Guest Post by Willis Eschenbach
There seem to be a host of people out there who want to discuss whether humanoids are responsible for the post ~1850 rise in the amount of CO2. People seem madly passionate about this question. So I figure I’ll deal with it by employing the method I used in the 1960s to fire off dynamite shots when I was in the road-building game … light the fuse, and run like hell …
First, the data, as far as it is known. What we have to play with are several lines of evidence, some of which are solid, and some not so solid. These break into three groups: data about the atmospheric levels, data about the emissions, and data about the isotopes.
The most solid of the atmospheric data, as we have been discussing, is the Mauna Loa CO2 data. This in turn is well supported by the ice core data. Here’s what they look like for the last thousand years:
Figure 1. Mauna Loa CO2 data (orange circles), and CO2 data from 8 separate ice cores. Fuji ice core data is analyzed by two methods (wet and dry). Siple ice core data is analyzed by two different groups (Friedli et al., and Neftel et al.). You can see why Michael Mann is madly desirous of establishing the temperature hockeystick … otherwise, he has to explain the Medieval Warm Period without recourse to CO2. Photo shows the outside of the WAIS ice core drilling shed.
So here’s the battle plan:
I’m going to lay out and discuss the data and the major issues as I understand them, and tell you what I think. Then y’all can pick it all apart. Let me preface this by saying that I do think that the recent increase in CO2 levels is due to human activities.
Issue 1. The shape of the historical record.
I will start with Figure 1. As you can see, there is excellent agreement between the eight different ice cores, including the different methods and different analysts for two of the cores. There is also excellent agreement between the ice cores and the Mauna Loa data. Perhaps the agreement is coincidence. Perhaps it is conspiracy. Perhaps it is simple error. Me, I think it represents a good estimate of the historical background CO2 record.
So if you are going to believe that this is not a result of human activities, it would help to answer the question of what else might have that effect. It is not necessary to provide an alternative hypothesis if you disbelieve that humans are the cause … but it would help your case. Me, I can’t think of any obvious other explanation for that precipitous recent rise.
Issue 2. Emissions versus Atmospheric Levels and Sequestration
There are a couple of datasets that give us amounts of CO2 emissions from human activities. The first is the CDIAC emissions dataset. This gives the annual emissions (as tonnes of carbon, not CO2) separately for fossil fuel gas, liquids, and solids. It also gives the amounts for cement production and gas flaring.
The second dataset is much less accurate. It is an estimate of the emissions from changes in land use and land cover, or “LU/LC” as it is known … what is a science if it doesn’t have acronyms? The most comprehensive dataset I’ve found for this is the Houghton dataset. Here are the emissions as shown by those two datasets:
Figure 2. Anthropogenic (human-caused) emissions from fossil fuel burning and cement manufacture (blue line), land use/land cover (LU/LC) changes (white line), and the total of the two (red line).
While this is informative, and looks somewhat like the change in atmospheric CO2, we need something to compare the two directly. The magic number to do this is the number of gigatonnes (billions of tonnes, 1 * 10^9) of carbon that it takes to change the atmospheric CO2 concentration by 1 ppmv. This turns out to be 2.13 gigatonnes of carbon (C) per 1 ppmv.
Using that relationship, we can compare emissions and atmospheric CO2 directly. Figure 3 looks at the cumulative emissions since 1850, along with the atmospheric changes (converted from ppmv to gigatonnes C). When we do so, we see an interesting relationship. Not all of the emitted CO2 ends up in the atmosphere. Some is sequestered (absorbed) by the natural systems of the earth.
Figure 3. Total emissions (fossil, cement, & LU/LC), amount remaining in the atmosphere, and amount sequestered.
Here we see that not all of the carbon that is emitted (in the form of CO2) remains in the atmosphere. Some is absorbed by some combination of the ocean, the biosphere, and the land. How are we to understand this?
To do so, we need to consider a couple of often conflated measurements. One is the residence time of CO2. This is the amount of time that the average CO2 molecule stays in the atmosphere. It can be calculated in a couple of ways, and is likely about 6–8 years.
The other measure, often confused with the first, is the half-life, or alternately the e-folding time of CO2. Suppose we put a pulse of CO2 into an atmospheric system which is at some kind of equilibrium. The pulse will slowly decay, and after a certain time, the system will return to equilibrium. This is called “exponential decay”, since a certain percentage of the excess is removed each year. The strength of the exponential decay is usually measured as the amount of time it takes for the pulse to decay to half its original value (half-life) or to 1/e (0.37) of its original value (e-folding time). The length of this decay (half-life or e-folding time) is much more difficult to calculate than the residence time. The IPCC says it is somewhere between 90 and 200 years. I say it is much less, as does Jacobson.
Now, how can we determine if it is actually the case that we are looking at exponential decay of the added CO2? One way is to compare it to what a calculated exponential decay would look like. Here’s the result, using an e-folding time of 31 years:
Figure 4. Total cumulative emissions (fossil, cement, & LU/LC), cumulative amount remaining in the atmosphere, and cumulative amount sequestered. Calculated sequestered amount (yellow line) and calculated airborne amount (black) are shown as well.
As you can see, the assumption of exponential decay fits the observed data quite well, supporting the idea that the excess atmospheric carbon is indeed from human activities.
Issue 3. 12C and 13C carbon isotopes
Carbon has a couple of natural isotopes, 12C and 13C. 12C is lighter than 13C. Plants preferentially use the lighter isotope (12C). As a result, plant derived materials (including fossil fuels) have a lower amount of 13C with respect to 12C (a lower 13C/12C ratio).
It is claimed (I have not looked very deeply into this) that since about 1850 the amount of 12C in the atmosphere has been increasing. There are several lines of evidence for this: 13C/12C ratios in tree rings, 13C/12C ratios in the ocean, and 13C/12C ratios in sponges. Together, they suggest that the cause of the post 1850 CO2 rise is fossil fuel burning.
However, there are problems with this. For example, here is a Nature article called “Problems in interpreting tree-ring δ 13C records”. The abstract says (emphasis mine):
THE stable carbon isotopic (13C/12C) record of twentieth-century tree rings has been examined1-3 for evidence of the effects of the input of isotopically lighter fossil fuel CO2 (δ 13C~-25‰ relative to the primary PDB standard4), since the onset of major fossil fuel combustion during the mid-nineteenth century, on the 13C/12C ratio of atmospheric CO2(δ 13C~-7‰), which is assimilated by trees by photosynthesis. The decline in δ13C up to 1930 observed in several series of tree-ring measurements has exceeded that anticipated from the input of fossil fuel CO2 to the atmosphere, leading to suggestions of an additional input ‰) during the late nineteenth/early twentieth century. Stuiver has suggested that a lowering of atmospheric δ 13C of 0.7‰, from 1860 to 1930 over and above that due to fossil fuel CO2 can be attributed to a net biospheric CO2 (δ 13C~-25‰) release comparable, in fact, to the total fossil fuel CO2 flux from 1850 to 1970. If information about the role of the biosphere as a source of or a sink for CO2 in the recent past can be derived from tree-ring 13C/12C data it could prove useful in evaluating the response of the whole dynamic carbon cycle to increasing input of fossil fuel CO2 and thus in predicting potential climatic change through the greenhouse effect of resultant atmospheric CO2 concentrations. I report here the trend (Fig. 1a) in whole wood δ 13C from 1883 to 1968 for tree rings of an American elm, grown in a non-forest environment at sea level in Falmouth, Cape Cod, Massachusetts (41°34’N, 70°38’W) on the northeastern coast of the US. Examination of the δ 13C trends in the light of various potential influences demonstrates the difficulty of attributing fluctuations in 13C/12C ratios to a unique cause and suggests that comparison of pre-1850 ratios with temperature records could aid resolution of perturbatory parameters in the twentieth century.
This isotopic line of argument seems like the weakest one to me. The total flux of carbon through the atmosphere is about 211 gigtonnes plus the human contribution. This means that the human contribution to the atmospheric flux ranged from ~2.7% in 1978 to 4% in 2008. During that time, the average of the 11 NOAA measuring stations value for the 13C/12C ratio decreased by -0.7 per mil.
Now, the atmosphere has ~ -7 per mil 13C/12C. Given that, for the amount of CO2 added to the atmosphere to cause a 0.7 mil drop, the added CO2 would need to have had a 13C/12C of around -60 per mil.
But fossil fuels in the current mix have a 13C/12C ration of ~ -28 per mil, only about half of that requried to make such a change. So it is clear that the fossil fuel burning is not the sole cause of the change in the atmospheric 13C/12C ratio. Note that this is the same finding as in the Nature article.
In addition, from an examination of the year-by-year changes it is obvious that there are other large scale effects on the global 13C/12C ratio. From 1984 to 1986, it increased by 0.03 per mil. From ’86 to ’89, it decreased by -0.2. And from ’89 to ’92, it didn’t change at all. Why?
However, at least the sign of the change in atmospheric 13C/12C ratio (decreasing) is in agreement with with theory that at least part of it is from anthropogenic CO2 production from fossil fuel burning.
CONCLUSION
As I said, I think that the preponderance of evidence shows that humans are the main cause of the increase in atmospheric CO2. It is unlikely that the change in CO2 is from the overall temperature increase. During the ice age to interglacial transitions, on average a change of 7°C led to a doubling of CO2. We have seen about a tenth of that change (0.7°C) since 1850, so we’d expect a CO2 change from temperature alone of only about 20 ppmv.
Given all of the issues discussed above, I say humans are responsible for the change in atmospheric CO2 … but obviously, for lots of people, YMMV. Also, please be aware that I don’t think that the change in CO2 will make any meaningful difference to the temperature, for reasons that I explain here.
So having taken a look at the data, we have finally arrived at …
RULES FOR THE DISCUSSION OF ATTRIBUTION OF THE CO2 RISE
1. Numbers trump assertions. If you don’t provide numbers, you won’t get much traction.
2. Ad hominems are meaningless. Saying that some scientist is funded by big oil, or is a member of Greenpeace, or is a geologist rather than an atmospheric physicist, is meaningless. What is important is whether what they say is true or not. Focus on the claims and their veracity, not on the sources of the claims. Sources mean nothing.
3. Appeals to authority are equally meaningless. Who cares what the 12-member Board of the National Academy of Sciences says? Science isn’t run by a vote … thank goodness.
4. Make your cites specific. “The IPCC says …” is useless. “Chapter 7 of the IPCC AR4 says …” is useless. Cite us chapter and verse, specify page and paragraph. I don’t want to have to dig through an entire paper or an IPCC chapter to guess at which one line you are talking about.
5. QUOTE WHAT YOU DISAGREE WITH!!! I can’t stress this enough. Far too often, people attack something that another person hasn’t said. Quote their words, the exact words you think are mistaken, so we can all see if you have understood what they are saying.
6. NO PERSONAL ATTACKS!!! Repeat after me. No personal attacks. No “only a fool would believe …”. No “Are you crazy?”. No speculation about a person’s motives. No “deniers”, no “warmists”, no “econazis”, none of the above. Play nice.
OK, countdown to mayhem in 3, 2, 1 … I’m outta here.
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tonyb says:
June 27, 2010 at 2:49 am
Your 12.38 message was presumably aimed at Jeff Glassman-I never said anything about the subject :
Sorry, copied the wrong header…
Callendar and Suess and many others of his time (even Arrhenius before them) did see the greenhouse effect of CO2 as a positive item. The alarmists did come later… Besides that, the criteria hCallendar used did result in a graph that 50 years later was confirmed by CO2 measurements in ice cores, firn, even roughly in stomata data…
Most of the historical measurement methods were accurate to +/- 3% of the measurement or for a 300 ppmv level about +/- 10 ppmv. Not even accurate enough to detect the seasonal variability. The NDIR method, together with the calibration as developed by Keeling, is better than +/- 0.1 ppmv since the start of the measurements over 50 years ago.
