matter of solubility, they suppressed the measurements, removing Figure 7.3.10c from the final report.
A word for the readers on thermodynamic equilibrium. It is the toughest of standards, good only for the field of thermodynamics, a field that deals with unmeasurable, unobservable macroparameters. Examples are a global average surface temperature, and a global average Bond albedo. In thermodynamic equilibrium, all motion has ceased, as has all heat, the flow of thermal energy. The surface ocean is stirred vigorously by various forces, including thermal energy that is in perpetual exchange with the atmosphere and deep space.
So the surface ocean is in perpetual disequilibrium. Science has no model by which to establish the mix ratio of CO2(aq) and its reactants. IPCC claims to have demonstrated the validity of the buffering by evidence that the build-up in atmospheric CO2 bears the fingerprint of human activity. Those demonstrations involve a misunderstanding of ice core data and its low frequency filtering effect, and two outright fraudulent graphical demonstrations that the burning of fossil fuels produces a predicted reduction in the atmospheric mix of CO2 isotopes, and that the build-up of CO2 corresponds to the depletion of atmospheric O2 according to a stoichiometric relation for burning fossil fuels.
While CO2 is a greenhouse gas, meaning that it does contribute to the blanket effect of the atmosphere, but the incremental amount is infinitesimal and saturating. So all this straightening out of IPCC is fighting a five alarm fire, and for the likes of Phil, it is blowing out matches.

Jeff Glassman says:
July 4, 2010 at 8:10 am
Stoichiometry describes the proportions in which chemical species combine.
CH4 + 2O2 –> CO2 + 2H2O
Indeed that is a stoichiometric reaction, going completely to the right side, it is practically irreversable. But:
CO2 + H20 -> <- CO3(–) + 2 H(+)
is not a stoichiometric reaction, it is a dynamic equilibrium reaction leading to a “steady state composition” (which reaction constants in many cases are determined from stoichiometric start conditions). That may be read from the same source:
http://www.cbu.edu/~rprice/lectures/multrxn.html
Thus the rest of your explanation is based on -again- a wrong interpretation of a chemical equilibrium reaction, where there isn’t any need for stoichiometric (start) conditions.

Re Ferdinand Engelbeen, 7/5/10 at 12:07 pm:
I checked your authority, Randel M. Price, Assoc. Prof., Chemical Engineering, at the URL you gave, which is to his class notes for students.
I did not use the term stoichiometric reaction. I used the term stoichiometric equation, citing authority. Price does not define what is or what is not a stoichiometric equation.
You mention that the reaction you cite is “practically irreversible”. Price does give names to reactions based on whether they are reversible or irreversible.
Price says,
>>If the reaction mixture is held under controlled conditions, eventually it will balance out to a fixed composition. This “long time” condition is called equilibrium, and the “equilibrium composition” (“steady state composition”) is of great importance.
but Price does not use either of the terms “equilibrium reaction” and “stoichiometric reaction” which you argue are “quite different”. What Price seems to be saying is that any reaction mixture will reach an equilibrium state, which looks like Le Chatelier’s principle, does it not? Nothing too profound here, and nothing that makes a point in this dialog.
Price does not mention the phrase you promote and again cite, “dynamic equilibrium”.
You rely on “stoichiometric (start) conditions”. Price doesn’t even use the word “start”, much less your term.
To the contrary, the authorities I cited require thermodynamic equilibrium, and they are the same people cited by IPCC. Price does not require equilibrium.
The authorities I cite provide a stoichiometric equilibrium constant, K_2 and K_2*, for the reaction you claim is not stoichiometric. Z&W-G, op. cit., chart 3. (Note: the asterisk might be to distinguish between a constant for chemical equilibrium rather than thermodynamic equilibrium.) That is strongly suggestive that the reaction is indeed stoichiometric, though I have no authority so elementary that it would say that the “stoichiometric equilibrium constant” applies to stoichiometric equations.
You accuse me of making “a wrong interpretation”. On that subject, Price carries this important passage:
>>WARNING!: Different authorities use different definitions of some of these terms. If you bring information in from an outside source, be sure you know how it defines selectivity, etc.
You have thrown that caution to the wind, providing no authority * for substituting dynamic equilibrium for thermodynamic equilibrium, * for declaring equations not to be stoichiometric when they fit the stoichiometric definition provided, * for declaring Henry’s Law to involve the partial pressure difference when the elementary authority provided said the Law’s dependence on pressure only involves pCO2(g), • for restricting the meaning of calibration to the laboratory while IPCC uses calibration to indicate post-laboratory adjustments among and between stations in a network, • for endorsing the use of Henry’s Law to determine the rate of CO2 flux instead of what the Law provides: the total CO2 in solution.
P.S.
With regard to your amplifying post at 1:39 pm, some of the work that needs to be posted here is a challenge. It seems impossible under the imposed html limitations for the site, especially showing a stoichiometric equation with its constant placed above the reaction symbol. I did not rely on the typography of your post.

You have thrown that caution to the wind, providing no authority * for substituting dynamic equilibrium for thermodynamic equilibrium, * for declaring equations not to be stoichiometric when they fit the stoichiometric definition provided, * for declaring Henry’s Law to involve the partial pressure difference when the elementary authority provided said the Law’s dependence on pressure only involves pCO2(g), • for restricting the meaning of calibration to the laboratory while IPCC uses calibration to indicate post-laboratory adjustments among and between stations in a network, • for endorsing the use of Henry’s Law to determine the rate of CO2 flux instead of what the Law provides: the total CO2 in solution.
I can return the compliment by saying that you base your definitions on a misunderstood halve sentence and after that ignore what the authors and other sources from different authors and especially what the data show. No matter how much proof of the contrary is given, you stay by your opinion, which is mainly yours only:
for substituting dynamic equilibrium for thermodynamic equilibrium
thermodynamic equilibrium is one form of dynamic equilibrium, chemical equilibrium like the reaction of CO2 with water to form bicarbonate and back is another form.
for declaring equations not to be stoichiometric when they fit the stoichiometric definition provided
The reaction “constant” is defined stoichiometric and can be used whatever the initial mixture was, as the reaction constant, remains… constant (at constant thermodynamic conditions). These were already used in the 1920’s, including compensation for temperature, salt content and pressure.
for declaring Henry’s Law to involve the partial pressure difference when the elementary authority provided said the Law’s dependence on pressure only involves pCO2(g)
I never said that Henry’s Law involves partial pressure differences. Henry’s Law only shows the ratio’s of CO2 in the atmosphere and free CO2 in solution when a thermodynamic equilibrium is reached. If there is no partial pressure difference between what is in solution and in the gas phase above it, then both are in (thermodynamic) equilibrium. If the partial pressure of the ocean surface is higher or lower (as defined), then there is no equilibrium and the speed of transfer is in ratio with the partial pressure difference. The latter is used by Takahashi and many others.
