On CO2 residence times: The chicken or the egg?

While some model based claims say that CO2 residence times may be thousands of years, a global experiment in measurable CO2 residence time seems to have already been done for us.

By Christopher Monckton of Brenchley

Is the ~10-year airborne half-life of 14CO2 demonstrated by the bomb-test curve (Fig. 1, and see Professor Gösta Pettersson’s post) the same variable as the IPCC’s residence time of 50-200 years? If so, does its value make any difference over time to the atmospheric concentration of CO2 and hence to any consequent global warming?

clip_image002

Figure 1. The decay curve of atmospheric 14C following the ending of nuclear bomb tests in 1963, assembled from European records by Gösta Pettersson.

The program of nuclear bomb tests that ended in 1963 doubled the atmospheric concentration of 14CO2 compared with its cosmogenic baseline. However, when the tests stopped half the 14C left the atmosphere in ten years. Almost all had gone after 50 years. Why should not the other isotopes of CO2 disappear just as rapidly?

Mr. Born, in comments on my last posting, says the residence time of CO2 has no bearing on its atmospheric concentration: “It’s not an issue of which carbon isotopes we’re talking about. The issue is the difference between CO2 concentration and residence time in the atmosphere of a typical CO2 molecule, of whatever isotope. The bomb tests, which tagged some CO2 molecules, showed us the latter, and I have no reason to believe that the residence time of any other isotope would be much different.”

He goes on to assert that CO2 concentration is independent of the residence time, thus:

The total mass m of airborne CO2 equals the combined mass m12 of 12,13CO2 plus the mass m14 of 14CO2 (1):

(1) clip_image004.

Let CO2 be emitted to the atmosphere from all sources at a rate e = e12 + e14 and removed by uptake at a rate u. Then the rate of change in CO2 mass over time is given by

(2) clip_image006,

which says the total mass m of CO2, and thus its concentration, varies as the net emission, which is the difference between source e and sink u rates.

For example, if e = u, the total mass m remains unchanged even if few individual molecules remain airborne for long. Also, where e > u, m will rise unless and until u = e. Also, unless thereafter u > e, he thinks the mass m will remain elevated indefinitely. By contrast, he says, the rate of change in 14CO2 mass is given by

(3) clip_image008,

which, he says, tells us that, even if e were to remain equal to u, so that total CO2 concentration remained constant, the excess 14CO2 concentration

(4) clip_image010,

which is the difference between the (initially elevated) 14CO2 concentration and the prior cosmogenic baseline 14CO2 concentration, would still decay with a time constant m/u, which, therefore, tells us nothing about how long total CO2 concentration would remain at some higher level to which previously-elevated emissions might have raised it. In this scenario, for example, the concentration remains elevated forever even though x decays. Mr. Born concludes that the decay rate of x tells us the turnover rate of CO2 in the air but does not tell us how fast the uptake rate u will adjust to increased emissions.

On the other hand, summarizing Professor Pettersson, reversible reactions tend towards an equilibrium defined by a constant k. Emission into a reservoir perturbs the equilibrium, whereupon relaxation drains the excess x from the reservoir, re-establishing equilibrium over time. Where µ is the rate-constant of decay, which is the reciprocal of the relaxation time, (5) gives the fraction ft of x that remains in the reservoir at any time t, where e, here uniquely, is exp(1):

(5) clip_image012.

The IPCC’s current estimates (fig. 2) of the pre-industrial baseline contents of the carbon reservoirs are 600 PgC in the atmosphere, 2000 PgC in the biosphere, and 38,000 PgC in the hydrosphere. Accordingly the equilibrium constant k, equivalent to the baseline pre-industrial ratio of atmospheric to biosphere and hydrosphere carbon reservoirs, is 600 / (2000 + 38,000), or 0.015, so that 1.5% of any excess x that Man or Nature adds to the atmosphere will remain airborne indefinitely.