Indeed, Keeling did know nothing about CO2 when he joined Scripps, but he not only was a fast learner, but also had an enormous analytical insight and practical skills, which made him one of the greatest scientists of the previous century, whatever he did think about global warming. As somebody else wrote: we could only hope that the temperature measurements were set up and controlled in an equal way…
Jeff Glassman says:
June 26, 2010 at 1:30 pm
Tried to post this, now in two parts, as it doesn’t show up…
R. F. Keeling and S. Piper were IPCC contributing authors for both the TAR and AR4.
Thus every contributing author of the IPCC (including Spencer, McIntyre,…) is on your personal blacklist of fraudsters of the IPCC?
The yes part of his two-way answer is wrong. Nowhere is the ocean in equilibrium, which is the ultimate state of stagnation. In equilibrium, there are no currents and no heat transfer (to use the redundant term). One cannot even say that something is close to equilibrium. A system either is or it is not in equilibrium. The surface layer is in turmoil, including all thin slices of it.
OK, if you insists: include in all mentionings of “equilibrium” that 99% of all engineers in the world talk about a dynamic equilibrium, never a static one, as that doesn’t exist in the real world. Thus the ultimate surface layer of the oceans always is in dynamic equilibrium with the atmosphere, although a lot of molecules can be transfered both ways… But as the layers below it aren’t in equilibrium with the atmosphere (at most places), there is always a difference in transfer rates. This results in a lot of CO2 degassing at the equator and a lot of absorbance near the poles. But in the past at least 420,000 years, the whole CO2 system was in dynamic equilibrium, where the level in the atmosphere was only influenced by temperature changes. That changed 150 years ago with the human emissions.
This is not correct. The conclusion from Zeebe, et al., is for a fictional surface layer perpetually restrained to be in equilibrium. That conclusion relies on the stoichiometric equations of equilibrium, and the solution given graphically in the Bjerrum plot. The uptake and outgassing of CO2 is governed by Henry’s Law. Dissolution does not depend on the pressure difference or pressure gradient. Except for the fact that this air-sea exchange model is crucial to justifying AGW, it is a surprising error from a prominent, contributing, PhD professor of geophysics, and from someone who claims credentials as a chemist.
If you think that “Dissolution does not depend on the pressure difference or pressure gradient.”, you simply demonstrate that you don’t understand the physics and chemistry involved. If there was no pressure gradient between free CO2 in the water and in the atmosphere (that means equal transfer of molecules from water to air as reverse), then there was zero (net) flux (or a dynamic equilibrium).
What you are saying is that only temperature (via Henry’s Law) is involved in the amount of (free) CO2 in seawater and hence the flux in either direction between ocean and atmosphere. This is completely wrong. The amount of free CO2 in seawater depends of a lot of other items than temperature alone: pH, salt content, DIC content. From
http://www.soest.hawaii.edu/oceanography/faculty/zeebe_files/Publications/WolfGladrowMarChem07.pdf
you can learn (page 289) that pH and DIC have a direct influence on (dissolved free) CO2 concentration at a constant temperature and salt content. Thus any use of temperature alone doesn’t show what is really happening in solution, thus not what will happen in reality. pCO2, measured or calculated, is the only realistic parameter which may give the difference between oceanic and atmospheric CO2 pressure, thus the direction and to a certain extent the quantity of the flux.
This is your error, not somebody’s else (including many who have published, measured and calculated pCO2 from the oceans).
On 6/27/10 at 12:38 am, Ferdinand Engelbeen said,
>>Like on many items, you have your own ideas about definitions, which differs from what others mean. In the case of two systems in radiation balance, the whole process is in thermodynamic equilibrium and each of them is in thermodynamic equilibrium as their state doesn’t change, as for each of them and both together, all the inputs equal the outputs. Where for near all people in the world with some technical/scientific knowledge is implied the word “dynamic”, without mentioning it, except for you.
>>Climate never is in dynamic equilibrium, as the inputs and outputs continuously change and mostly not in an equal way.
>>But it certainly is reversible.
First rational dialog cannot exist without solid definitions. AGW as a political movement doesn’t require definitions any more than other forms of politics do. Climate, though, is science, and in fact a branch of thermodynamics. Here, definitions are essential. I will assume all terms are drawn from the field of thermodynamics. However, if you want to introduce another term, I’m willing to accommodate your peculiar definitions.
IPCC said,
>>The air-sea exchange of CO2 is determined largely by the air-sea gradient in pCO2 between atmosphere and ocean. Equilibration of surface ocean and atmosphere occurs on a time scale of roughly one year. Gas exchange rates increase with wind speed (Wanninkhof and McGillis, 1999; Nightingale et al., 2000) and depend on other factors such as precipitation, heat flux, sea ice and surfactants. The magnitudes and uncertainties in local gas exchange rates are maximal at high wind speeds. In contrast, the equilibrium values for partitioning of CO2 between air and seawater and associated seawater pH values are well established (Zeebe and Wolf-Gladrow, 2001; see Box 7.3). AR4, ¶7.3.4.1 Overview of the Ocean Carbon Cycle, p. 528.
For openers, the first sentence is false.
>>Carbonate chemistry
>>In thermodynamic equilibrium, gaseous carbon dioxide (CO2(g)), and [CO2] are related by Henry’s law:
>>CO2(g) = [CO2] (at K_0), (1)
>>where K_0 is the temperature and salinity dependent solubility coefficient of CO2 in seawater (Weiss, 1974). The concentration of dissolved CO2 and the fugacity of gaseous CO2, fCO2, then obey the equation [CO2] = K_0 × fCO2, where the fugacity is virtually equal to the partial pressure, pCO2 (within ~1%). Zeebe, R. E., and D. A. Wolf-Gladrow, “Carbon dioxide, dissolved (ocean).” Encyclopedia of Paleoclimatology and Ancient Environments, Ed. V. Gornitz, Kluwer Academic Publishers, Earth Science Series, in press 2008, p. 1. http://www.soest.hawaii.edu/oceanography/faculty/zeebe_files/Publications/ZeebeWolfEnclp07.pdf
And
>> The pCO2 of a seawater sample refers to the pCO2 of a gas phase in equilibrium with that seawater sample. Id., p. 3.
Conclusions: Equilibrium, which IPCC does not define, should be thermodynamic equilibrium because climate is a thermodynamic problem. IPCC’s own authorities confirm that their work on which IPCC relies is for thermodynamic equilibrium. Furthermore, the thermodynamic relationships follow from Henry’s Law, which IPCC ignores and Engelbeen discounts. And those reactions of dissolution depend on the partial pressure of CO2 in the gas phase, and not on the fantastic “air-sea gradient in pCO2”.
Contrary to Engelbeen’s assertion, climate can be well modeled as being in dynamic equilibrium. As in all science, it’s a matter of the accuracy demanded of the model. For over a half million years, the global surface temperature has been about 14ºC (5ºC to +17ºC). Dynamic equilibrium may be exactly the same as steady state. IPCC uses the term “dynamic equilibrium” just once in its two last Assessment Reports, and that is with respect to ground water. AR4, ¶5.5.5.4, p. 418. IPCC uses the phrase “steady state” 47 times in those Reports.
Apparently Engelbeen has observed reversible processes in his experience.
>>[A] reversible process is one that is performed in such a way that, at the conclusion of the process, both the system and the local surroundings may be restored to their initial states, without producing any changes in the rest of the universe. A process that does not fulfill these stringent requirements is said to be irreversible.
>>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.
Engelbeen’s problem is not so much, as he says, that English is not his first language, as it is that his experience is in a different universe.
Ferdinand
I merely wanted to establish the historic record accurately as I diasagreed with one of your earlier statements . We now seem to be agreed that whilst Keeling may have become one of the great brains over time, he was a complete novice when he started at Mauna Loa
That he managed to immediately build a piece of equipment 100 times more accurate than the combined efforts of hundreds of great scientists during the 130 years of Co2 sampling prior to his appointment is something we will never agree on, nor the reliabilty of CO2 ice cores.
However I think we must be agreed that IF CO2 was a constant 280ppm before mans intevention, and yet we recorded dramatic changes in the climate, then CO2 is a very weak climate driver and natural variability is a far more significant factor.
All the best
Tonyb
Jeff Glassman says:
June 27, 2010 at 7:56 am
Furthermore, the thermodynamic relationships follow from Henry’s Law, which IPCC ignores and Engelbeen discounts. And those reactions of dissolution depend on the partial pressure of CO2 in the gas phase, and not on the fantastic “air-sea gradient in pCO2″.
The IPCC neither I ignore Henry’s Law, you ignore that temperature is not the only parameter in CO2 solubility in seawater and temperature is only one factor. In your own pages, you only show one graph of solubility of CO2 in water with a fixed salt content, that fits part of the Vostok curve. But real seawater shows huge differences in salt content, DIC and pH. Each of them influences the pCO2 of seawater in equilibrium with the atmosphere.
Your own Hawaii universityreference is clear about that:
The dissolved carbonate species react with water, hydrogen and hydroxyl ions and are related by the equilibria:
CO2 + H2O = HCO3(-) + H(+) = CO3(2-) + 2 H(+)
where the = sign is a bidirectional reaction sign and between () means upper case.
Thus if the pH is lower (for whatever reason), or the carbonate content is higher (for whatever reason), the reactions are pushed to the left side, and more CO2 is set free at identical salt content and temperature. That is what lacks in all your reasoning about Henry’s law and the solubility curve. The increase of plankton (blooms) in summer have a profound effect on CO2 in solution, because of bicarbonate use to build their shells, that reduces the pCO2 of the ocean surface, thus releasing less CO2 to the atmosphere.
Further:
The pCO2 of a seawater sample refers to the pCO2 of a gas phase in equilibrium with that seawater sample.
Why the emphasis on seawater? This is the definition of the pCO2 of seawater, not of the gas phase above it… If the gas phase has a higher pCO2 than the pCO2 of seawater, then CO2 from the gas phase will be pushed into the seawater, if the pCO2 of the gas phase is lower, CO2 will come out of the water. If both are equal, the system is in equilibrium. The transfer rate in all cases is proportional to the difference in pCO2 between water and the atmosphere above it. Negative, positive and zero.
Please note that they don’t use “dynamic”, while in all three cases there are dynamics involved, as molecules are continuously transfered in both directions. Thus the IPCC and I are completely right that one need to look at the difference between the pCO2 of seawater and the pCO2 of the atmosphere, because that is the driving force for uptake or release.
No further discussion about the “irreversable” climate, as that is not relevant here.
For tonyb and Ferdinand Engelbeen, passim:
For a different historical perspective, I recommend Spencer Weart’s online work, “The Discovery of Global Warming”. He gives major credit to Roger Revelle, who hired Dave Keeling early in Dave’s career. Weart says,
>> Before scientists would take greenhouse effect warming seriously, they had to get past a counter-argument of long standing. It seemed certain that the immense mass of the oceans would quickly absorb whatever excess carbon dioxide might come from human activities. Roger Revelle discovered that the peculiar chemistry of sea water prevents that from happening. His 1957 paper with Hans Suess is now widely regarded as the opening shot in the global warming debates. This essay not only describes Revelle’s discovery in detail, but serves as an extended example of how research found essential material support and intellectual stimulus in the context of the Cold War.
Revelle discovered nothing. He realized that CO2 emissions were not near large enough to support the model that CO2 caused global warming. So he advanced a conjecture that a buffer existed in sea water to cause manmade(!) CO2 to accumulate in the atmosphere. He couldn’t quantify his model, so he engaged Han Suess for the task. Together they produced the 1957 article. It was not a technical paper, but a pitch for a share of the funds for the upcoming (1958) International Geophysical Year that Revelle was promoting. In their pitch, Revelle and Suess confirmed that they could not set the parameters of the problem to show that CO2 accumulated in the atmosphere, hence more funds were required. Isn’t it always the case?