for restricting the meaning of calibration to the laboratory while IPCC uses calibration to indicate post-laboratory adjustments among and between stations in a network
Totally nonsense, as can be seen in the raw measurements, both from flask data and continuous measurements, airplane and satellite data compared to the “adjusted” data. All CO2 data from 1,000 m high over land and from sealevel over the oceans to the stratosphere all over the world show variations within +/- 2% over a year. That is within the definition of “well mixed”.
for endorsing the use of Henry’s Law to determine the rate of CO2 flux instead of what the Law provides: the total CO2 in solution
Every textbook of chemistry (including Zeebe & Co) shows that Henry’s Law only determines free CO2 in solution (and back!) at equilibrium. If there is disequilibrium, either by changes in atmospheric CO2 or by changes in free CO2 in solution, a flux will occur against the direction of the disturbance. That is e.g. the case for a change of ocean pH or total CO2 in solution, as the Wattenberg measurements showed. The change of the chemical equilibrium by pH or DIC is not part of Henry’s Law, but influences the concentration of free CO2, thus Henry must work harder to restore the thermodynamic equilibrium…

Re Ferdinand Engelbeen, 7/6/10 at 4:37 & 5:41 am:
On 7/4/10 at 8:10, I provided you a sorely needed definition of stoichiometric equations. It happened to be from Randel Price, an authority you have also used, although the article is merely notes for his students (that is, I note, not subject to review). Regardless, his definition included defining the stoichiometric coefficients. Except for that definition, I have not used the term stoichiometric coefficients anywhere.
In my next paragraph to the Price citation, I referred to Z&W-G “stoichiometric equilibrium constant[s]” as “coefficients”. This misled you. I did not intend a reference to stoichiometric coefficients, but instead to the reaction coefficients that appear above the reaction arrows. My post on 7/5/10 at 2:25 by its reference to the K_2 coefficients should have clarified the matter. Sorry about the confusion.
You claim that I, too, have thrown caution to the wind by not providing references for my terms and models. To the contrary, I claimed to have provided those references in the same “You have thrown caution to the wind” paragraph. If you believe that I have taken any kind of controversial position without authority, I would be happy to rectify the omission. I have laboriously provided citations during the dialog.
For example, on 6/26/10 at 2:03 pm, I provided you a textbook definition of thermodynamic equilibrium, using Zemansky. It excludes a state in which matter or heat is being exchanged internally or with the external world. That pretty much excludes whatever you mean by “dynamic equilibrium”. You continue to defend that phrase, going so far as to say,
>> thermodynamic equilibrium is one form of dynamic equilibrium, chemical equilibrium like the reaction of CO2 with water to form bicarbonate and back is another form.
Surely whatever definition you might be using, dynamic equilibrium would hold all the way down to no dynamics at all, so I would expect thermodynamic equilibrium, a defined term, to be a subset of dynamic equilibrium, should that term ever be defined and brought into this discussion. However, thermodynamic equilibrium even viewed as a subset of dynamic equilibrium is a highly restrictive, theoretical state. Therefore, it must not be ignored where a model specifies that state as a condition.
You claim,
>>I never said that Henry’s Law involves partial pressure differences.
when you had asserted
>>Henry’s Law still is working, but the amount of free CO2 at the surface is not only influenced by temperature, but by a host of other factors. At last it is the real partial pressure of free CO2 in the last few cm of water which decides which way CO2 will go: in or out of the waters, if the difference with pCO2 of the atmosphere is higher or lower. Engelbeen, 6/22/10 at 5:03 am
That sounds like a contradiction to me.
You wrote,
>>>> for restricting the meaning of calibration to the laboratory while IPCC uses calibration to indicate post-laboratory adjustments among and between stations in a network

>>Totally nonsense, as can be seen in the raw measurements, … .
You response is irrelevant. The statement you call nonsense is about IPCC’s use of calibration AFTER the lab work, meaning AFTER the raw measurements. You return to endorsing the lab work. Besides, IPCC doesn’t even publish raw data, at least as far as CO2 concentrations are concerned.
You claim,
>>All CO2 data from 1,000 m high over land and from sea level over the oceans to the stratosphere all over the world show variations within +/- 2% over a year.
That is one brave claim! If it is true, why didn’t IPCC use that information, instead of inserting a “linear gain factor” to adjust non-MLO sites to agree with MLO? If ± 2% is significant, why didn’t IPCC use a number like that instead of its qualitative, undefined “well-mixed” characteristic? I don’t have the time to check a pair of raw CO2 data records, much less all such pairs, to cure my skepticism about your claim. And I have no idea what kind of smoothing you used to calculate your annual variation. Is this comparison published, perhaps on your website?
You wrote,
>>>>for endorsing the use of Henry’s Law to determine the rate of CO2 flux instead of what the Law provides: the total CO2 in solution

>>Every textbook of chemistry (including Zeebe & Co) shows that Henry’s Law only determines free CO2 in solution (and back!) at equilibrium. If there is disequilibrium, either by changes in atmospheric CO2 or by changes in free CO2 in solution, a flux will occur against the direction of the disturbance.
First, “total CO2 in solution” means total CO2(aq). Your criticism is to deny what I did not say: that Henry’s Law somehow applies to DIC or DIC+DOC+POC, where DIC is CO2(aq)+HCO3-+CO3–. (If you need an authority, let me know.) Here is one of the places where you and other IPCC believers go far off track. You fix the ratio of DIC:DOC:POC, like 2000:38:1, AR4, ¶7.3.4.1) and the concentrations of CO2(aq):HCO3-:CO3—(about 1%:91%:8%, TAR, Box 3.3, p. 1079; <1%:90%:9% at pH = 8.2, Zeebe & Wolf-Gladrow, slide 8). You use the fixed ratios determined for thermodynamic equilibrium for an ocean never in thermodynamic equilibrium. You use the equations for thermodynamic equilibrium for the state of dynamic equilibrium, which you seem unable to define, for equations that are inapplicable.
As a result you convert Henry's Law from determining the concentration of CO2(aq), but locked to the whole ocean system of CO2(aq):HCO3-:CO3–:DOC:POC. You create an equilibrium bottleneck to defeat Henry's Law. Because the ratios are fixed in your model, you could equally well express Henry's Law for any one of the forms of CO2, the total CO2 in all forms, or any subtotal.