Empirically, Petterson finds the value of the rate-constant of decay µ to be ~0.07, giving a relaxation time µ–1 of ~14 years and yielding the red curve fitted to the data in Fig. 1. Annual values of the remaining airborne fraction ft of the excess x, determined by me by way of (5), are at Table 1.

clip_image014

Figure 2. The global carbon cycle. Numbers represent reservoir sizes in PgC, and carbon exchange fluxes in PgC yr–1. Dark blue numbers and arrows indicate estimated pre-industrial reservoir sizes and natural fluxes. Red arrows and numbers indicate fluxes averaged over 2000–2009 arising from CO2 emissions from fossil fuel combustion, cement production and land-use change. Red numbers in the reservoirs denote cumulative industrial-era changes from 1750–2011. Source: IPCC (2013), Fig. 6.1.

t = 1 .932 .869 .810 .755 .704 .657 .612 .571 .533 .497
11 .464 .433 .404 .377 .362 .329 .307 .287 .268 .251
21 .235 .219 .205 .192 .180 .169 .158 .148 .139 .130
31 .122 .115 .108 .102 .096 .090 .085 .080 .076 .071
41 .067 .064 .060 .057 .054 .052 .049 .047 .045 .042
51 .041 .039 .037 .036 .034 .033 .032 .030 .029 .028
61 .027 .027 .026 .026 .024 .024 .023 .022 .022 .021
71 .021 .021 .020 .020 .019 .019 .019 .019 .018 .018
81 .018 .018 .017 .017 .017 .017 .017 .017 .016 .016
91 .016 .016 .016 .016 .016 .016 .016 .016 .016 .016
101 .016 .015 .015 .015 .015 .015 .015 .015 .015 .015
111 .015 .015 .015 .015 .015 .015 .015 .015 .015 .015

Table 1. Annual fractions ft of the excess x of 14CO2 remaining airborne in a given year t following the bomb-test curve determined via (5), showing the residential half-life of airborne 14C to be ~10 years. As expected, the annual fractions decay after 100 years to a minimum 1.5% above the pre-existing cosmogenic baseline.

Now, it is at once evident that Professor Pettersson’s analysis differs from that of the IPCC, and from that of Mr. Born, in several respects. Who is right?

Mr. Born offers an elegantly-expressed analogy:

“Consider a source emitting 1 L min–1 of a fluid F1 into a reservoir that already contains 15.53 L of F1, while a sink is simultaneously taking up 1 L min–1 of the reservoir’s contents. The contents remain at a steady 15.53 L.

“Now change the source to a different fluid F2, still supplied at 1 L min–1 and miscible ideally with F1 as well as sharing its density and flow characteristics. After 50 minutes, 96% of F1 will have left the reservoir, but the reservoir will still contain 15.53 L.

“Next, instantaneously inject an additional 1 L bolus of F2, raising the reservoir’s contents to 16.53 L. What does that 96% drop in 50 minutes that was previously observed reveal about how rapidly the volume of fluid in the reservoir will change thereafter from 16.53 L? I don’t think it tells us anything. It is the difference between source and sink rates that tells us how fast the volume of fluid in the reservoir will change. The rate, observed above, at which the contents turn over does not tell us that.

“The conceptual problem may arise from the fact that the 14C injection sounds as though it parallels the second operation above: it was, I guess, adding a slug of CO2 over and above pre-existing sources. But – correct me if I’m wrong – that added amount was essentially infinitesimal: it made no detectable change in the CO2 concentration, so in essence it merely changed the isotopic composition of that concentration, not the concentration itself. Therefore, the 14C injection parallels the first step above, while Man’s recent CO2 emissions parallel the second step.”

However, like all analogies, by definition this one breaks down at some point.

clip_image016

Figure 3. Comparison between the decay curves of the remaining airborne fraction ft of the excess x of CO2 across the interval t on [1, 100] years.

As Fig. 3 shows, the equilibrium constant k, the fraction of total excess concentration x that remains airborne indefinitely, has – if it is large enough – a major influence on the rate of decay. At the k = 0.15 determined by Professor Pettersson as the baseline pre-industrial ratio of the contents of the atmospheric to the combined biosphere and hydrosphere carbon reservoirs, the decay curve is close to a standard exponential-decay curve, such that, in (5), k = 0. However, at the 0.217 that is assumed in the Bern climate model, on which all other models rely, the course of the decay curve is markedly altered by the unjustifiably elevated equilibrium constant.