IPCC seized on Revelle’s buffer as if the Revelle & Suess article were a technical paper, and tried to resurrect Revelle’s conjecture in its Fourth Assessment Report. It said,
>>Carbon Cycle Feedbacks to Changes in Atmospheric Carbon Dioxide
>>Chemical buffering of anthropogenic CO2 is the quantitatively most important oceanic process acting as a carbon sink. Carbon dioxide entering the ocean is buffered due to scavenging by the CO3^(2–) ions and conversion to HCO3^(–), that is, the resulting increase in gaseous seawater CO2 concentration is smaller than the amount of CO2 added per unit of seawater volume. Carbon dioxide buffering in seawater is quantified by the Revelle factor (‘buffer factor’, Equation (7.3)), relating the fractional change in seawater pCO2 to the fractional change in total DIC after re-equilibration (Revelle and Suess, 1957; Zeebe and Wolf-Gladrow, 2001): … AR4, ¶7.3.4.2, p. 531.
In case this isn’t perfectly clear, what is most important is the Revelle conjecture: that seawater, while acting as a CO2 sink, must buffer against ACO2 absorption in order for AGW to work. Note also that IPCC again refers to “seawater pCO2″, the fictional parameter that contradicts their authorities, Zeebe and Wolf-Gladrow.
IPCC’s effort failed, but one wouldn’t notice from a casual reading of its Report. When IPCC’s effort turned out to be a rediscovery of solubility, IPCC concealed the information. See discussion, rocketscientistsjournal.com, ” On Why CO2 Is Known Not To Have Accumulated in the Atmosphere, etc.”, Part 5, re. Figures 3 and 4.
Dave Keeling’s contribution was to help advance the state of the art in CO2 measurements, a pet project he was pursuing for fun at Big Sur, California, circa 1955. His long held ambition was to work outdoors, and to establish a global baseline for atmospheric CO2 concentration. Sadly that was a failure and irrelevant to climate.
In 1956, Keeling’s CO2 work came to the attention of Harry Wexler, director, Division of Meteorological Research, US Weather Bureau, whose pet project was the building and staffing of a new observatory at Mauna Loa. So while cautioning that measurements should not be made within the influence of sinks or sources, Keeling managed to collect data from a spot smack in the plume of the ocean’s massive, wind-modulated, CO2 outgassing.
Concurrently, Keeling’s work came to the attention of Roger Revelle, Director of Scripps, who was already championing CO2 as Callendar’s greenhouse agent causing global warming. Revelle hired Keeling. In September, 1956, Revelle with Hans Suess wrote a pitch for IGY funding for Keeling’s measurements. The ocean’s aversion to ACO2 was going to cause it to build up and produce global warming. What has withstood the tests of time and reason is their sentence turned slogan: “Thus human beings are now carrying out a large scale geophysical experiment of a kind that could not have happened in the past nor be reproduced in the future.”
Keeling says that he wasn’t convinced until 1965 after working with Revelle on the President’s Science Advisory Committee Panel on Environmental Pollution.
An article published in the initial issue of Cosmos by Roger Revelle and shortly before his death concluded, “The scientific basis for greenhouse warming is too uncertain to justify drastic’ action at this time.” The article seemed out of character and inconsistent with other recent pronouncements by Revelle. AGW proponents allege Roger Revelle, in failing health, was tricked into signing a paper drafted by others.
But now, 45 years later, we can say with confidence that CO2 has nothing to do with the climate. See rocketscientistsjournal.com. And the time for drastic action has arrived! Isn’t it also time for a couple of posthumous Nobel peace prizes?
tonyb says:
Hi, tonyb!
Actually, that doesn’t follow at all. How can you tell if CO2 is a strong or weak driver when it isn’t changing? If it changes significantly and climate doesn’t, then you have a logical argument. In your case, not so much. (And, of course, whether the changes in climate…especially on a global scale…were that dramatic over the last few thousand years is debatable, but even leaving that aside, your argument doesn’t follow.)
Ferdinand Engelbeen, 6/27/10 at 7:14 am said,
>>Thus every contributing author of the IPCC (including Spencer, McIntyre,…) are on your personal blacklist of fraudsters of the IPCC?
I made no such accusations against Keeling and Piper. You had said,
>>The IPCC isn’t involved in calibrations or procedures around CO2.
To prove you wrong, I quoted the calibration techniques applied to the those monthly records data you say are pure laboratory data. Those techniques included an unquantified “linear gain factor”, applied not to MLO but to SP and BH. After that “linear gain factor”, which may be variable in time and station dependent, the trends at SP, BH, and MLO data all agree. That is called “calibration” in the IPCC world. It involves CO2. It was reported by IPCC contributing authors. IPCC IS involved in calibrations and procedures around CO2.
You took my citation out of context, and supplied your own meaning with no justification, just to hurl an ad hominem attack. Shame.
You wrote,
>>If you think that “Dissolution does not depend on the pressure difference or pressure gradient.”, you simply demonstrate that you don’t understand the physics and chemistry involved. If there was no pressure gradient between free CO2 in the water and in the atmosphere (that means equal transfer of molecules from water to air as reverse), then there was zero (net) flux (or a dynamic equilibrium).
I gave you an encyclopedic treatment of the subject written by Zeebe and Wolf-Gladrow in support of the physics as I stated it. I quoted the misinterpretation by IPCC, referenced to the same writers. Regardless, you continue to hold with IPCC’s version.
In the spirit of science and accuracy, I will concede that there is indeed a pressure gradient between the partial pressure of CO2 in the atmosphere and the partial pressure of CO2 in the water. The latter is zero. When a gas is dissolved in a solvent, it exerts no more gas pressure. Therefore, the gradient you and IPCC endorse is equal to the partial pressure of CO2 in the atmosphere. Is that better?
You wrote,
>>What you are saying is that only temperature (via Henry’s Law) is involved in the amount of (free) CO2 in seawater and hence the flux in either direction between ocean and atmosphere. This is completely wrong. The amount of free CO2 in seawater depends of a lot of other items than temperature alone: pH, salt content, DIC content.
And
>>Henry’s law holds for one level of pH, DIC and salt content of seawater.
What do you mean by “free CO2”? Is that total CO2 = DIC + DOC + POC, or just one of them, or is it molecular (un-ionized) CO2? What I am saying is that Henry’s Law applies to total gas dissolved in a solvent, and that it depends on temperature, pressure, salinity, and by conjecture, on molecular weight. Further, it is an equilibrium property. With regard to the air-sea flux, the gas of concern is CO2 and the solvent is sea water. The rate of dissolution is also proportional to wind velocity. With regard to the air-sea flux, pressure and salinity don’t vary significantly, and wind velocity averages out, all with respect to temperature. Ocean acidity (pH) and relative DIC content are effects of dissolved CO2, and not contributors to dissolution. Henry’s Law is not known to depend on pH or DIC.
To the extent that your physics is different, I challenge you to provide unbiased evidence as I have done for my position. If you rely on IPCC, including any of its authors, you will fail my challenge.
With regard to your following observations,
>> The pCO2 of seawater is measured routinely on seaships by simply spraying seawater in a closed air system at the temperature of the seawater and measuring the CO2 level of that air. Thus pCO2 of seawater is what the atmosphere would get if both seawater and air were in dynamic equilibrium at that temperature. Any partial pressure of CO2 in the real atmosphere above that would give a flux into the oceans and vv. Temperature is important, but only one of the parameters involved. pCO2 gives the right answer…
Good enough. But you fail to see that in the procedure you describe, the partial pressure measured is that in the air, not in the seawater. When we speak of the partial pressure of CO2 in water, that is jargon, meaning we deem the water to have that partial pressure. Underlying the jargon, the reference is to the pCO2 which only exists in the air. Dissolved CO2 exerts no pressure.
And to the contrary of your last two sentences, temperature of seawater is the key parameter.
The partial pressure, pCO2, is important, too, because the ocean will dissolve CO2 out of the atmosphere in proportion to pCO2, that is, in proportion to the CO2 concentration in the atmosphere immediately above the water. Water exposed to the CO2 rich air emitted from the Equatorial outgassing will absorb more CO2 than would water at the same temperature not exposed to that outgassing.
Water exposed to CO2-depleted air in the polar regions will dissolve less CO2 than would water at the same temperature exposed to richer air. Water in transit from the tropics to the poles will adjust its CO2 content along its path, following the local partial pressure. At the time of the descent of what is the THC at the poles, seawater will be loaded with CO2 corresponding to its solubility at about 0ºC and at the local partial pressure in the polar atmosphere.
Your reference on 6/27/10 at 1:42 quoting U. of Hawaii is no different than what anyone else is saying, including IPCC and Zeebe & Wolf-Gladrow. Please note that in every case, the chemical equations relate to the state of equilibrium. Those equations will hold once the surface layer of the ocean reaches equilibrium, and not a moment before. Because equilibrium is a state and not a continuous measure, we can’t even say that the conditions in the surface layer approach the equilibrium conditions in any sense.
I have mentioned the solution to those equations in posts here, and you have not responded. As I said, it is solved graphically in the Bjerrum plot. You might want to read about it on rocketscientistsjounal.com, “On Why CO2 is Known Not To Have Accumulated in the Atmosphere, etc.”, which was the source of Steve Hempell’s 6/7/10 query to Willis Eschenbach that kicked off his baseless diatribe early in this thread. I would draw your attention first to Figures 7 and 8. I infer that you are aware of this graphical solution because you note the “reactions are pushed to the left side”.
Instead you talk about the solution as if you were introducing it for the first time on this thread. But then, you utterly confuse cause and effect. The pH and the concentration of ions in the surface layer do not regulate Henry’s Law, the dissolution of CO2. They do not create a bottleneck.
Nor is the reverse true. The dissolution of CO2 does not shift the Bjerrum plot one way or the other, that is, until equilibrium is reached. And that never happens.
You say,
>>If the gas phase has a higher pCO2 than the pCO2 of seawater, then CO2 from the gas phase will be pushed into the seawater, if the pCO2 of the gas phase is lower, CO2 will come out of the water. If both are equal, the system is in equilibrium. The transfer rate in all cases is proportional to the difference in pCO2 between water and the atmosphere above it. Negative, positive and zero.
This is pure balderdash. Even Henry’s Law tells us nothing about the rate of exchange. Since the stoichiometric equations of equilibria and the dissolution of CO2 in water are governed by the same Law, isn’t it gratifying that the physics tells us nothing about the trajectory of the state of the system?
And isn’t it ironic that so much time is spent on CO2, that it has been thoroughly misunderstood by IPCC, and in the end it has no measurable affect on climate?
Joel Shore
Great to hear from you!
I think you missed the implied smiley after my comment. Ferdinand and I go back a long way…
I think it would be perfectly possibly to make a logical argument that natural variability is by far the bigges factor in our climate change but I wasn’t seriously attempting to do that here. The argument between Ferdinand and Jeff is far too entertaining for me to want to hijack the thread. Perhaps another time.
Tonyb
Ps I have missed you and Scott Mandia posting over here as regularly as you once did.
Jeff Glassman says:
June 27, 2010 at 4:08 pm
Revelle discovered nothing. He realized that CO2 emissions were not near large enough to support the model that CO2 caused global warming. So he advanced a conjecture that a buffer existed in sea water to cause manmade(!) CO2 to accumulate in the atmosphere.
Well, if you can prove that Revelle was wrong in his “conjecture”, there are hundreds of scientific works confirming it. The basics of buffering solutions are teached in first years chemistry classes…
His long held ambition was to work outdoors, and to establish a global baseline for atmospheric CO2 concentration. Sadly that was a failure and irrelevant to climate.