Your theory is essential to AGW. Not enough ACO2 is emitted in any year to be the alleged cause of global warming, so it must be accumulating in the atmosphere (while preposterously natural CO2 is not!). This fixing of the ratios creates that bottleneck. Thus the atmosphere is an accumulator of a certain species of CO2, while the ocean adjusts all its ratios, including its pH (a fear bonus), all based on games played with equilibrium. In this theory, the atmosphere is a buffer in the sense of being an accumulator of ACO2, and the ocean is a buffer in the sense of a resistance against dissolution of CO2(g). This buffer, viewed either equivalent way, is the Revelle buffer.
Of course, your model that you share with IPCC, including the Revelle buffer, is balderdash. In ordinary physics, that is, excluding climatology, Henry's Law runs according to established theory to load the surface layer of the ocean with an unrestricted amount of CO2(aq), up to the limits for its temperature. This dissolution is just one more source of disequilibrium for the surface layer (along with solar radiation, long wave radiation to space, wind, ocean currents, ocean biology, etc.). In short, CO2(aq):HCO3-:CO3—is not in any predetermined ratio. The Bjerrum plot will have no meaning in disequilibrium, the real world.
The buffer holding excess CO2 is not the atmosphere. Under Henry's Law, the CO2 buffer in the system is the surface layer of the ocean. Henry does not have to work at all. He just watches.
Now this is all a tempest in a teapot because radiative forcing (RF) is not proportional to the logarithm of the concentration of CO2(g). The theory for radiation absorption in a gas is the Beer-Lambert Law, the next major law different only in the climatology consensus. The radiative forcing follows an S-curve, meaning that the effects of CO2 are (a) bounded and (b) saturate. Under the logarithm model, CO2 can absorb more than 100% of its absorption bands, and the RF can grow to infinity.
Even with these corrections to the IPCC model, we still have a tempest in a teapot. That is because climate is regulated by the slow negative feedback of cloud albedo when Earth is in a warm state ("interglacials", AR4, Glossary, p. 948). IPCC's climate sensitivity could be a tenth of its "very likely value of about 3ºC" with an immeasurably small change in cloud albedo, or it might lie in the range of 0.4ºC and 0.5ºC, according to Lindzen. See RSJ, “The Acquittal of CO2”, response to John, Channel Isles, 11/4/09. Citations for the fact that Earth’s climate is regulated by cloud albedo on request.

Re Ferdinand Engelbeen, 7/6/10 at 9:22 am
Thank you for the encouraging response.
Your interpretation of the “current definition of thermodynamic equilibrium” is correct. However, I would be most reluctant to admit an alternative definition, especially just to accommodate the climatology consensus, meaning the AGW dogma.
Sometimes science or math makes interesting strides in a new direction when an axiom is revised. A new geometry arose from letting parallel lines meet, and relativity arose by abandoning the Newtonian axiom that a universal, unidirectional clock exists. This is true for axioms, but is it ever true for laws? Perhaps the laws of thermodynamics are ripe for a revision on a cosmic scale. Who knows where the crazy cosmologists will go next as their standard theory becomes an ever more bizarre crazy-quilt of patches. The Laws of Thermodynamics are not suitable for revision on a microscopic scale because thermodynamics by definition is a macro or bulk science.
I note that your Wikipedia reference says,
>>Classical thermodynamics deals with dynamic equilibrium states.
I eagerly clicked on “Dynamic equilibrium” hoping to find the missing definition. Instead, I found this:
>>A dynamic equilibrium exists when a reversible reaction ceases to change its ratio of reactants/products, but substances move between the chemicals at an equal rate, meaning there is no net change. It is a particular example of a system in a steady state.
That is not a definition. It is a particular example stating where and when dynamic equilibrium occurs in chemical processes. Is dynamic equilibrium applicable only to chemical processes?
I clicked on the link to steady state, hoping to find clarification. Wikipedia provides that steady state occurs when the partial derivative of any property of the system with respect to time is zero. That doesn’t help. Its not a poor definition of steady state because of a problem that arises in the very example, above. Dynamic equilibrium only requires that the flux in equal the flux out, not that they are both zero.
The problem is that one needs to define steady state with respect to a system, defined by a fixed set of parameters. The partial derivative of those parameters must be zero. So, the system needs to be defined at the outset in terms of net flux.
Zemansky solves this problem. The definition I supplied earlier defines thermodynamic equilibrium in terms of changes to a system, in particular of (unbalanced) forces, structure, or coordinates. This leads to another definition from Zemansky, p. 4:
>>Macroscopic quantities having a bearing on the internal state of a system are called thermodynamic coordinates.
So if we were to define our air-sea system with care, we’d be sure to use the net flux across the boundary. Wikipedia’s example would come closer to being a definition cast in terms of a system and its coordinates. Then the dynamic equilibrium would be equivalent to thermodynamic equilibrium except for one additional problem: Wikipedia requires the process by which dynamic equilibrium is achieved to be reversible. As we have discussed above, reversible processes never occur in nature. That’s a violation of the Second Law. Furthermore, reversibility is a restriction not required for thermodynamic equilibrium.
To the extent that the Wikipedia entry reflects the definition of dynamic equilibrium, it is more restrictive than thermodynamic equilibrium. When Zeebe & Wolf-Gladrow required thermodynamic equilibrium for the solution to the carbonate system, that was sufficient.
Re calibration:
You say,
>>Here the note for Mauna Loa from Keeling Sr. from an older file (2004):
>>>>The “annual” average is the arithmetic mean of the twelve monthly values. In years with one or two missing monthly values, annual values were calculated by substituting a fit value (4-harmonics with gain factor and spline) for that month and then averaging the twelve monthly values.
>>The two columns differ from each other in the second decimal only…
Thus the “linear gain factor” has absolutely nothing to do with calibration, the IPCC or after-the-fact manipulation.
We already discussed this. I gave you citations for the fact that IPCC authors did not use the linear gain factor at MLO, and your citation only confirms that point. On the other hand, they used a linear gain factor for Barrow, Alaska (BRW) and one (which we must assume is different) for the South Pole (SPO). Then IPCC plotted the MLO and the SPO data on top of one another, and they matched. Surprise! Then they did the same thing for MLO and BRW, and they again matched. Wonder of wonders! Thus CO2 appeared to be well-mixed, and hence MLO concentrations were global. Do this on a government contract in the US and you might go to jail. IPCC calls it calibration.
Re fixed ratios:
The fixed ratios I gave were merely numerical examples used by advocates from IPCC Reports. For DIC, those ratios correspond to the Bjerrum plot at some pH, the abscissa. The Bjerrum plot defines fixed ratios by the relationships between simultaneous concentration curves dependent on pH. The plot by implication fixes those ratios. The fixed ratios are functions of pH.