On this ground alone, one would expect CO2 to linger more briefly in the atmosphere than the Bern model and the models dependent upon it assume. To use Mr. Born’s own analogy, if any given quantum of fluid poured into a container remains there for less time than it otherwise would have done (in short, if it finds its way more quickly out of the container than the fixed rate of exit that his analogy implausibly assumes), then, ceteris paribus, there will be less fluid in the container.

Unlike the behavior of the contents of the reservoir described in Mr. Born’s analogy, the fraction of the excess remaining airborne at the end of the decay curve will be independent of the emission rate e and the uptake rate u.

Since the analogy breaks down at the end of the process and, therefore, to some degree throughout it, does it also break down on the question whether the rate of change in the contents of the reservoir is, as Mr. Born maintains in opposition to what Pettersson shows in (5), absolutely described by e – u?

Let us cite Skeptical Science as what the sociologists call a “negative reference group” – an outfit that is trustworthy only in that it is usually wrong about just about everything. The schoolboys at the University of Queensland, which ought really to be ashamed of them, feared Professor Murry Salby’s assertion that temperature change, not Man, is the prime determinant of CO2 concentration change.

They sought to dismiss his idea in their customarily malevolent fashion by sneering that the change in CO2 concentration was equal to the sum of anthropogenic and natural emissions and uptakes. Since there is no anthropogenic uptake to speak of, they contrived the following rinky-dink equationette:

(6) clip_image018 clip_image020.

The kiddiwinks say CO2 concentration change is equal to the sum of anthropogenic and natural emissions less the natural uptake. They add that we can measure CO2 concentration growth (equal to net emission) each year, and we can reliably deduce the anthropogenic emission from the global annual fossil-fuel consumption inventories. Rearranging (6):

(7) clip_image018[1] clip_image022.

They say that, since observed ea ≈ 2ΔCO2, the natural world on the left-hand side of (7) is perforce a net CO2 sink, not a net source as they thought Professor Salby had concluded. Yet his case, here as elsewhere, was subtler than they would comprehend.

Professor Salby, having shown by careful cross-correlations on all timescales, even short ones (Fig. 4, left), that CO2 concentration change lags temperature change, demonstrated that in the Mauna Loa record, if one examines it at a higher resolution than what is usually displayed (Fig. 4, right), there is a variation of up to 3 µatm from year to year in the annual CO2 concentration increment (which equals net emission).

clip_image024clip_image026

Figure 4. Left: CO2 change lags and may be caused by temperature change. Right: The mean annual CO2 increment is 1.5 µatm, but the year-on-year variability is twice that.

The annual changes in anthropogenic CO2 emission are nothing like 3 µatm (Fig. 5, left). However, Professor Salby has detected – and, I think, may have been the first to observe – that the annual fluctuations in the CO2 concentration increment are very closely correlated with annual fluctuations in surface conditions (Fig. 5, right).

clip_image028clip_image030

Figure 5. Left: global annual anthropogenic CO2 emissions rise near-monotonically and the annual differences are small. Right: an index of surface conditions (blue: 80% temperature change, 20% soil-moisture content) is closely correlated with fluctuations in CO2 concentration (green).

Annual fluctuations of anthropogenic CO2 emissions are small, but those of atmospheric CO2 concentration are very much larger, from which Professor Salby infers that their major cause is not Man but Nature, via changes in temperature. For instance, Henry’s Law holds that a cooler ocean can take up more CO2.

In that thought, perhaps, lies the reconciliation of the Born and Pettersson viewpoints. For the sources and sinks of CO2 are not static, as Mr. Born’s equations (1-4) and analogy assume, but dynamic. Increase the CO2 concentration and the biosphere responds with an observed global increase in net plant productivity. The planet gets greener as trees and plants gobble up the plant food we emit for them.