It was Keeling, who was a smart enough to see why there were large CO2 variations over land, except in the afternoon, when atmospheric mixing shows similar values everywhere. It was his idea that one could find a “background” CO2 level, if measured on remote places. And he did find that in 95% of the atmosphere. Far from a failure, he was and is proven right. For his very interesting story, read his autobiography:
http://scrippsco2.ucsd.edu/publications/keeling_autobiography.pdf
In case this isn’t perfectly clear, what is most important is the Revelle conjecture: that seawater, while acting as a CO2 sink, must buffer against ACO2 absorption in order for AGW to work. Note also that IPCC again refers to “seawater pCO2″, the fictional parameter that contradicts their authorities, Zeebe and Wolf-Gladrow.
Again you haven’t get even the basics if what pCO2 means: the partial pressure of CO2 from a seawater sample as can be measured in air above it when at (dynamic) equilibrium. That is routinely measured and can be calculated from the other parameters (including, but not solely, Henry’s Law). The pressure difference between the pCO2 (=volume ratio) in the atmosphere and pCO2 from the ocean water is what drives the direction and strength of the CO2 flux. There is not the slightest contradiction with Zeebe or others, as also your own references show.
Keeling managed to collect data from a spot smack in the plume of the ocean’s massive, wind-modulated, CO2 outgassing.
Your own idea of the speed of outgassing/absorption… Not backed up by any real world observation. Near identical values were found at the South Pole, which was measured first, before Mauna Loa. I don’t think that there is much outgassing nor sinks in thousands meters of ice.
But now, 45 years later, we can say with confidence that CO2 has nothing to do with the climate.
You have a quite strong manner of categoric statements. I should say the “CO2 has little to do with climate”, much less than the GCM’s try to convince us of. But “nothing” can’t be said, as we simply have not enough data to show the effect of more CO2 in the atmosphere, one way or the other.
Jeff Glassman says:
June 27, 2010 at 6:11 pm
To prove you wrong, I quoted the calibration techniques applied to the those monthly records data you say are pure laboratory data. Those techniques included an unquantified “linear gain factor”, applied not to MLO but to SP and BH.
I never said that the monthly average data are pure laboratory data. The raw hourly averages are pure (calculated) laboratory data. All further averages are based on a selection of these data, by the different organisations, not the IPCC. The selection doesn’t change the average, curvatory or trend of the raw data, neither the differences between different stations, as I have repeatedly shown in the combined graphs of Mauna Loa with Samoa and with South Pole data. The “linear gain factor” is the difference of the seasonal curves of the present with the previous year as can be seen here:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/mlo_co2_seasons.jpg
Nothing sinister here and again, the IPCC is not involved in any way.
Correction procedures for missing data used for the averages may change over time, as good for Mauna Loa as for other stations. See WUWT of some time ago:
http://wattsupwiththat.com/2008/08/06/post-mortem-on-the-mauna-loa-co2-data-eruption/
In all cases there is no difference in average or trend between the “pure” laboratory data and the monthly averaged data beyond a few tenths of a ppmv.
If you have any indication of a change in these factors between the raw data and the published averages, we can discuss this further. Otherwise stop your allegations, you only make yourself unbelievable.
In the spirit of science and accuracy, I will concede that there is indeed a pressure gradient between the partial pressure of CO2 in the atmosphere and the partial pressure of CO2 in the water. The latter is zero. When a gas is dissolved in a solvent, it exerts no more gas pressure. Therefore, the gradient you and IPCC endorse is equal to the partial pressure of CO2 in the atmosphere. Is that better?
This should close the books for any first years chemistry student, give him/her an F grade with the urgent request to look for another study, as far away as possible from chemistry (or even physics).
Even Henry’s Law shows something different:
CO2(g) = [CO2] (at K_0), (1)
Where [CO2] is gaseous CO2 in the wather, thus free, not dissolved, CO2 in the liquid phase. This excerts a pressure to get out of the water, which is indirectly measured by getting it in equilibrium with a small amount of air above it. That is what Henry’s law says. For seawater it is never zero and called the pCO2 of the water phase, which may differ from the pCO2 in the atmosphere above it. While measured indirectly, it is the real pressure of free CO2 dissolved in the water, otherwise it would never come out again. In physical terms, it is called the “fugacity” of the dissolved CO2.
From http://www.britannica.com/EBchecked/topic/221428/fugacity
a measure of the tendency of a component of a liquid mixture to escape, or vaporize, from the mixture. The composition of the vapour form of the mixture, above the liquid, is not the same as that of the liquid mixture; it is richer in the molecules of that component that has a greater tendency to escape from the liquid phase. The fugacity of a component in a mixture is essentially the pressure that it exerts in the vapour phase when in equilibrium with the liquid mixture.
What I am saying is that Henry’s Law applies to total gas dissolved in a solvent
There it is where you go wrong: Henry’s Law is not “total” gas dissolved in a solvent, the right term [CO2] is the concentration of not ionized CO2 in solution (including H2CO3). Bicarbonate and carbonate ions are not part of Henry’s law, but part of the ionic buffer reactions and all together form DIC. If for any reason more [CO2] is formed (lower pH by undersea volcanic HCl) or less (by algal blooms), then the result of Henry’s Law is influenced as [CO2] is changed, even if the temperature and salinity didn’t change. That is the difference between a cola/fresh water/champagne bottle and seawater.
More details here:
http://www.eoearth.org/article/Marine_carbonate_chemistry#Dissolved_Carbon_Dioxide
Some excerpts:
The sum of [CO2(aq)] and [H2CO3] is denoted as [CO2].
At typical surface seawater pH of 8.2, the speciation between [CO2], [HCO3(-)], and [CO3(2-)] hence is 0.5%, 89%, and 10.5%, showing that most of the dissolved CO2 is in the form of HCO3- and not CO2
Thus a doubling of CO2 in the atmosphere will double [CO2] from 0.5% to 1% in first instance, and that will increase bicarbonate and carbonate somewhat, but will not double these two, thus seawater doesn’t double in CO2 content.
This shows where you are wrong and makes that several assumptions made with the wrong idea about Henry’s Law are wrong too. More about that later…
Sorry, a mistake in the previous message:
Where [CO2] is gaseous CO2 in the wather, thus free, not dissolved, CO2 in the liquid phase.
Of course it is dissolved in the liquid phase, be it still as CO2 (and for a small part as H2CO3), but not ionised.
Ferdinand Engelbeen, 6/28/10 at 3:51 am said,
>> Well, if you can prove that Revelle was wrong in his “conjecture”, there are hundreds of scientific works confirming it. The basics of buffering solutions are teached in first years chemistry classes…
Expect proofs in logic and mathematics, not science. You will find a thorough treatment in rocketscientistsjournal.com, “On Why CO2 is Known Not To Have Accumulated in the Atmosphere, etc.”, Part 5, especially the discussion around Figures 3 to 5.
If there are hundreds of scientific works confirming Revelle, about one such citation that’s freely available on-line?
Here’s an interesting passage from Charles Keeling’s autobiography:
>>Because I could by then, in retrospect, see a seasonal variation in the carbon isotopic ratios of CO2 in my earlier afternoon data from Caltech, I proposed that the activity of plants growing on land was the cause of the seasonal cycle. This activity explained why maximum CO2 concentrations in both hemispheres were observed in the spring, when most plants begin to grow. The observed year by year rise in concentration was close to that expected if all of the industrial CO2 from combustion of fossil fuels remained in the air. Aware, however, of Revelle’s conviction that the oceans must be absorbing some of that CO2, I noted that longer records might cause a revision in the estimated rise. This was a good judgment call. In the 1970s, with much longer records of CO2, a coworker, Robert Bacastow, discovered that a transient release of CO2 from natural sources, associated with a powerful E1 Niño event in 1958, had exaggerated the average rise in these early data.
So at first, Keeling required 100% of ACO2 from fossil fuels to remain in the atmosphere. That could not be substantiated, and what he witnessed in his early data was attributed to El Niño. In 2006, A. C. Manning and Keeling’s son, R. F. Keeling, re-examined the seasonal variability Charles had attributed to terrestrial growing seasons. The said,
>>In conclusion, we have shown that a significant fraction of the
short-term variability in our CO2 and O2/N2 data at MLO can be
explained by real atmospheric variability rather than by artifacts
of our flask sampling procedure or analysis. We have suggested
that this variability may be related to seasonal north-south
concentration gradients that exist in the tropics as a result of
opposing seasonal variations at middle latitudes in either
hemisphere and have given statistical evidence to support this.
Manning, A.C. and R. F. Keeling, “Correlations in Short-Term Variations in Atmospheric Oxygen and Carbon Dioxide at Mauna Loa Observatory”, 11/8/06.
Apparently the authors didn’t accept that that the MLO variations were due to terrestrial biology. In fact, biological effects are not even a candidate source for the MLO variations. Also, note that Manning and Keeling restrict their study to MLO, and not some alleged global data set. The authors are not even explicit in identifying that the MLO short term variations they address are on the seasonal scale. Regardless, Manning and Ralph Keeling leave the matter by saying that based on the data available, the best estimate for the cause of the seasonal effects at MLO is north-south seasonal transport between the hemispheres, coupled with their differing CO2 concentrations. My suggestion to them is to examine the lie of the plume of the oceanic outgassing as it follows the seasonal trade winds across Hawaii.
You protest the physics of the partial pressure of a gas by repeating the same fiction. Your model does not agree with Zeebe and Wolf-Gladrow. As I quoted on 6/27/10, the latter state that the concentration of dissolved CO2 is proportional to the partial pressure of CO2 in the gas above the solvent, where the constant of proportionality depends on temperature and salinity. Your model is a contradiction because it involves a partial pressure gradient.
I made no claims about the “speed of outgassing/absorption” beyond saying that it is affected by the wind and is otherwise irrelevant because it is much faster than climate time scales and has no net global effect. Keeling’s data are backed by Keeling’s data. As I have painfully laid out for you in detail with full references, IPCC made the South Pole data look “near identical” to MLO by applying a “linear gain factor”, whose form and value it keeps secret.
How can one object to having more data? What we need before we spend any money on data collection is a review of climate based an honest and complete model fitting the data we already have and contradicting none.
Further discussion…
The partial pressure, pCO2, is important, too, because the ocean will dissolve CO2 out of the atmosphere in proportion to pCO2, that is, in proportion to the CO2 concentration in the atmosphere immediately above the water.
No, it is the difference between pCO2 of the atmosphere and pCO2 of the oceans which drives the local direction and speed (together with other factors like wind speed). As the (largely temperature driven) oceanic pCO2 values show, the pCO2 difference air-ocean surface is highly negative near the equator and positive near the poles. In the mid-latitudes, the difference is positive in summer and negative in winter.
At the time of the descent of what is the THC at the poles, seawater will be loaded with CO2 corresponding to its solubility at about 0ºC and at the local partial pressure in the polar atmosphere.
The measured pCO2 of seawater near the North Pole is about 230 microatm. The measured pCO2 of the atmosphere at 7 m height at Barrow is about 390 microatm. It is that difference which drives the uptake. There is little difference between the atmospheric pCO2 near Barrow (raw or selected data…) and near the equator and at Antarctica. Barrow is higher than at the equator and that is higher than near Antarctica. The yearly average difference is less than 5 ppmv.
Please note that in every case, the chemical equations relate to the state of equilibrium. Those equations will hold once the surface layer of the ocean reaches equilibrium, and not a moment before.
Again you are completely lost: these equations are describing a dynamic equilibrium, not a static one. All reactions shift if the concentration of one of the constituents changes, including [H(+)] (pH).
The pH and the concentration of ions in the surface layer do not regulate Henry’s Law, the dissolution of CO2.
Yes, they do influence [CO2], thus the dissolution of CO2. Henry’s Law only regulates the next step between [CO2] and CO2(atm).
And isn’t it ironic that so much time is spent on CO2, that it has been thoroughly misunderstood by IPCC, and in the end it has no measurable affect on climate?