You may not rely on the Bjerrum plot, the solution to the stoichiometric equations for the carbonate system in the surface layer, until you establish that thermodynamic equilibrium exists in the surface layer. Of course, it does not. For the same reason, you may not rely on dynamic equilibrium, because, as inferred from your source, it is even more restrictive than thermodynamic equilibrium.
The idea that you may not rely on a law, theory, or model in general without satisfying its boundary conditions is so fundamental that it is not even mentioned as a scientific postulate. Also the fact that a modeled relation can be measured in no way validates the model. For example, the Revelle factor is defined as a ratio. Call it r. So RF = r, and r is assumed measurable all over the ocean. But so is RF’ = r +r^2, or = r^(1/2).
The Bjerrum plot is used by IPCC believers as a state diagram. As you have urged and implied, added CO2 obeys the equations, shifting the plot left to a more acidic state. We could plot the system state on the Bjerrum plot before and after the added CO2.
Unfortunately, the CO2(aq) graph on the Bjerrum plot of the three components of DIC has no meaning in disequilibrium. The CO2(aq) will be different. It might be shifted up by a constant. In disequilibrium, the intersections with the ion graphs become meaningless. This shifting is necessary to accommodate Henry’s Law for added atmospheric CO2, meaning added pCO2.
You say,
>>Thus while the atmospheric CO2 content increased with 30% to 800 GtC over the past 150 years or so, the ocean surface layer total carbon increased only with 3% from ~1000 to ~1030 GtC in the same period. So far the buffer working of the ocean surfaces.
During that 150 year period, SST increased, causing the ocean to release CO2(g) according to the solubility curve. Added pCO2 causes uptake to increase proportionally, but outgassing to decrease in inverse proportion. This requires a mass balance analysis, which is missing from IPCC reports. With reasonable estimates for temperature increase over the past 150 years, and using IPCC’s outgassing of 90 GtC/yr and its uptake of 92 GtC/yr, your 30% increase in CO2 problem may over specify the problem and have no solution. IPCC assumes this problem away by (a) not revealing its mass balance analysis, (b) assuming nCO2 to be in balance, and then (c) treating ACO2 on the margin. The problem is nonlinear, invalidating IPCC’s radiative forcing paradigm, i.e., the response to ACO2 is not additive with the response to nCO2.
I suspect your 3% number is an estimate, being merely one tenth of 30%, where the number of one tenth comes from thermodynamic equilibrium equations, a state that never exists in the surface ocean. This is my guess because the buffer, at least as defined by IPCC, depends on thermodynamic equilibrium for its existence when thermodynamic equilibrium is not present.
If you could provide a reference for the calculation I might confirm whether my guess is right.

Re Ferdinand Engelbeen, 7/8/10 at 5:01 Pm
1. Re Species of Equilibrium
You discovered in Wikipedia, a notoriously risky source, what I already gave you from Zemansky, a supreme source. Then you say,
>>But as on earth we have an external source of heat, many natural processes are in dynamic equilibrium.
I can’t let you get away with a wishy-washy definition of dynamic equilibrium. Because it’s a term you, and not I, insist on using, you have the burden of providing an authoritative definition. The definition I inferred from your Wikipedia citation is the best that has been supplied on this thread. A reasonable inference from that article is that dynamic equilibrium implies thermodynamic equilibrium, but not the reverse.
>>Here on earth no system is isolated from the rest of the earth, or the universe.
We model earthly systems all the time without concern for such academic, cosmic worries. What you have stated is true, but so extreme as to be irrelevant.
That argument is not the reason for saying that the surface layer of the ocean is not in thermodynamic equilibrium. It is not in mechanical equilibrium because it is stirred by winds, currents, biology and geology. It is not in thermal equilibrium because it is heated by the Sun and cooled by radiation to space, and heat is exchanged by conduction and convection to the deeper ocean. It is not in chemical equilibrium because of biology and the carbonate process, as a minimum. All three equilibria, however, must be satisfied to be in thermodynamic equilibrium.
The reason the surface layer is not in equilibrium is not a cosmic argument, but a local, observable argument, enmeshed in the more complex climate models. The notion of surface layer equilibrium is, to be kind, unreasonable.
You wrote:
>>Thermodynamic equilibrium doesn’t necessary mean a dynamic equilibrium, but doesn’t exclude it either.

Thermodynamic equilibrium is a state, independent of the processes by which it was attained. According to the definiton on the table, dynamic equilibrium is a state with not just active processes, but with idealized, reversible processes.
Thermodynamic equilibrium is an idealized condition, too, involving rarely or never observable macroparameters, like entropy and enthalpy, and much more. Arguably, thermodynamic equilibrium exists nowhere on Earth. Dynamic equilibrium, though, is a more severe constraint, involving reversible processes, which, if they existed, would violate the Second Law. Thermodynamic equilibrium is hypothetical, but not a violation of the laws of the discipline. In summary, dynamic equilibrium, as interpreted from the Wikipedia article, is a thermodynamic equilibrium in which the Second Law is violated.
Later you say,
>>It is established that a thermodynamic equilibrium exists for any point of the oceans.
This is preposterous, as shown by the discussion above. For the AGW story to have any validity, ACO2 must accumulate in the atmosphere. The model that makes that happen is the Revelle buffer factor. That factor is derived from the stoichiometric equilibrium equations, for which the solution is the Bjerrum plot. That solution applies only in thermodynamic equilibrium.
The whole model hinges on the existence of thermodynamic equilibrium. You may not simply proclaim that thermodynamic equilibrium exists.
Perhaps you are assuming, maybe without realizing it, that the Bjerrum plot is valid and applicable, and therefore that the surface ocean must be in equilibrium. You must start from the other end, and show the impossible: that the surface layer is in thermodynamic equilibrium.
You claim, unnecessarily as it turns out, that the surface ocean is in dynamic equilibrium. For this to be true, the CO2 flux from air to sea would have to balance the flux from sea to air. However, you also rely on the fact that two fluxes are not equal in your argument justifying the Takahashi analysis. That, you claim, is what causes CO2 to be absorbed. You can’t have it both ways. You may not rely on a net flux of zero for the Bjerrum solution to hold, and assume a positive flux for the ocean in absorbing CO2, or vice versa for outgassing.
2. Re the Well Mixed assumption
You say,
>>You are so determined to show that CO2 is not well mixed, that you accuse everybody on this earth who has anything to do with CO2 measurements of manipulating the data.