Similarly, if the weather gets a great deal warmer, as it briefly did during the Great el Niño of 1997/8, outgassing from the ocean will briefly double the annual net CO2 emission. But if it gets a great deal cooler, as it did in 1991/2 following the eruption of Pinatubo, net annual accumulation of CO2 in the atmosphere falls to little more than zero notwithstanding our emissions. It is possible, then, that as the world cools in response to the continuing decline in solar activity the ocean sink may take up more CO2 than we emit, even if we do not reduce our emissions.

Interestingly, several groups are working on demonstrating that, just as Professor Salby can explain recent fluctuations in Co2 concentration as a function of the time-integral of temperature change, in turn temperature change can be explained as a function of the time-integral of variations in solar activity. It’s the Sun, stupid!

It is trivially true that we are adding newly-liberated CO2 to the atmosphere every year, in contrast to the 14C pulse that ended in 1963 with the bomb tests. However, the bomb-test curve does show that just about all CO2 molecules conveniently marked with one or two extra neutrons in their nuclei will nearly all have come out of the atmosphere within 50 years.

To look at it another way, if we stopped adding CO2 to the atmosphere today, the excess remaining in the atmosphere after 100 years would be 1.5% of whatever we have added, and that is all. What is more, that value is not only theoretically derivable as the ratio of the contents of the atmospheric carbon reservoir to those of the combined active reservoirs of the hydrosphere and biosphere but also empirically consistent with the observed bomb-test curve (Fig. 1).

If the IPCC were right, though, the 50-200yr residence time of CO2 that it imagines would imply much-elevated concentrations for another century or two, for otherwise, it would not bother to make such an issue of the residence time. For the residence time of CO2 in the atmosphere does make a difference to future concentration levels.

To do a reductio ad absurdum in the opposite direction, suppose every molecule of CO2 we emitted persisted in the atmosphere only for a fraction of a second, then the influence of anthropogenic CO2 on global temperature would be negligible, and changes in CO2 concentration would be near-entirely dependent upon natural influences.

Atmospheric CO2 concentration is already accumulating in the atmosphere at less than half the rate at which we emit it. Half of all the CO2 we emit does indeed appear to vanish instantly from the atmosphere. This still-unexplained discrepancy, which the IPCC in its less dishonest days used to call the “missing sink”, is more or less exactly accounted for where, as Professor Pettersson suggests, CO2’s atmospheric residence time is indeed as short as the bomb-test curve suggests it is and not as long as the 50-200 years imagined by the IPCC.

And what does IPeCaC have to say about the bomb-test curve? Not a lot:

“Because fossil fuel CO2 is devoid of radiocarbon (14C), reconstructions of the 14C/C isotopic ratio of atmospheric CO2 from tree rings show a declining trend (Levin et al., 2010; Stuiver and Quay, 1981) prior to the massive addition of 14C in the atmosphere by nuclear weapon tests which has been offsetting that declining trend signal.”

And that is just about all They have to say about it.

Has Professor Pettersson provided the mechanism that explains why Professor Salby is right? If the work of these two seekers after truth proves meritorious, then that is the end of the global warming scare.

As Professor Lindzen commented when Professor Salby first told him of his results three years ago, since a given CO2 excess causes only a third of the warming the IPCC imagines, if not much more than half of that excess of CO2 is anthropogenic, and if it spends significantly less time in the atmosphere than the models imagine, there is nowhere for the climate extremists to go. Every component of their contrived theory will have been smashed.

It is because the consequences of this research are so potentially important that I have set out an account of the issue here at some length. It is not for a fumblesome layman such as me to say whether Professor Pettersson and Professor Salby (the latter supported by Professor Lindzen) are right. Or is Mr. Born right?

Quid vobis videtur?

Get notified when a new post is published.
Subscribe today!
5 1 vote
Article Rating
288 Comments
Inline Feedbacks
View all comments
November 22, 2013 11:31 am

I just checked the coins in my purse. I’m dutch so they are euro coins. Eleven years ago all my coins were dutch euros with our queen. Now all my coins are not dutch because of the dilution of the dutch coin pool with the european coin pool. Atmospheric c14 is similar, because of the huge dilution pool that is available in the ocean. The bomb test curve measures cash flow. Not profit and loss.