While one can have a lot of critique on the other cornerstone of the AGW theory, there is little doubt that humans are responsible for the recent increase in the atmosphere. All known observations support that. None contradict that. To counter the “consensus” on this, one need very solid arguments. If these are based on wrong assumptions, that works counterproductive for the arguments used for the other points where the “consensus” is on more shaky grounds.
Ferdinand 9.27am
I wonder if we can agree on the cornerstones of AGW? This will help us to focus on countering the weak points
Hypothesis
1) Human introduced co2 causes substantial and alarming warming. (radiative physics)
This ’cause’ has had the following (claimed) effects;
2) Sea levels are rising through thermal expansion/glacier melt
3) Land temperatures have been rising since 1880
4) The Earths climate has been relatively static throughout history until introduction of (1) causing temperature to rise.
I am not asking anyone to agree or disagree as to cause and effect, just whether this sums up the four cornerstones which need to be demolished.
Tonyb
Jeff Glassman says:
June 28, 2010 at 8:56 am
While looking at part 5 of your “why CO2 has not accumulated…”, I saw the Takahashi diagram, where you say:
For the minimum values of each Takahashi cell, the total outgassing, uptake, and net would be (-4.11, 6.64, -3.44) GgmC/yr, at average they are (-3.32, 1.20, -2.12) GgmC/yr, and at maximum, (-2.54, 1.73, -8.05) GgmC/yr. {Begin rev. 12/30/09}The values should be on the order of 90 PetagmC/yr, an unresolved discrepancy of 10^7.
What you haven’t seen is that the Takahashi diagram is about the net release/uptake of CO2 for each cell, that is the integrated fluxes plus and min for each cell over a year. The net total result is about 2 GtC net uptake by all ocean surfaces together.
While there are cells near the equator which show permanent release of CO2 and cells near the poles show permanent uptake, the bulk of the cells in the mid-latitudes show release in summer and uptake in winter. Thus a (large) part of the 90/92 GtC transfer is in/out the same cells within a year and some (smaller) part is released from the equator and absorbed near the poles. See the summer-winter difference of the same diagram at:
http://www.pmel.noaa.gov/pubs/outstand/feel2331/images/fig03.jpg
This is what makes the residence time which (in the case of the ocean-atmosphere and vegetation-atmosphere) is largely bidirectional in the same cells and only a smal part is unidirectional and even a smaller part is really differential uptake/release. The latter is what governs the decay rate, not the residence time.
If there are hundreds of scientific works confirming Revelle, about one such citation that’s freely available on-line?
See “Changes in the Carbon Dioxide Content of the Atmosphere and Sea due to Fossil Fuel Combustion” by Bert Bolin and Erik Eriksson, 1958. On line at:
http://onramp.nsdl.org/eserv/onramp:16573/n8._Bolin___Eriksson__1958corrected.pdf
One relevant quote:
An addition of CO2 to the water will change the pH and thereby decrease the dissociation resulting in a larger portion of CO2 and H2CO3 molecules. Since the pressure of CO2 in the gas phase being in equilibrium with CO2 dissolved in water is proportional to the number of CO2 and H2CO3 molecules in the water, an increase of the partial pressure occurs which is much larger (about 12.5 times) than the increase of the total content of CO2 in the water.
Also interesting, the history behind the Revelle factor:
http://www.aip.org/history/climate/Revelle.htm
With a reference to the ocean pCO2 measurements of Buch (1933!):
Observations in the 1930s had established the key data (such as how the partial pressure of CO2 in sea water varied as a function of acidity).(5*)
http://www.biokurs.de/treibhaus/literatur/buch/buch1939.pdf
I hope that you can understand some German…
———–
So at first, Keeling required 100% of ACO2 from fossil fuels to remain in the atmosphere. That could not be substantiated, and what he witnessed in his early data was attributed to El Niño. In 2006, A. C. Manning and Keeling’s son, R. F. Keeling, re-examined the seasonal variability Charles had attributed to terrestrial growing seasons.
Your interpretation of Manning and R.F. Keeling:
Regardless, Manning and Ralph Keeling leave the matter by saying that based on the data available, the best estimate for the cause of the seasonal effects at MLO is north-south seasonal transport between the hemispheres, coupled with their differing CO2 concentrations.
Again, it seems that you are a master of misinterpretation of what some others say: Manning and Keeling Jr. saw that there were disturbances to the “normal” NH seasonal variability at MLO and these were probably caused by the short term disturbances from opposing flows between the NH and SH. The latter don’t cause the seasonal variability at MLO, only the disturbances of the seasonal variability. Any other station in the NH shows a similar, but more pronounced seasonal variability at about twice the amplitude of MLO. And the maxima are in winter/spring, the minima in summer/fall, opposite to your supposed seawater temperature/outflow influence:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/month_2002_2004_4s.jpg
Where Barrow is at the edge of the cold Arctic Ocean, but receives air from the mid-latitudes via the Ferell cells.
the latter state that the concentration of dissolved CO2 is proportional to the partial pressure of CO2 in the gas above the solvent, where the constant of proportionality depends on temperature and salinity. Your model is a contradiction because it involves a partial pressure gradient.
You still don’t get it. Let us try to put it in another way: one establishes the “fictional” pCO2 of seawater by spraying seawater in a small volume of air and measuring the pCO2 of the that small volume. The sea surface water used for this experiment thus has a theoretical pCO2 as found in the test.
Now assume that the ambient air at sea level has – surprisingly – the same pCO2. What will happen then with the CO2 flows between the atmosphere and the oceans? Nothing, no net flow at all, as both have the same pCO2 . If there was zero CO2 in the ocean surface, you would be right. But there is already CO2 in the oceans. Depending of the pCO2 in water, based on Henry’s Law, and pCO2 in the atmosphere, there would be a CO2 flow in direction and ratio with the difference between the partial pressures involved…
IPCC made the South Pole data look “near identical” to MLO by applying a “linear gain factor”, whose form and value it keeps secret.
Completely false allegation, based on misinterpretation of the meaning of “linear gain factor”, repeatedly shown false as the raw data show identical averages as the “manipulated” data within a few tenths of a ppmv…
tonyb says:
June 28, 2010 at 12:46 pm
I think that indeed these are the cornerstones. There are a lot more derivatives, some are widely accepted by the IPCC, others not widely accepted, but still are used by the more extreme alarmists:
Widely accepted:
– spread of vector deseases
– more intense storms/hurricanes
– intenser drought at some other parts of the globe
Not widely accepted
– THC shutdown and NH freezing
– runaway warming
I suppose one can find several more…
Ferdinand Engelbeen, 6/28/10 at 8:56 am said,
>>What you haven’t seen is that the Takahashi diagram is about the net release/uptake of CO2 for each cell, that is the integrated fluxes plus and min for each cell over a year. The net total result is about 2 GtC net uptake by all ocean surfaces together.
I said nothing different, and you cite nothing from me to show that I overlooked that fact.
You said,
>>Thus a (large) part of the 90/92 GtC transfer is in/out the same cells within a year and some (smaller) part is released from the equator and absorbed near the poles.
Perhaps you would agree that the average output for a single cell is its net output for the interval, keeping track of positive being absorption and negative being outgassing. And perhaps you would agree that the average output for the sum of all cells is the sum of the averages for all cells, which is the net for the whole ocean. I took the sum over all net positive cells to be the net absorption, and the sum over all net negative cells to be the net outgassing. The yearly net absorption I took to be about 92 GtC, and the yearly net outgassing to be about 90 GtC, according to IPCC AR4 Figure 7.3, p. 515, and thus the net was about 2 GtC absorbed. Clearly you disagree in the details.
You seem to have determined that the 90 GtC is the sum of the output from all cells while they are outgassing, and 92 GtC to be the sum while they are absorbing, and so these are not apparent in Takahashi’s analysis. I would agree that you get the same net result for the ocean, preserving the signs. What leads you to believe that this is what IPCC’s figures of 90 and 92 mean?
If the Takahashi diagram is correct, what do the partial sums of all positive cells and all negative cells in the diagram mean?
What do you think causes cells to absorb and outgas, if its not the solubility effect?
IPCC says,
>>In winter, cold waters at high latitudes, heavy and enriched with CO2 (as DIC) because of their high solubility, sink from the surface layer to the depths of the ocean. This localised sinking, associated with the Meridional Overturning Circulation (MOC; Box 5.1) is termed the ‘solubility pump’. Over time, it is roughly balanced by a distributed diffuse upward transport of DIC primarily into warm surface waters. AR4, ¶7.3.1.1, The Natural Carbon Cycle, p. 514.
Are the cold waters at high latitudes much different in winter than in summer? Isn’t the polar water where it descends approximately ice water? This water in the MOC, also known as the THC, returns to the surface in warm waters. CO2 was absorbed because of solubility, it says. Do you believe that it was returned later to the atmosphere because of solubility, now in warm waters? Are you familiar with the flow in the THC? It’s in the range of a few to a couple of dozen Sv. Have you checked the solubility curve to see if the difference in temperature and the flow rate work out to about 90 GtC or so? I have, and they do. A temperature difference of 30ºC from the headwaters to the discharge fits a flow of 5 Sv, and a difference of 10ºC fits 10 Sv.
This is a continuous flow, a river of CO2, and the output of natural CO2 depends on the SST at venting.
The geographical distribution of the discharge is somewhat uncertain, but the Takahashi diagram provides a hint. The Takahashi diagram also has a strong resemblance to SST. Does he explain why? Some of his key papers are only for purchase or in larger university libraries.
You said,
>>The measured pCO2 of seawater near the North Pole is about 230 microatm.
Surely you jest! You can’t even show that seawater has a pCO2. It is deemed to exist, to be the pCO2 of the air above it when in equilibrium. This error contributes to your misunderstanding of Henry’s Law. Even Wikipedia, the Internet sorted, manages to get this right. It says,
>>In chemistry, Henry’s law is one of the gas laws, formulated by William Henry in 1803. It states that:
>>At a constant temperature, the amount of a given gas dissolved in a given type and volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid.
>>An equivalent way of stating the law is that the solubility of a gas in a liquid at a particular temperature is proportional to the pressure of that gas above the liquid. Henry’s law has since been shown to apply for a wide range of dilute solutions, not merely those of gases.
It’s the pressure of “that gas above the liquid”, not your alleged pressure gradient. Accord: Zeebe & Wolf-Gladrow, quoted for you on 6/27/10 at 7:56 am.
You insist otherwise, repeatedly, as in:
>>Depending of the pCO2 in water, based on Henry’s Law, and pCO2 in the atmosphere, there would be a CO2 flow in direction and ratio with the difference between the partial pressures involved…
I can see no reason for you to have inserted “based on Henry’s Law” where you did, but the only reasonable interpretation I can find is that you think Henry’s Law depends on both partial pressures. Can you provide a citation for that dual dependence?
You wrote,
>>>>(quoting me) What I am saying is that Henry’s Law applies to total gas dissolved in a solvent
>>There it is where you go wrong: Henry’s Law is not “total” gas dissolved in a solvent, the right term [CO2] is the concentration of not ionized CO2 in solution (including H2CO3).
You are quite right. I miswrote. And your correction is supported in Zeebe & Wolf-Gladrow just above my citation on 6/27/10. Do bear in mind that CO2 dissolves in water even without equilibrium. The mass balance of CO2 works using the solubility curve, and it fits the Vostok data, regardless that Zeebe et al.’s derivation applies only to “thermodynamic equilibrium”. That includes their statement that
>>At typical surface seawater pH of 8.2, the speciation between [CO2], [HCO3^−], and [CO3^2−] is 0.5%, 89%, and 10.5%, respectively, showing that most of the dissolved CO2 is in the form of HCO3− and not in the form of CO2 … . The low ratio of molecular CO2 is valid only in thermodynamic equilibrium. Before equilibrium, no theory tells us the ratio of the forms.