Your accusation is unwarranted. IPCC manipulated the data, and I provided you the evidence. You refuse to respond to that evidence, except to revert to the claim that the laboratory work was all honest and competent. You ask me to study the laboratory work, saying it will only take a half hour. But time is not the issue. The problem is that all that could be demonstrated from such a study is whether IPCC’s fraud penetrated to the laboratory level. AGW exists only because of IPCC, and that makes demonstrating the crime involved dependent on what IPCC provided as the basis for its claim. The fraud is contained in the IPCC Assessment Reports, which do not include either laboratory data, or, most pointedly, calibration data.
You quote the May 2005 version of the monthly data explanation for SPO, and claim it is “exactly the same as for Mauna Loa”. The URL in your reference inexplicably carries a 2009 date. It includes a “gain factor” for SPO, called a “linear gain factor” in the later 2008 report, and which you strangely site as the “origin of my confusion”. I didn’t find an old MLO report to go with your 2005 data, but the latest MLO report does not include a gain factor anywhere, and including the point where it is included for other stations.
You need to show, and have failed to do so, that the MLO data not only includes a “gain factor”, but that it is identical to the SPO gain factor. You also need to show that your data were the latest in effect at the time of the Fourth Assessment Report.
Further, I am not “determined to show that CO2 is not well mixed”. I am convinced from good evidence, now including satellite imagery, from superior modeling, from the lack of a criterion for well-mixed, and from IPCC’s fraudulent treatment of data that the claim of CO2 being well-mixed in the atmosphere is without merit. At the same time, I am aware of the great importance of that well-mixed assumption to the AGW model, and hence the motivation for the abuses of science practiced by the Panel and its authors.
You say,
>>Thus there is not the slightest shred of evidence left that the IPCC or any of its authors has biased the data from any station.
First, real world data records are neither as well-behaved internally as are the MLO, Baring Head, BRW, and SPO records in IPCC reports, nor do they overlay one another with such precision as IPCC shows. IPCC graphs of these records are naïve, simplistic, unrealistic, and highly suspicious. I would remind you also that uncorrelated data subjected to mathematical smoothing can become correlated.
Second, IPCC admits making inter-network and intra-network calibrations. This is tantamount to a confession.
Third, IPCC does not report its calibration values, suggesting an intent to deceive.
3. Re Immediate reaction assumption
IPCC says,
>>Carbon dioxide entering the surface ocean IMMEDIATELY reacts with water to form bicarbonate (HCO3–) and carbonate (CO3 2–) ions. CAPS added, AR4, ¶7.3.1.1, p. 514.
Accordingly, you say,
>>Because the three components are always NEAR INSTANTLY in (dynamic and thermodynamic) equilibrium… . CAPS added.
No evidence exists to support this conclusion. It is a presumably necessary assumption to make the Bjerrum solution valid so that the ocean will create a buffer against solubility, and so that added CO2 will cause another crisis by acidifying the ocean. The motivation behind this naked assumption is clear and objectionable.
Furthermore, even if the reactions were nearly instantaneous, we might assume them to be equally fast in reverse on the same authority. When the ocean outgasses to the atmosphere, we might justifiably assume equilibrium remains in the surface layer so that CO2(aq) is created instantaneously from the ions in the reverse reactions as fast as it is outgassed as CO2(g).
In other words, I could accept your instantaneous conversion of CO2(aq) to HCO3^- and CO3^– if you would grant instantaneous conversion from HCO3^- and CO3^– to CO2(aq), and to boot, instantaneous CO2(aq) CO2(g). In this way, the surface ocean can be considered to be in equilibrium at a single point, i.e., a single pH on the Bjerrum plot, and Henry’s Law can proceed apace – no buffer (no bottleneck) and no acidification. I don’t care whether the surface ocean is modeled as being in disequilibrium or in a hypothetical state of equilibrium, so long as the physics of solubility of CO2 in water is respected, and the notions of the Revelle factor and acidification are left as failed conjectures.
4. Calculated bootstrap evidence for thermodynamic equilibrium
At your invitation, I read “The Interannual to Decadal Variability of the Ocean Carbon Cycle” from the website of the Marine Biogeochemistry Lab. First I would observe the realistic APPEARANCE of the data graphed in Figure 1, normalized DIC, normalized TA [Total Alkalinity], pCO2, and pH. Data points are connected in follow-the-dots fashion, which is OK here, and the trend lines are graphed separately. This is distinctly different from various smoothing techniques IPCC applied to shift curves, and then to have the points represent plot points instead of data points. Also the data appear to have not unreasonable noise in amplitude and phase.
The legend for Figure 1 says, “Figure prepared for the IPCC 4th Assessment, in preparation 2004”. It says,
>>pCO2 data was [sic] calculated from DIC and alkalinity data using dissociation constants and theoretical considerations outlined in Bates et al., 1996. … pH data was [sic] calculated from DIC and alkalinity data using dissociation constants and theoretical considerations outlined in Bates et al., 1996.
That IPCC Report would issue three years later, with just the pCO2 and pH data merged into Figure 5.9, p. 404. This legend confirms that “Values of pCO2 and pH were CALCULATED from DIC and alkalinity at … BATS [Bermuda Atlantic Time-series Study] … .” CAPS added.
I found this likely, though not unique, reference on other pages from the same Lab: Bates, N.R., Michaels, A.F., and Knap, A.H., 1996, “Seasonal and interannual variability of the oceanic carbon dioxide system at the U.S. JGOFS Bermuda Atlantic Time-series Site. Deep-Sea Research II, 43(2-3), 347-383”. I retrieved a pdf image copy, and found the following:
>> The oceanic CO2 system can be characterized by measuring two of the parameters (i.e. pH, pCO2 or fCO2, TCO2, and TA), with the other two parameters CALCULATED USING THERMODYNAMIC RELATIONSHIPS (Stoll et al., 1993; Millero et al., 1993b; DOE, 1994). …
>>TCO2, TA, temperature, discrete salinity and nutrient data were used to CALCULATE pCO2 AND pH VALUES USING THE ALGEBRAIC RELATIONSHIPS given in Peng et al. (1987) AND DISSOCIATION CONSTANTS for carbonic acid (Goyet and Poisson, 1989), borate (Dickson, 1990), and phosphate (DOE, 1994). CAPS added.
The pH and pCO2 records look like data because they were calculated from noisy data.
Your observations relative to these articles are:
>> pCO2(g) increased about 30 ppmv in the period 1984-2004 or about 10%.
pCO2(aq) in the same period increased with about 25 ppmv or about 7.5%.
nDIC in the same period increased with 0.8%.
>>Remarkable that they could manage to obtain so many observed data for something that is not measurable.
You’ve been hoodwinked. What is remarkable is that the only records from Bermuda (BATS) reported by IPCC were calculated, not measured. Specifically, the pCO2 on which you rely to demonstrate the 10:1 relationship given by the Bjerrum plot, the solution to the thermodynamic equilibrium chemical equations, were computed using those relationships.