Editor
November 22, 2013 11:36 am

Lord Monckton, thank you for your response. You say that you are not mixing up the residence time and the response/adjustment/e-folding time, which I call the “e-folding time” to avoid misunderstanding..
However, your article starts by saying:

Is the ~10-year airborne half-life of 14CO2 demonstrated by the bomb-test curve (Fig. 1, and see Professor Gösta Pettersson’s post) the same variable as the IPCC’s residence time of 50-200 years?

The first of these measures the average residence time of an individual CO2 molecule in the atmosphere, using the half-life of 14CO2.
The second of these is an estimate of the time constant for the decay towards equilibrium of an injected pulse of CO2.
So clearly, the answer is no, they are not “the same variable”.
It appears to me that the thrust of your argument is that the answer to your opening question is an emphatic “yes” … if I’m wrong, please explain.
I got into this question in my normal fashion … by using the historical emissions and atmospheric concentration data to actually do the calculations for the e-folding time for an injected pulse of CO2. My calculations put it at about 38 years.
And in fact, one reason that I think that humans are responsible for the majority of the increase in CO2 is the quality of the fit between a very simple exponential decay model, and the observed reality. Here are the results of that analysis.

That analysis was done using single-time-variable exponential decay of the estimated emissions (including emissions from biomass). My calculations for that graph used an e-folding time of 38 years …
This is quite similar to the e-folding time calculated by Jacobsen, who found a figure of 43 years (including emissions from biomass).
So in answer to your question,

Is the ~10-year airborne half-life of 14CO2 demonstrated by the bomb-test curve (Fig. 1, and see Professor Gösta Pettersson’s post) the same variable as the IPCC’s residence time of 50-200 years?

I would say the answer is, emphatically no. They are two different variables. One is the molecular atmospheric residence time, call it 5-10 years. The other is the e-folding time for the decay of a pulse of injected CO2. Jacobsen and I put that at about 40 years.
The IPCC, on the other hand, uses the “Bern Model“, which I understand and have done the calculations for, but which I find unphysical and unbelievable. In any case, the Bern model divides the atmospheric CO2 into parts with different e-folding times. These are on the order of 3, 18, and 171 years for the various atmospheric fractions. So the IPCC says there is no one single fixed e-folding time for CO2.
Best regards,
w.

November 22, 2013 11:41 am

Ferdinand Engelbeen says:
November 22, 2013 at 3:41 am
– Salby is wrong about the impossibility to make a distinction between fossil fuels and plant decay:
Fossil fuels are completely devoid of 14C, plants are not.

===================================================================
A question. Is the line in bold based on assumption or actual analysis?

November 22, 2013 11:42 am

Mike Jonas says:
November 22, 2013 at 6:05 am
Downwellings and upwellings obviously do move between the surface and the deep.
One need to make a differentiation between the ocean suraface layer (the mixed layer) and the deep oceans. The former is where most sunlight enters, most biolife is present and wind stirrs the waters and makes a rapid exchange between water and atmosphere possible. The latter is for 90% of the area isolated from the surface, as there is very little migration between the deep oceans and the surface. The only relative important carbon flux is by dead bio material dropping out of the surface layer.
The main sink places are of course part of the surface, but they are sinking directly into the deep (or intemediate waters from the Southern Ocean). That are the places where the largest CO2 uptake happens without mixing with the rest of the ocean surface. The same for the upwelling: of course that gets to the surface, but again without much mixing with the rest of the surface layer before upwelling. Only afterwards, the upwelling spreads to a larger area where the extra CO2 content is released thanks to increased temperature.
The exchange of CO2 between the deep oceans and the atmosphere thus is mostly independent of what happens in the mixed layer. And a lot slower because of the limited exchange rate (directly or indirectly) between the atmosphere and the deep oceans…
But the Revelle effect then kicks in, and most of the CO2 changes chemically, allowing the ocean to take up a lot more CO2. Thus the Revelle effect greatly increases the ocean’s ability to absorb CO2. As you say, about 10 times.
Sorry, but that is a misinterpretation of the Revelle factor, which says that a change in CO2 of the atmosphere induces a change of CO2 in (sea)water which is a lot smaller: an increase of 30% CO2 in the atmosphere gives an increase of 3% in total carbon (DIC) in the ocean surface layer. That indeed is about 10 times more than what is dissolvable in fresh water, but only 10% of the change in the atmosphere.
That is an important point, as of the 9 GtC human emissios, 4.5 GtC/yr is the increase in the atmosphere, only ~0.5 GtC/yr is absorbed by the ocean’s mixed layer, ~1 GtC/yr is absorbed by vegetation and ~3 GtC by the deep oceans…