You quote the identical ratio from a different source. Then you conclude,
>>Thus a doubling of CO2 in the atmosphere will double [CO2] from 0.5% to 1% in first instance, and that will increase bicarbonate and carbonate somewhat, but will not double these two, thus seawater doesn’t double in CO2 content.
This would be true — if only the system were in thermodynamic equilibrium. Too bad, for your model. Also, equilibrium is not a continuum, a measurable condition. There is no phase trajectory through the parameters leading to equilibrium. A small disturbance might precipitate a huge shift in the ratio, perhaps even making CO2(aq) the overwhelming majority in the ratio. No theory exists to guide us in disequilibrium.
Takahashi says,
>>Only about 0.5% of the total CO2 molecules dissolved in seawater communicate with air via gas exchange across the sea surface. This quantity is called the partial pressure of CO2 (pCO2), which represents the CO2 vapor pressure. The seawater pCO2 depends on the temperature, the total amount of CO2 dissolved in seawater and the pH of seawater. Takahashi, T and SC Sutherland, “CO2 Partial Pressure Data for Global Ocean Surface Waters”, v. 1.0, 10/20/06, p. 2.
This passage relies on Henry’s Law and equilibrium in the surface layer. It continues,
>>The rate of transfer of CO2 across the sea surface is estimated by: (sea-air CO2 flux) = (transfer coefficient) x (sea-air pCO2 difference). The transfer coefficient depends primarily on the degree of turbulence near the interface, and is commonly expressed as a function of wind speed.
In another online document I deduce was due to Takahashi, he says,
>> The regional and global net CO2 values have been computed using (wind speed)2 and (windspeed)3 formulations for the wind speed dependence on the gas transfer rate with wind speeds at 10 meters and 0.995 sigma level (about 40 meters above the sea surface). http://www.ldeo.columbia.edu/res/pi/CO2/carbondioxide/pages/air_sea_flux_1995.html
Several aspects of the Takahashi analysis are worth noting. (1) If the ocean equilibrated with the atmosphere instantaneously, Takahashi’s flux rate would be zero even if CO2 had crossed the interface instantaneously. (2) Takahashi uses SST temperature, for example to reject biased samples, but not as a prime parameter for flux. Nevertheless, his diagram has a striking appearance as a measure of SST. This is evidence of Henry’s Law. (3) Most of the net outgassing is in the Equatorial regions, roughly 20º to 30º wide, skewed north in the Indian Ocean and south in the Atlantic. Outside these outgassing regions, a patch of seawater being carried on prevailing currents, which have a general poleward component, absorbs CO2 all along its path, and increasingly so. An interesting analysis would be to integrate the Takahashi cells along the paths of prevailing currents to arrive at a total outgassing and then re-uptake.
Your own reference trips you up. It says,
>>Gaseous carbon dioxide (CO2(g)), and [CO2] are related by Henry’s law in THERMODYNAMIC EQUILIBRIUM: … (Caps added)
and
>>The pCO2 of a seawater sample refers to the pCO2 of a gas phase in equilibrium with that seawater sample.
In other words, the pCO2 of a seawater sample does not refer to a real gas pressure in the solvent. The pressure gradient the experimenters are measuring may be a measure of disequilibrium, indicating that only the dissolution is incomplete.
On this point, you wrote,
>>Again you are completely lost: these equations are describing a DYNAMIC EQUILIBRIUM, not a static one. All reactions shift if the concentration of one of the constituents changes, including [H(+)] (pH). (Caps added.)
This is false. You introduced “dynamic equilibrium”, and without reason or authority. As I took great care to explain on this thread, dynamic equilibrium is not thermodynamic equilibrium. IPCC, being unaware of the differences, uses just plain “equilibrium”, but its own authorities make clear that what is required for their analysis is thermodynamic equilibrium. Furthermore, where a pressure gradient appears to exist, the process is not even in dynamic equilibrium.
Climatology and oceanography are not unique in that the steady state or equilibrium assumption make intractable problems tractable. This is all à priori modeling, and requires validation with experiment before it can advance from hypothesis to theory.
You wrote,
>>>>(quoting me) If there are hundreds of scientific works confirming Revelle, about one such citation that’s freely available on-line?
>>See “Changes in the Carbon Dioxide Content of the Atmosphere and Sea due to Fossil Fuel Combustion” by Bert Bolin and Erik Eriksson, 1958. On line at: http://onramp.nsdl.org/eserv/onramp:16573/n8._Bolin___Eriksson__1958corrected.pdf
First, note that Bert Bolin was the first chairman of IPCC, from 1988 to 1997. He doesn’t qualify as a confirming source for anything IPCC might have written.
Bolin and Eriksson wrote:
>>Towards the end of their paper Revelle and Suess point out, however, that the sea has a buffer mechanism acting in such a way that a 10 % increase of the CO2-content of the atmosphere NEED MERELY BE BALANCED by an increase of about 1 % of the total CO2 content in sea water, TO REACH A NEW EQUILIBRIUM. The crude model of the sea they used assuming it to be one well-mixed reservoir of CO2, did not permit them to study the effect of this process more in detail. (Caps added.)
The last sentence is a tactful way of saying that the R&S were not successful in their paper. B&E don’t exactly confirm R&S, but attempt to correct their buffer effort by providing a better model for the ocean.
Note, too, that R&S didn’t say that a 10% increase WAS in fact balanced by a 1% increase in TCO2, only that it need be so to reach a new equilibrium. Theirs was an analysis passing from equilibrium to equilibrium. So was this effect ever confirmed? B&K say,
>>The change of pH in the sea will shift the dissociation equilibrium also for the carbon dioxide containing C14. We may assume an equilibrium rapidly being established and have … . P. 137
A scientist may make any assumptions he wishes. He can throw in magic, or violate the laws of thermodynamics. However, whatever assumptions he does make put a caveat on his model. The Revelle buffer is a relationship between parameters that can be estimated, meaning that a number can be assigned. Without a predicted buffer factor with which to compare the empirical number, however, the model is not validated. The mere quantification of the factor constitutes no validation whatsoever. A measure of confirmation might also accrue to a model if it agrees with another, independent model. However, the ultimate confirmation is validation of a nontrivial prediction by some experimental method.
Bolin & Eriksson repaired the failed Revelle buffer factor, but did not confirm it — even after it was fixed. The Revelle factor was an attempt to show how CO2, and in particular ACO2, would accumulate in the atmosphere to cause manmade global warming. The analysis required the assumption of thermodynamic equilibrium, and since that does exist in the climate, neither B&E nor R&S have linked ACO2 to global warming.
Bolin & Eriksson is interesting because it links IPCC’s errors through one of its founding fathers going back 30 years before IPCC was founded, and two years before that to Revelle & Suess.
You wrote,
>>Manning and Keeling Jr. saw that there were disturbances to the “normal” NH seasonal variability at MLO and these were probably caused by the short term disturbances from opposing flows between the NH and SH. The latter don’t cause the seasonal variability at MLO, only the disturbances of the seasonal variability.
So you determined that Manning and RF Keeling were talking about the variability of the variability! Did you actually find that in their paper, because it is not true. They talk about the “short-term variability”, appearing first in the title of their paper, and defined by them in the following:
>>As a measure of short-term variability, we have computed the residuals in O2/N2 and CO2 relative to smooth curves through the data. Manning & RF Keeling, “Correlations in Short-Term Variations etc.”, p. 1 of 3.
These residuals are the full, peak to peak, seasonal parts of the records. Their graphs confirm it. If they were examining the variability in the seasonal records, they would have had to subtract not just the “smooth curves”, but also an estimate of the seasonal variation. They never reported doing that.
>>This paper will try to establish whether the residuals of the flask data from the smooth curves fitted through the data are due to experimental artifacts or real atmospheric variability; that is, whether there is some problem with the sampling procedure used to collect the air samples at MLO or whether there are one or more natural processes affecting the air at MLO, and in a manner not seen at other SIO stations. Id.
>>This agreement [between the variability of the O2/N2 and CO2 residuals] suggests that the north-south transport may indeed be implicated as a source of variability at MLO. Id., p. 2 of 3.
What they have said is that “the north-south transport may indeed be implicated as a source of [the short-term variability, that is, the full seasonal cycle] at MLO”. There is no variability in the seasonal cycle compared to some idealized seasonal cycle.
>>In chemistry, Henry’s law is one of the gas laws, formulated by William Henry in 1803. It states that:
>>At a constant temperature, the amount of a given gas dissolved in a given type and volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid.
Strictly Henry’s Law doesn’t apply to CO2 in water because CO2 reacts with water but it’s a good approximation.
A small disturbance might precipitate a huge shift in the ratio, perhaps even making CO2(aq) the overwhelming majority in the ratio. No theory exists to guide us in disequilibrium.
Rubbish, Le Chatelier’s principle and reaction kinetics do just fine.
CO2 is constantly flowing in and out of solution, under constant conditions a constant ratio between the gas phase concentration and liquid phase concentration is the Henry’s Law coefficient. In the case of CO2/water you have the more complicated system of CO2(g)⇋CO2(l)+H2O⇋H2CO3⇋HCO3− + H+⇋CO32− + H+
The rate constants and equilibrium constants for all of these are known, change the concentration of CO2(g) and the forward rate of production of CO2(l) goes up and exceeds the rate of flow back into the gas phase so the concentration of CO2(l) goes up and so the production of H2CO3 goes up and so on until all the species are in equilibrium with each other. The time it takes to reach the new equilibrium state is determined by the rates of all the forward/backward reactions, of course if the pCO2 changes too rapidly the equilibrium will never be actually achieved. One way the rates can be measured is to add CO2 containing C13 or C14 and observe the rates of accumulation of the isotope in the various species. Basically the way the experiment was conducted in the Earth’s atmosphere during the nuclear bomb tests in the 60s.
Jeff Glassman says:
June 29, 2010 at 7:34 pm
The yearly net absorption I took to be about 92 GtC, and the yearly net outgassing to be about 90 GtC, according to IPCC AR4 Figure 7.3, p. 515, and thus the net was about 2 GtC absorbed.
That is right. But you say:
For the minimum values of each Takahashi cell, the total outgassing, uptake, and net would be (-4.11, 6.64, -3.44) GgmC/yr, at average they are (-3.32, 1.20, -2.12) GgmC/yr, and at maximum, (-2.54, 1.73, -8.05) GgmC/yr. {Begin rev. 12/30/09} The values should be on the order of 90 PetagmC/yr, an unresolved discrepancy of 10^7.
There is no unresolved discrepancy. For every cell, Takahashi calculated the yearly average flux, by integrating the positive and negative fluxes over a year. Simply compare the winter/summer and yearly plots. For a lot of cells in the mid-latitudes, than means out of the oceans in summer and into the oceans in winter. No matter if you believe in pCO2 or temperature influence only. In all cases, the positive fluxes are part of the 92 GtC uptake of the oceans and the negative fluxes are part of the 90 GtC outgassing. Thus not all 90/92 GtC is in the continuous flow between the equator and the poles, a lot is in the intermittent part. For the residence time, it doesn’t matter if the exchange is local intermittent or hemispheric continuous. It only shows up in the thinning of the isotope ratio’s, as deep ocean d13C/d14C ratio’s are different from upper ocean ratio’s and not influenced by current day changes.
If the Takahashi diagram is correct, what do the partial sums of all positive cells and all negative cells in the diagram mean?
The partial sums of all positive/negative cells only shows that the net result over a year for those cells is positive or negative. That doesn’t give any clue if the individual cell in that year was continuously positive, negative or intermittent positive and negative. Just look at the differences in each cell between winter and summer. The 90/92 GtC are the integral of separated all positive and all negative flows within a year apart, not the integral of the net fluxes over a year.