5. Re Mass Balance
You asked,
>>What kind of mass balance do you need?
Answer: the same as suggested by IPCC when it said,
>>[T]wo methods can be used to quantify the net global land-atmosphere flux: … (2) inferring the land-atmosphere flux simultaneously with the ocean sink by inverse analysis or MASS BALANCE COMPUTATIONS using atmospheric CO2 data, … . CAPS added, AR4, ¶7.3.2.2.2, p 519.
The boundary conditions for the necessary mass balance include the following. IPCC showed the air-ocean “sink” for the 1990s in Figure 7.3, p. 515. It absorbed 92.2 GtC/yr from the atmosphere and outgassed 90.6 GtC/yr into an atmosphere of 762 GtC. Meanwhile the ACO2 emissions were 6.4 GtC/yr from fossil fuels, plus other terrestrial fluxes. IPCC showed the MLO and Baring Head CO2 concentrations increased from about 320 ppm in 1970 to about 380 in 2005. IPCC also showed an isotopic lightening of the atmosphere from about -7.6 per mil in 1981 to roughly -8.1 per mil in 2003. (I believe I confused the names Baring Head and Point Barrow (BRW) previously.)
The mass balance needs to cover the periods of 1750 to about a century into the future. For a first cut, the terrestrial fluxes may be assumed to have a net zero effect, and the process may be assumed for the first cut to be isothermal. Then, the absorption of CO2 into the ocean must be set proportional the atmospheric concentration of CO2, equivalently the pCO2. The outgassing must be inversely proportional to pCO2. The change in total CO2 in the atmosphere must be equal to the sum of the outgas plus the ACO2, less the amount absorbed. Certain reasonable assumptions are required, including the shape of the rise in ACO2 emissions, and the isotopic mixes of the atmosphere, and hence the absorbed CO2, and of the outgassing CO2, presumed dominantly to be from ancient waters. These assumptions may be tested by the mass balance model.
Later, temperature effects may be added to make the outgassing proportional to solubility curve for CO2 in water as a function of a reasonable model for SST.
As you say,
>>It’s as simple as that.
6. Re Henry’s Law, temperature, and atmospheric CO2 increases
You previously hypothesized a 30% rise in atmospheric CO2 to 800 GtC over the past 150 years. Here’s a simplified model for the partial effect of temperature, using your data and a physical model instead of an arbitrary comparison of the growth of CO2 concentration and temperature.
Your increase in atmospheric CO2 concentration, C, is from 615.4 to 800, or 184.6 GtC. Assume that to be linear at 0.0163 GtC/yr. IPCC’s estimate for the ocean’s CO2 outgas, O0, was 90 GtC for the 1990s. In this partial model, the uptake (I) is always at ice water temperature, so does not participate. The outgas is inversely proportional to X, the solubility factor (Henry’s coefficient) at an effective temperature roughly corresponding to tropical waters. The solubility is approximately linear at these temperatures, X(T) = X0 – mT. At 30ºC, X0 is 0.1257 and m is – 0.0035/ºC. At 20ºC, X0 = 0.1688 and m = -0.0049/ºC. Handbook of Chemistry & Physics, 34th ed., 1953, Solubility of Gases in Water, p. 1532. Slopes are calculated from the table entries at the specified temperature and the next lower temperature.
With these assumptions, delta outgas, DelO = O – O0 ~ O0*m*T/X0. We use delta outgas because the question is about the marginal effects of a change from the initial conditions of the 1990s. Let T = i*DelT, a linear temperature rise, so O – O0 = O0*m*DelT*i/X0. The total added ocean flux for the 150 years is O0*m*DelT/X0 times the sum of i from 0 to 150. That sum is N*(N+1)/2 = 11325. Set the total added flux for 150 years equal to your atmospheric increase of 184.6 GtC, and solve for DelT. For T0 = 30ºC, DelT = -0.006505ºC and the total temperature increase over the past 150 years is 0.976ºC. For T0 = 20ºC, DelT = -0.00624ºC and the total temperature rise was 0.936ºC.
Thus the temperature effects alone COULD account for the increase in atmospheric CO2 based on Henry’s Law, a reasonable natural temperature rise, and the natural CO2 flux, which IPCC negligently rendered constant and benign within its model of the carbon cycle. This analysis is by the partial derivative with respect to temperature, keeping the responses to pressure constant. It shows why a more complete mass balance treatment is necessary. Ocean uptake is proportional to C, and its outgas is inversely proportional to C.
A mass balance analysis is a scenario obeying principles of physics and IPCC’s boundary conditions. It might show that solubility accounts for the estimated rise in atmospheric CO2 as a feedback from atmospheric pressure, with SST having a negligible effect. The analysis can account for the proportion of that rise due to ACO2 (it is not 50% of the added ACO2!), and it can account for the observed change in the isotopic ratio. It should also show why IPCC’s model in which it adds the natural CO2 response to the ACO2 response is a modeling error. The carbon cycle is nonlinear so the response of the sum of forcings, nCO2 and ACO2, is not equal to the sum of the individual responses. Symbolically, R(nCO2 + ACO2) ≠ R(nCO2) + R(ACO2). The radiative forcing paradigm is invalid.
7. Re Regional data in global models
A final observation is that climate is a thermodynamic problem, meaning that it is a problem in macroparameters. A model that mixes macroparameters, mesoparameters, and microparameters is in grave danger of not converging to a useful model, that is, one that makes non-trivial predictions.
The following are examples of relevant macroparameters: global average surface temperature, SST, Bond albedo, and the key parameter, climate sensitivity. For these a global model is required for the ocean. Phenomena like the Atlantic gyre (Englebeen, 7/2/10), the Bermuda ocean water, above, and salinity are regional phenomena, confounding considerations already taken into account in the assumed global ocean model. So, too, is the Takahashi analysis, and considerations found here and there, in the literature and in the blogosphere, for the atmospheric temperature lapse rate and longwave radiation at various altitudes. The thermodynamic solution to climate is not likely sensitive to these mesoparameters.
Another way of looking at the problem is that regional effects, whether horizontal or vertical, are not uniquely determined by a state specified by thermodynamic coordinates for climate. Attempting to include irrelevant regional phenomena will most likely have the effect of preventing the global model from converging. This is Occam’s Razor raised from the subjective realm of elegance and simplicity to the objective realm of a modeling imperative.

Re Ferdinand Engelbeen, 7/11/10 at 7:43 am
After I pointed out we have already discussed this reversibility matter, you insisted,
>>Come on Jeff, Wiki shows that the Second Law also is applicable for reversible processes. And almost all processes in nature are reversible. Only for isolated systems in disequilibrium, the process is irreversible. Which is not the case for many processes on this earth.