dikranmarsupial
November 22, 2013 11:47 am

Gunga Din, yes, the radioactive half life of C14 is about 5,000 years, but fossil fuels have been underground for hundreds of millions of years, so virtually all of the C14 will have decayed long ago.

November 22, 2013 11:47 am

Monckton of Brenchley on November 22, 2013 at 10:01 am
[bold emphasis by me-JW]
Mr. Whitman says I quoted Professors Lindzen and Salby on 14C. I did no such thing. I quoted Salby on the notion that the integral of surface temperature change is very closely correlated with CO2 concentration change, and Lindzen as supporting Salby’s conclusions. I only mentioned Salby (and hence Lindzen) at all because the head posting was speculating on whether Professor Pettersson’s theory might help to explain both Salby’s result and the embarrassingly large “missing sink” of CO2.”
. . . ”

– – – – – – – –
Christopher Monckton,
I appreciate your response. Thank you.
Please re-review my comment to you; here it is for your convenience. Please see bold emphasized text.

John Whitman on November 22, 2013 at 9:40 am said
[@Christopher Monckton]
I have enthusiastically followed both Lindzen’s and Salby’s public talks and written words since 2008 and 2011 respectively, however, I do not recall either of them discussing the 14C from atmospheric atomic bomb tests.
<b<Monckton does not quote them but uses his own words to relate private conversations on 14C.
I would like to have their own direct words publicly documented on the 14C topic.
Does anyone know if Lindzen or Salby have publicly addressed formally and specifically the 14C topic?
John

So, in bold you see that I did not say as you stated “Mr. Whitman says I quoted Professors Lindzen and Salby on 14C”, instead I clearly stated you did not quote Lindzen or Salby on 14C.
Instead of you quoting Salby, I said that you did relate, in your own words, a conversation you said you had with Salby. Here are your words,

WUWT Guest Post ‘Towards a theory of climate’ by Christopher Monckton of Brenchley
“. . .
First, I [Christopher Monckton] asked [Murry Salby] whether the rapid, exponential decay in carbon-14 over the six decades following the atmospheric nuclear bomb tests had any bearing on his research. He said that the decay curve for carbon-14 indicated a mean CO2 atmospheric residence time far below the several hundred years assumed in certain quarters. It supports Dick Lindzen’s estimate of a 40-year residence time, not the IPCC’s imagined 50-200 years.
. . .”

And that quote of yours is also a part of the basis of me inferring that you were referring to something Richard Lindzen related to you in conversation which was directly or indirectly related to 14C.
Again, I would like to see Salby and Lindzen directly address the excellent dialog we are having wrt Joe Born’s 14C position which you (CM) have teed up so well for WUWT.
John

November 22, 2013 11:56 am

Check the euro dilution process in the Netherlands with increasing foreign Euro coins.
http://www.knm.nl/CmsData/FCKUploads/image/grotesneller.jpg

Editor
November 22, 2013 12:05 pm

Ferdinand Engelbeen says:
November 22, 2013 at 11:42 am

… One need to make a differentiation between the ocean surface layer (the mixed layer) and the deep oceans. The former is where most sunlight enters, most biolife is present and wind stirrs the waters and makes a rapid exchange between water and atmosphere possible. The latter is for 90% of the area isolated from the surface, as there is very little migration between the deep oceans and the surface. The only relative important carbon flux is by dead bio material dropping out of the surface layer.