Have you checked the solubility curve to see if the difference in temperature and the flow rate work out to about 90 GtC or so? I have, and they do.
The solubility curve you use fits only for one DIC and pH. As there are relevant differences in DIC and pH between the equator and the poles, there is no 90 GtC going directly from the atmosphere into the deep oceans, but much less. That is what Feely/Takahashi say and what can be deduced from d13C changes in atmosphere and oceans, due to human emissions. Here a graph which shows the different d13C trends for different atmosphere – deep ocean exchanges, based on the influence on d13C in the atmosphere from fossil fuel burning:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/deep_ocean_air_zero.jpg
That includes indirect exchanges via the upper-deep ocean exchanges (not directly via the THC) and excludes vegetation exchanges (which are largely bidirectional), which may explain the discrepancy in the earlier years.
Thus my “best guess” is that the total atmosphere – deep ocean exchange is about 40 GtC/year, not the full 90/92 GtC you expect.
————–
Surely you jest! You can’t even show that seawater has a pCO2. It is deemed to exist, to be the pCO2 of the air above it when in equilibrium.
This is what makes discussions with you that difficult: near everybody in the world, who is involved in CO2 levels uses the pCO2 of seawater, as defined as the pCO2 of the atmosphere above seawater when both are in equilibrium, except you. Indeed it can’t be measured in seawater itself (but it can be calculated), but it simply represents the fugacity of CO2 to get out of the water.
If the air above the seawater had no CO2 content at all, CO2 from the solution will get out of the water until the equilibrium is reached. That is a dynamic equilibrium, as the fluxes in and out at that moment are equal.
If the real atmosphere has a higher pCO2, that will push more CO2 into the water and reverse. These are all dynamic equilibria, which have time constraints, partly by the pCO2 difference, partly by the mechanical mixing and moleculare diffusion speed of the upper oceans. The average equilibrium time constant is about a year. That doesn’t play much role at the equator and poles, but it is important in the mid-latitudes, as the temperature and biolife of the upper oceans there changes (opposite) over the seasons.
In other words, the pCO2 of a seawater sample does not refer to a real gas pressure in the solvent. The pressure gradient the experimenters are measuring may be a measure of disequilibrium, indicating that only the dissolution is incomplete.
This says it all: if there was no intention of CO2 in solution to come out, the pCO2 of seawater as defined, would be zero. Henry’s Law is not unidirectional: if the amount of CO2 in solution is proportional to the pCO2 of the atmosphere at a given temperature and salt content, the opposite is true too. Thus if there is a certain amount of free [CO2] in the solution, that would come out until the pressure of CO2 in the atmosphere is in equilibrium with the tendency of the CO2 in solution to get out. Thus pCO2 of water is well defined and is about the tendency of CO2 in water to escape, and has nothing to do with the actual pCO2 of the atmosphere. The difference between the two is what drives the fluxes, as the pCO2 of seawater is directly related to what is already dissolved as free CO2 in the liquid. The higher that is, the slower the flux.
This is false. You introduced “dynamic equilibrium”, and without reason or authority. As I took great care to explain on this thread, dynamic equilibrium is not thermodynamic equilibrium.
Again you are completely wrong. Near everybody say “equilibrium” while meaning “dynamic equilibrium”, as that is what in about every case happens in nature. In all cases, time constraints are active, which means that no natural system is actually momentarely in (dynamic) equilibrium, but the equilibria shift continuously with the change in parameters. That is e.g. the case for solubility and fluxes of CO2 with temperature in the mid-latitudes.
Further, Henry’s Law only covers only one thermodynamic part of the equilibrium. If the concentration of free CO2 in the liquid changes for any reason, that will influence the result of Henry’s Law in the (equilibrated) atmosphere above it. Simple experiment:
Add a small amount of a strong acid (HCl) to seawater and see what happens: CO2 will come out (in equilibrium) into the atmosphere above it, even if the temperature and salt content hardly changed. That is the chemical part of it, which together with Henry’s Law makes the pCO2 of seawater.
However, the ultimate confirmation is validation of a nontrivial prediction by some experimental method.
If Bolin may not be used as confirmation of the buffer effect of CO2, even if that was already established in the 1930’s, who can convince you?
Maybe Zeebe is good enough?
http://www.eoearth.org/article/Marine_carbonate_chemistry
While the increase in surface ocean dissolved CO2 is proportional to that in the atmosphere (upon equilibration after ~1 y), the increase in TCO2 is not. This is a result of the buffer capacity of seawater. The relative change of dissolved CO2 to the relative change of TCO2 in seawater in equilibrium with atmospheric CO2 is described by the so-called Revelle factor:
R = (d[CO2]/[CO2]) / (d[TCO2]/[TCO2]) (7)
which varies roughly between 8 and 15, depending on temperature and pCO2. As a consequence, the man-made increase of TCO2 in surface seawater (ocean acidification) occurs not in a 1:1 ratio to the increase of atmospheric CO2 (the latter being mainly caused by fossil fuel burning). Rather, a doubling of pCO2 only leads to an increase of TCO2 of the order of 10%.
Or take some lessons at Warwick University from Dr. G.P. King, who describes in detail the reactions of CO2 in seawater, including the Revelle factor:
http://www.eng.warwick.ac.uk/staff/gpk/Teaching-undergrad/es427/Exam%200405%20Revision/Ocean-chemistry.pdf
————-
These residuals are the full, peak to peak, seasonal parts of the records. Their graphs confirm it. If they were examining the variability in the seasonal records, they would have had to subtract not just the “smooth curves”, but also an estimate of the seasonal variation. They never reported doing that.
Please read carefully what they have written at
http://www.esrl.noaa.gov/gmd/publications/annrpt22/MANNING.pdf
In first instance, the whole story is about the O2/N2 variability discrepancy against the CO2 variability. The seasonal variability is mainly in the NH and mainly from vegetation changes. That is largely confirmed by the seasonal O2/N2 changes and d13C changes, as well as at MLO as in all other NH stations.
Second, the text shows the following sentences:
Keeling and Shertz [1991] pointed out that there appeared to be greater relative short-term variability in O2/N2 at MLO than at other sites, but were unsure of the cause.
If that was about the full seasonal cycle, this would be opposite to reality: the seasonal cycle at Barrow, Alert and other NH places is (much) larger for CO2 and O2/N2 and d13C than at Mauna Loa.
Then from Fig. 1:
The curves shown (from which all residuals are calculated) were calculated with a least-squares fit to a function of two harmonics (annual and semi-annual periodicity) and a stiff Reinsch spline. [my bold]
The two harmonics makes the (smoothed) seasonal variability and the spline is the year-by-year increase. The residuals between the smoothed seasonal curve and the observations is the short time variability for which they are looking for an explanation. Not for the seasonal variability itself, of which the cause is largely known.
The seasonal variations are known from a lot of stations and air flights and nowadays satellite measurements. There is a huge north-south gradient and is most pronounced in the mid-latitudes:
http://www.esrl.noaa.gov/gmd/ccgg/globalview/co2/co2_intro.html
Re Phil, 6/29/10 at 9:18 am:
Phil’s like the kid who just woke up in the middle of the lecture and shouted out. He appears to have studied chemistry, at least through the lectures on equilibria, but never grasping either logic, e.g., if … then construction, argumentation, e.g., point – counterpoint, laboratory work, e.g., “the experiment was conducted” [period], or analysis, e.g., “Le Chatelier’s principle and reaction kinetics do just fine” [period].
Phil’s first two paragraphs are lifted verbatim out of Wikipedia, but without attribution or quotations. He strangely offsets his second paragraph (“>>”) as if it were a quote from somewhere on high. (A tip for the Phils of the world: Wikipedia is a great source for linking to research, but a risky one for quoting.)
Phil restates the stoichiometric equations as if that added to the dialog. The discussion has gone way beyond that stage. Those equations are explicit in IPCC’s Fourth Assessment Report, attributed to Zeebe & Wolf-Gladrow. That authority makes explicit that the equations apply to thermodynamic equilibrium. Even though climate is a fine example of a thermodynamic problem, IPCC not once mentions the term “thermodynamic equilibrium” (it does manage “equilibrium thermodynamics once) in its last two Assessment Reports. IPCC uses equilibrium repeatedly, and even implying the surface layer is in equilibrium by applying the equations Phil just repeated. But IPCC and some of the contributors to this thread, including Phil, do not grasp the implication.
Phil inserts Le Chatelier’s principle as if it applied. It is an axiom about systems saying they will transition between equilibrium states, given the chance. It says nothing about the trajectory between equilibrium states. I made the point that nothing is known about any trajectory between equilibrium states, to which Phil said “Rubbish” and for proof dropped the names “Le Chatelier’s principle and reaction kinetics” as if that meant something.
Phil interrupts the dialog to say,
>> Strictly Henry’s Law doesn’t apply to CO2 in water because CO2 reacts with water but it’s a good approximation.
To the contrary, Henry’s Law does indeed apply to CO2 in water. The application is analogous to applying blackbody radiation to Earth or the Moon. Of course it applies – just don’t leave out the empirical factor called emissivity. That adjusts the à priori model to fit the real world. In construction, it’s what is called a butch plate. A solubility curve exists for CO2. It is empirical in origin, and has undergone refinements for climate. So even though CO2 in solution undergoes a chemical reaction, forbidden in the reasoning behind Henry’s Law, the CO2 coefficient is a nice butch plate that brings the à priori into accord with experiment.
How well does solubility work? The test is in the application, and as I reported here recently, it works quite well for closure between THC flow rate and air-sea flux estimates. It also provides a best estimate for the relationship between CO2 and temperature in the Vostok record.
How well, then, do the stoichiometric equilibrium equations work for the surface layer? Answer: not very well at all. They lead to the Revelle buffer factor nonsense, and the build up of atmospheric ACO2 but not nCO2, and they make AGW work. But in the process, they violate Henry’s Law, which actually does work.
As I wrote here recently while Phil was asleep,
>>More important is that Henry’s Law informs us of the physics involved in a qualitative way, as fundamental as the recognition that balls roll down hill.
The issue here is not the equilibrium relationships repeated by a startled Phil. It is the application of those relationships where neither thermodynamic equilibrium nor even chemical equilibrium exists.
Could Phil be thinking that Le Chatelier’s principle is instead a law that proves equilibrium exists? He must do what others on this thread and IPCC have failed to do: first establish the existence of thermodynamic equilibrium, then rely they can rely on equilibrium relationships. Equilibrium first, then Le Chatelier’s principle. Equilibrium first, then the stoichiometric equations with the Bjerrum solution.
In addition, about the last part of my previous message, the clear explanation of what was done by Manning and Keeling Jr., in the text of the first page:
As a measure of short-term variability, we have computed the residuals in O2/N2 and CO2 relative to smooth curves through the data.
Clear to me that they looked at the variability around the seasonal variability…
Re Ferdinand Engelbeen, 6/30/10 at 5:39 am:
Your explanation of the unresolved discrepancy made no sense to me. Sorry. I don’t want to be repetitive, but I have to fall back on the sum of the net positive cells is the net positive uptake for the ocean, and vice versa. This is based on the sum of the averages being the average of the sums. The sums for the Takahashi diagram provide the correct net difference between uptake and outgassing, but not the uptake and outgassing separate estimates.
You say,
>>The solubility curve you use fits only for one DIC and pH.
Excellent! A commitment to shoot at. So you must have data that show a change in the CO2 solubility curve for a change in water DIC or pH!
Not only is the dependence amazing, but so is the fact that measuring it was practical. The first and second order effects of dissolution are temperature and pressure (including partial pressure), the ranking depending on the application. The third order effect is salinity. A conjecture for a fourth order effect is molecular weight. We’re already into difficult to measure territory. Now you add two more parameters, DIC concentration and pH. How do you think these might rank in order of importance?