Just to sharpen the focus and to help others you don’t want to search through this long, long thread, here’s what I posted previously:
>>>>The question immediately arises as to whether natural processes, i.e., the familiar processes of nature, are reversible or not. The purpose of this chapter is to show that it is a consequence of the second law of thermodynamics that all natural processes are irreversible. Zemansky, M. W., “Heat and Thermodynamics”, Ch. 8, Reversibility and Irreversibility, McGraw-Hill, Fourth Ed., 1957, p. 151-2.


We are at an impasse on dynamic equilibrium, and I can contribute no further. I must skip every paragraph you write in which you rely on this ill-defined concept, one that contradicts the conditions actually imposed for the chemical equations, the Bjerrum plot solution, and the Revelle factor conjecture to be valid.
You wrote,
>>SPO doesn’t use a gain factor, except if there are too many missing data from maximum two months.
The CDIAC material doesn’t say that. Can you provide an authority for this claim?
For support, you referenced a paper, “How we measure background CO2 levels on Mauna Loa”:
http://www.esrl.noaa.gov/gmd/ccgg/about/co2_measurements.html#instrument
A book could be written about this procedure. A few critical items are the subjective nature of what it calls “‘outlier rejection'”, a most problematic procedure, and of the rejection of data for various conditions, mostly associated with the wind vector, which seems not to have been recorded. The lab rejects data, but says reassuringly, “No data are thrown away.” The lab computes minute and hourly averages, plus monthly and yearly means. The latter are not shown, but they are for comparison with the Scripps reductions. The graphs in this paper look like real data, unlike the records published by IPCC.
Scripps and MLO use different data selection methods, the paper says without explanation. It mentions no smoothing performed on the monthly and yearly records prior to comparing them, yet smoothing is apparent in the IPCC reports. Smoothing alone could account for the apparent agreement reported in the paper. The monkey business with the CO2 data seems to occur with the smoothing and the linear gain factors. Your observations and conclusions about the handling of data prior to those processes adjustments are to no avail.
The procedure says nothing about a linear gain factor, which is not surprising because CDIAC omits that factor for MLO data. Still, the MLO procedure seems to have a procedure in place for computing its averages in spite of not having a gain factor. Therefore, I am skeptical of your claim that the gain factor used at the other stations is for adjusting for missing data. Linear extrapolation might compensate for missing data, but that should not be called a gain factor.
The procedure notes that the MLO data might “be representative of … hopefully, the globe”. It spends some ink on discussing local phenomena and global phenomena, mentioning even human activity. It never mentions the massive natural outgassing from the ocean and the convection and wind currents that carry that CO2 rich air across Hawaii, where it is modulated by the local and seasonal winds. Keeling warned about relying on CO2 measurements taken near sources and sinks, but these investigators have yet to discover that MLO sits in the plume of ocean outgassing that is nominally 15 times as great as man’s puny emissions.
You say,
>>As the differences in CO2 levels in 95% of the atmosphere are less than 2% in absolute level, that has not the slightest influence on the AGW model, as that is based on a doubling and more of CO2 in absolute levels.
First, the doubling model is based on the presumption that radiative forcing is dependent on the logarithm of the GHG concentration. This is fallacious, violating the Beer-Lambert Law. It quickly leads to impossible results, and obliterates the natural saturation effects revealed from application of Beer-Lambert.
Second, IPCC’s model for the doubling is open-loop with respect to the dominant feedback in all of climate, the cloud albedo effect. As I have reported previously, cloud albedo could reduce the climate sensitivity by a factor of 10 without even being measurable in the state-of-the-art of albedo estimation. Recent satellite measurements as reported by Lindzen show the climate sensitivity to be a factor of 4 less than estimated by IPCC.
Apply the Beer-Lambert Law and close the cloud albedo feedback loop, and you will see that while CO2 has a positive effect on global temperatures, it is too small to be measured – it is lost in the noise. Perfecting CO2 measurement techniques has great academic interest, but no effect on a practical climate model.
You wrote,
>>The reaction constants and speeds were established in the early 1900′s, long before there was any fear of acidifying the oceans or CAGW.
I had some link to the reaction speed, but can’t find it back. The slowest seems the two-way CO2 + H2O = HCO3(-) + H(+) conversion with 30 seconds half life at 37 C (in blood…), that is about 2 minutes at zero C. Not really slow for the three forms of carbon equilibrium at 1 or 100 m depth in the oceans, … .
So may I presume a slug of CO2 was inserted in blood at t=0 and that it exhibited a half life of 30 seconds? Was the half life shown to be constant, or at least linear with the size of the slug? When that slug was first inserted, what were the ratios of CO2(aq):HCO3-:CO3–? Now suppose a stream of CO2 is inserted into a solvent. What are those ratios?
You wrote,
>>As was demonstrated over 80 years ago, the calculated and measured pCO2(aq) values and pH values for any point in the oceans are equal. … That pCO2 calculated and directly measured are interchangeable, can be seen by the use of volunteer ships with automated pCO2(aq) (spray) measurements:
http://www.bios.edu/Labs/co2lab/research/PCO2VOS.html
If what you claim were true, science might be well along the way of validating the thermodynamic equilibrium model applied to the real ocean. I could find that claim nowhere.
Your link was to the Marine Biogeochemistry Lab blog, again. This time to a page called, “Measurements of Partial Pressure of CO2 on Volunteering Observing Ships (VOS)”. It had nothing to support your claim of an equivalence established between calculations and measurements. It did have three other links, with many links to other links, and so on. I searched through several levels and could find nothing to support your claim.
Nowhere in this search could I find an instance of the same parameter both calculated and measured. In every case that I searched, I came to the point where the data were interpreted according to assumption of thermodynamic equilibrium, or to a vague reference to one or more publications by Weiss (e.g., 1974, 1982), papers which are not freely available to the public.
Weiss (1974) is cited in Zeebe & Wolf-Gladrow’s encyclopedia article previously reference on this thread on 6/27 at 7:56 am. That source suggests that the results from Weiss (1974) apply in thermodynamic equilibrium. The CDIAC “Guide to Best Practices for Ocean CO2 Measurements”, 10/12/07, and the previous DOE “Handbook of Methods for the Analysis of the Various Parameters of Carbon Dioxide System in Sea Water”, 9/29/97, credit Weiss (1974) for the virial coefficients used to expand the ideal gas law from pV/RT to an expression for a real gas. Weiss (1974) may also be the source for reformulating Henry’s Law from pCO2 to fCO2, that is, from dependence on partial pressure to fugacity, a calculated parameter for a real gas equivalent to the partial pressure calculated for an ideal gas in a mixture of ideal gases.