Yours is novel physics. Novel means never before known physics, this time developed from climatology. There should be a Nobel prize in here somewhere.
With this new knowledge, we could use CO2 solubility to measure water pH and to measure the operating point on the Bjerrum plot.
For a couple of other reasons, CO2 is not significant to climate. (E.g., climate follows solar activity, Earth’s temperature response is regulated by albedo, and greenhouse gas absorption does not follow the logarithm of the concentration, but instead saturates, following an S curve according to the Beer-Lambert Law. IPCC manages to butcher all of these.) We have GCMs that don’t work as even first order models, and you want to refine the physics by what? A fifth order dependence on surface pH or DIC concentration?
You say,
>>This is what makes discussions with you that difficult: near everybody in the world, who is involved in CO2 levels uses the pCO2 of seawater, as defined as the pCO2 of the atmosphere above seawater when both are in equilibrium, except you.
But that is exactly what I have been saying. You seem to have accepted my argument, and now feedback my position saying I disagree with it. Perhaps I’ve not been clear enough.
The pCO2 of the atmosphere in equilibrium with the water is “taken to be”, “assumed to be”, “deemed to be”, or whatever synonym you want to use, the pCO2 for the water. The latter, of course, does not actually exist. My complaint is the novel model for Henry’s Law that you endorse in which solubility depends on the pCO2 gradient between gas and liquid. That is more novel physics.
As to “near everybody in the world”, (a) you need to get out more and (b) science is not about consensus. AGW is about consensus. Every new idea, every new direction comes from one person. Don’t expect a committee (a) to be correct or (b) to change course.
Takahashi used the pCO2 gradient to estimate the rate of flux. That is not the law of solubility. Henry’s Law says nothing about the rate of flux. It tells us how much CO2 is in the water after everything settles down, gms CO2 per 100 gms water usually, and how in climate at least, what counts most are temperature of the water and pCO2 or, equivalently, the atmospheric CO2 concentration.
Takahashi computed a hypothetical uptake per cell, inferred from empirical relationships about rates. His results might have been measured and reported in PgC/sec, but he multiplied his results by 3.2*10^7 to report in PgC/year. This gives the impression that the rate is the amount of CO2 the water in the cell absorbed in a year. Instead, it is the incremental, additional CO2 for the period of cell measurements. The water in the cell absorbs instantaneously (for all practical purposes) and moves on to the next cell for the next incremental uptake (and vice versa for outgassing). The surface ocean is not a stagnant pool.
The difference between Takahashi’s model, being about rates, and solubility, being an integral, seems to be a constant of integration. That is why I suggested an interesting paper might integrate a patch of water as it moves with ocean current, taking up CO2 at the Takahashi rates, and see what the total uptake or outgassing was for the path.
On 6/30/10 at 8:57, you said with respect to the Manning & RF Keeling paper,
>> Clear to me that they looked at the variability around the seasonal variability…
Your observation has some support in the paper. You have seen clearly, but not very far. The authors examined residuals with respect to smoothed curves fit to annual and semi-annual periodics, at least in the case of MLO. They provide neither formulas nor graphs for those residuals, but they talk about “the RESIDUALS of the flask data from the smooth curves fitted through the data”. Caps added. Their Figure 1 contains both flask data and the smoothed curves.
They go on to say
>>If variations in north-south transport are in fact causing the short-term variability at MLO, then we would expect the ratio of the instantaneous O2/N2 and CO2 GRADIENTS (shown in Figure 3) to be roughly equal to the ratio of the short-term covariations in O2/N2 and CO2. In other words, we would expect the ratio of the two vertical lines shown in Figure 3 to be roughly equal to the slope of the envelope of the flask residuals shown in Figure 2, for the same time period. In the period from December through March, when the ratio of the north-south gradient is at its most stable, the average absolute value of this north-south O2/N2 versus CO2 ratio is 15 ± 3 per meg ppmV-1, while a least squares fit to the flask residuals over this period results in a slope of 17 ± 4 per meg ppmV-1. This agreement suggests that the north-south transport may indeed be implicated as a source of variability at MLO. Caps added.
Figure 3 has no flask data, and the gradients are the differences between pairs of complete seasonal patterns. Two differences are involved, one for O2/N2, and the other for CO2. For each gas parameter, the differences are between La Jolla data and Cape Grim, Tasmania, data. The authors provide neither formula (fairly trivial) nor graphs for the gradients. The peak-to-peak seasonal variations in CO2 at Cape Grim are about 1.5 ppm, while at La Jolla, they are about 12.5 ppm. Consequently, La Jolla seasonal variations alone account for the CO2 gradient by a ratio of about 8:1.
So the authors employed two methods, one with residuals (your observation) and the other comparing only smoothed data (supporting my conclusion), and the methods agree. However, the methods don’t support the identical conclusion. The residual method supports a lesser included conclusion.
The residual method leads to the conclusion that the variations from the seasonal are likely due to “north-south transport”, leaving the door open for the CD Keeling’s conjecture that the seasonal cycles are due to terrestrial biology. The gradient method leads to the stronger conclusion that the total seasonal variations, smoothed fundamental plus residuals, are due to “north-south transport”. The gradient method is not consistent with CD Keeling’s conjecture.
In the authors’ formal conclusion, they generalize “north-south transport” to the parameter “real atmospheric variability”. This opens their conclusions to more than north-south transport, and in particular to include seasonal wind variations at the sites. The latter would be relatively unimportant if CO2 were well-mixed. The recognition that atmospheric CO2 is not well-mixed makes seasonal winds most significant.
Jeff Glassman says:
July 1, 2010 at 8:08 am
I have to fall back on the sum of the net positive cells is the net positive uptake for the ocean, and vice versa. This is based on the sum of the averages being the average of the sums.
The last sentence is right, the first is not: The sum of all positive periods and the sum of all negative periods within a cell is not equal to the average result of the cell, only the sum of both is equal to the average. The +90/-92 GtC out/inflows of total ocean surface added together are equal to the sum of averages of all cells at -2GtC, but each of them (as integrated separately) is much larger, as these represent all outflows and inflows, as represented in the monthly averages, not yearly averages.
Have a look at wintertime in the midlatitude cells:
http://www.pmel.noaa.gov/pubs/outstand/feel2331/images/fig03.jpg
A lot of them are relative strong absorbers, down to 30N
In summer, many of them are relative strong emitters.
Excellent! A commitment to shoot at. So you must have data that show a change in the CO2 solubility curve for a change in water DIC or pH!
See Zeebe and Wolf Fig. 1:
http://www.soest.hawaii.edu/oceanography/faculty/zeebe_files/Publications/ZeebeWolfEnclp07.pdf
Where the horizontal axis is the pH influence on the concentrations of the different species, including [CO2]. That is the Bjerrum plot you don’t like…
In fig. 2 one can see what happens with total alkalinity (~pH) if DIC changes.
Yours is novel physics. Novel means never before known physics, this time developed from climatology. There should be a Nobel prize in here somewhere.
Well, Svante Arrhenius earned the Nobel prize in chemistry, for his work on the greenhouse effect of CO2, although he was wrong with a large factor…
The influence of pH on CO2 solubility in seawater was established in the 1920’s (or even before?), long before CO2 was thought to be increasing in the atmosphere or anyway linked to catastrophic global warming. That resulted in formula’s to calculate the pCO2 of seawater from temperature, salinity and DIC/pH, together with practical methods to measure that even in (deep) ocean waters.
Here the table from the Wattenberg (deep) ocean measurements on board of the Meteor 1925-1927:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/wattenberg_ph_pco2.jpg
The Meteor trips are described here:
http://www.biokurs.de/treibhaus/literatur/wattenberg/meteor-reise.jpg
The theoretical calculations and real life measurements are here in three parts:
http://www.biokurs.de/treibhaus/literatur/wattenberg/wattp1.pdf
(the other parts at wattp2 and wattp3)
Sometimes it helps to know different languages…
That pH has such an influence is not a result of physics, it is the result of chemical reactions. Henry’s Law only describes the effect of gaseous CO2 concentration on free CO2 concentration in water and reverse, not on the other forms of CO2 in solution: bicarbonate and carbonate. pH influences the amount of free CO2 in solution, thus the ultimate effect of Henry’s Law.
Now back to basics.
The pCO2 of the atmosphere in equilibrium with the water is “taken to be”, “assumed to be”, “deemed to be”, or whatever synonym you want to use, the pCO2 for the water. The latter, of course, does not actually exist. My complaint is the novel model for Henry’s Law that you endorse in which solubility depends on the pCO2 gradient between gas and liquid. That is more novel physics.
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. What you seem to don’t understand is that Henry’s Law is going in both directions: The concentration of free CO2 in solution is in ratio with the concentration of free CO2 in the atmosphere when in equilibrium. With the same Law, the concentration of free CO2 in a small volume of air above a large amount of seawater is in ratio with the concentration of CO2 in the seawater, regardless of the initial amount of CO2 in the small volume of atmosphere.
Thus the pCO2 of seawater in any cell has nothing to do with the current pCO2 of the atmosphere above it, whatever that is, it simply reflects the tendency of CO2 in solution to come out. Thus it depends of the amount of CO2 already in the water.
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?
Indeed, the difference between pCO2 of the atmosphere and of the water doesn’t play much role in the ultimate (dynamic) equilibrium (that depends of the total quantities in both media involved), but it plays a role in the uptake/release speed, see next item.
The water in the cell absorbs instantaneously (for all practical purposes) and moves on to the next cell for the next incremental uptake (and vice versa for outgassing). The surface ocean is not a stagnant pool.
The water in the cell absorbs instantaneously for the skin of the surface, not the whole 100-200 m depth of the cell. 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. The release – uptake is not only from cell to cell (where you have gyres like the North Atlantic gyre, which are going from warm to cold and back to warm…), but within a year within several mid-latitude cells too. Several of these cells have no practical connection to the deep oceans, despite that these add to the uptake and release quantities.
Thus all together in summary, where we seem to disagree:
– Henry’s Law works bidirectional.
– pCO2 of seawater shows the tendency of free CO2 in seawater to escape, measured as pCO2 in a small volume of air above the water, which by Henry’s Law is directly proportional to [CO2] in the seawater of interest.
– besides temperature and salinity, pH and DIC play a huge role in the changes of free CO2 (denoted as [CO2]) in seawater.
– thus the pCO2 of seawater changes with temperature, salinity, pH and DIC.
– 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.
– dpCO2, the difference between seawater pCO2 and atmospheric pCO2 gives the direction and, together with wind speed, gives the transfer speed of CO2 (thus fluxes) between atmosphere and oceans.
– 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.
– 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.
——————-
They provide neither formulas nor graphs for those residuals
The residuals can be seen in Fig. 2 of their report:
http://www.esrl.noaa.gov/gmd/publications/annrpt22/MANNING.pdf
CO2 residuals are between -0.7 to +0.7 ppmv against the smoothed seasonal curve, which shows an amplitude of about +/- 3-4 ppmv. The disturbance of the seasonal curve thus is about 20% of the amplitude.
The peak-to-peak seasonal variations in CO2 at Cape Grim are about 1.5 ppm, while at La Jolla, they are about 12.5 ppm. Consequently, La Jolla seasonal variations alone account for the CO2 gradient by a ratio of about 8:1
All NH stations show huge seasonal variations, all SH stations show small seasonal variations, where NH and SH stations are opposite in seasonality. MLO’s seasonal variability is the result of the seasonal variability within the NH, not the result of any NH-SH gradient. The latter only influences the disturbances in the MLO data, which are not seen in the other NH stations data. In all cases, they write about “short term” variability around the seasonal variability…
In addition:
This opens their conclusions to more than north-south transport, and in particular to include seasonal wind variations at the sites. The latter would be relatively unimportant if CO2 were well-mixed. The recognition that atmospheric CO2 is not well-mixed makes seasonal winds most significant.
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?