Both handbooks cited provide this relevant passage:
>>Equations that describe the CO2 system in sea water
>>It is possible, in theory, to obtain a COMPLETE description of the carbon dioxide system in a sample of sea water at a particular temperature and pressure provided that the following information is known:
>>• the solubility constant for CO2 in sea water, K0,
>>• the equilibrium constants for each of the acid–base pairs that are assumed to exist in the solution,
>>• the total concentrations of all the non-CO2 acid–base pairs,
>>• the values of at least two of the CO2 related parameters: C_T , A_T , f(CO2), [H+].
>>The optimal choice of experimental variables is dictated by the nature of the problem being studied and remains at the discretion of the investigator. Although each of the CO2 related parameters is linearly independent, they are not orthogonal. For certain combinations there are limits to the accuracy with which the other parameters can be predicted from the measured data. These errors end up being propagated through the equations presented here. Such errors result from all the experimentally derived information, including the various equilibrium constants. As a consequence it is usually better to MEASURE a particular parameter directly using one of the methods detailed in Chapter 4 than to calculate it from other measurements. Italics converted to CAPS.
Here C_T is DIC, and A_T is the total alkalinity. Note, too, that it refers to a mere possibility in theory, meaning with certain hypothetical assumptions.
As qualitative as this handbook warning is, it contradicts your claim.
You claim,
>>The raw data and the monthly, “cleaned” data show exactly the same curve, trend and average, within tenths of a ppmv. They can be compared to flask data taken at the same place, by different labs, using different (calibration) methods. These differ not more than a few tenths of a ppmv.
Where are the data? You say “can be compared”, and then provide an accuracy. Don’t you mean, “were compared”, and don’t you need a citation?
If what you claim was true, why didn’t IPCC exploit that fact? Why do they display only the doctored monthly data? I would agree that THOSE data, the “‘cleaned'” records, differ by less than a few tenths of a ppmv.
You say,
>>>> The change in total CO2 in the atmosphere must be equal to the sum of the outgas plus the ACO2, less the amount absorbed.
>>Which is currently about +4 GtC/year in the atmosphere. There is not the slightest need to know the real amount of outgas or amount absorbed, because we know the difference between the two: -4 GtC. It is as simple as that.
Nonsense. IPCC claims the ocean outgassing is about 90 GtC per year and its uptake is about 92.2 GtC per year. You cannot work on the margin. The small difference between two large numbers is a classic error, and here it ignores the physics. IPCC keeps those number constant and in balance, when they must vary according to the law of solubility.
You continue,
>>To know the real amount of out gassing and absorption is of interest for the fine details of the carbon cycle, but not necessary for an overall mass balance, which shows that humans are to blame for the increase, not nature, as long as the increase in the atmosphere is less than the addition by humans.
What you are being shown is not the fine details, but the coarse details, the first order effects canceled by IPCC. Those first order effects are developed in the mass balance, an analysis IPCC implies that it made, but did not publish. You are quite right that the results from the IPCC show (according to IPCC, or better, “tend to show”) that humans are to blame. Of course, that was IPCC’s preconceived notion in its interpretation of its charter, and the rest of IPCC’s work is to select and to distort data to support its assumption. At the highest level, this is anti-science.
And lest we forget the rest of the story, the Revelle buffer, which IPCC elevated from a failed conjecture to a viable theory, is based on the same thermodynamic equilibrium assumption. And so, too, is the beautiful Takahashi diagram. These two pieces of the AGW conjecture are cast by IPCC as applying only to ACO2 or perhaps just fossil fuel emissions. Even if one were to accept that the surface layer of the ocean is close enough to thermodynamic equilibrium (close being a meaningless concept) for government work, the application of the results to ACO2 but not natural CO2 is ludicrous.
The mass balance analysis is crucial to a high fidelity modeling of the carbon cycle. It is not crucial to a climate model because that the carbon cycle is immaterial as a cause of global warming.
You wrote about
>>any point in the ocean
and
>>oceanic (CO2) hot spots
These may be examples of the ultimate in local phenomena. These reflect an inappropriate scale for the thermodynamic problem of the climate, and constitute a distraction from the ultimate question.
You asked,
>>Didn’t you forget something? If there is initially more out gassing and equal sink capacity, pCO2(g) will increase, thus reducing the speed of out gassing at the equator and increasing the speed of uptake near the poles (you know, the exchange needs time…).
No, and exactly! YOU postulated that CO2 increased by 30% over the past 150 years. Partial pressure is defined as the mole fraction of CO2 times the total pressure, where the total pressure here is about one atmosphere. Therefore pCO2(g) increases by the same 30% in your example. I was simply demonstrating how temperature alone could account for that increase, according to the law of solubility.
You claimed,
>>Thus at a certain moment, a new (dynamic…) equilibrium is reached and out gassing and uptake are equal again, at a higher level of pCO2(g) (and a slightly higher level of outflows and inflows).
Why would that happen? Are you claiming Le Chatelier’s principle applies to your dynamic equilibrium? Isn’t that rather like saying a cone balanced on its apex will tend to resume that balance after being disturbed?
The Vostok record shows, within its granularity, that for more than a half million years of natural climate, the CO2 never stabilized. The CO2 is coming and going from someplace, and as my paper “The Acquittal of Carbon Dioxide” shows, the best answer is the surface water and is a consequence of Henry’s Law.
You say,
>>Whatever the resolution of the Vostok record, the long-range average CO2 level in that period was 290 ppmv, with a sensitivity of CO2 for temperature changes of 8 ppmv/C.
Just bear in mind that the Vostok record is heavily smoothed. The closure time of the firn, being between several decades to as much as a millennium and a half, acts like a low pass filter. This sharply reduces the variability of the measurements compared to modern methods by a factor called the variance reduction ratio for the filter. An event like the one currently being observed at Mauna Loa, deemed to have existed for only 60 years or so, would be lost in the noise in the Vostok record. Also remember that Henry’s Law says that the CO2 fluxes are dependent on the relative concentration of CO2 in the atmosphere and not just on temperature. Once again what is need is a mass balance analysis.
You close with,
>>But we don’t need these details for an overall CO2 mass balance of the atmosphere, neither for the origin of the increase over the past 150+ years.
I agree. Those details, e.g., “exchanges between the different compartments” don’t participate in the mass balance analysis at all. And according to my unpublished mass balance model, the human caused part of atmospheric CO2 is approximately proportional to the ratio of its emissions to oceanic outgassing – about 6% to 10% all ’round.