Thanks, Ferdinand. Curiously, in many parts of the ocean this is not true. The largest migration on earth (in tonnes of living creatures) is the nightly migration of billions of sea creatures from their daytime depths of around 200-400 metres up to near the surface where they feed, and then back down to the deep ocean again. Since they are eating at or near the surface, and then returning to the depths each night, the nightly migration is one of the generally overlooked transport pathways in the full carbon cycle, although there is some research in that area.
Regards,
w.

November 22, 2013 12:13 pm

Bart says:
November 22, 2013 at 10:31 am
There is, and he reviews it. He is not just making an assertion. He is backing it up with analysis.
The theoretical migration in the Siple Dome ice core which was referenced by Ian W, was calculated from a measured increase of CO2 in the neighbourhood of remelt layers, not exactly a measured migration in “normal” layers of ice cores. But even if we accept this theoretical migration, then there is a 10% broadening of the resolution of that particular ice core over 2.7 kyr and a doubling of the resolution at full depth (70 kyr).
Thus all what this migration did is decreasing the resolution, which still should be sufficient to show an increase of 2 ppmv sustained over 40 years some 70,000 years later. Let it be that that similar increases as the 70 ppmv over the past 50 years would anyway be noticed.
That is very far from the 10-fold decrease in the peak-CO2 of 280-300 ppmv sustained over a period of 10,000 years that Salby claims…

Jquip
November 22, 2013 12:16 pm

michael hart: “Because CO2 and bicarbonate are indeed transposable to one another, but the reaction is quite slow compared to diffusion-limited reactions.”
No, this is irrelevant and related to the error I just mentioned. It is correct to state that Henry’s is equilbrium. And it is correct to state that the partial pressures give us a response time for a reservoir model; it satisfies all the constraints necessary for its proper use. It is wholly incorrect to state that the statistical instantaneous snapshot of CO2 states as ‘which DIC is which’ is relevant to that at all. If our disequilbrium is strong enough then it is correct to state that we will violate Revelle’s factor for a period of time when diffusing from the atmosphere to the sea. But then, Revelle’s factor isn’t a constant, nor a law, but a suggestion. And you can find that different oceans have different opinions on what the precise value should be. But what Revelle’s cannot do is modify the reservoir model in terms of sinking from the atmosphere to the sea. And your soda analogy does not address this at all; specifically it’s going in the other direction.

Jquip
November 22, 2013 12:26 pm

Ferdiand: “Sorry, but that is a misinterpretation of the Revelle factor, which says that a change in CO2 of the atmosphere induces a change of CO2 in (sea)water which is a lot smaller: an increase of 30% CO2 in the atmosphere gives an increase of 3% in total carbon (DIC) in the ocean surface layer.”
No, this is incorrect. Revelle’s doesn’t refer to DIC for that DIC which is still just CO2. What instantaneous statistical snapshot of what carbon is in which state is wholly irrelevant. As on time scales much shorter than our interest, each DIC is transposing into any other DIC constantly and as the molecule local conditions dictate.

November 22, 2013 12:36 pm

Gunga Din says:
November 22, 2013 at 11:41 am
Ferdinand Engelbeen says:
November 22, 2013 at 3:41 am
– Salby is wrong about the impossibility to make a distinction between fossil fuels and plant decay:
Fossil fuels are completely devoid of 14C, plants are not.
===================================================================
A question. Is the line in bold based on assumption or actual analysis?

dikranmarsupial says:
November 22, 2013 at 11:47 am
Gunga Din, yes, the radioactive half life of C14 is about 5,000 years, but fossil fuels have been underground for hundreds of millions of years, so virtually all of the C14 will have decayed long ago.

======================================================================
So the “yes” is that it’s assumed there is no carbon14 in fossil fuels?
Fossil fuels haven’t been tested for it?

Jquip
November 22, 2013 12:36 pm

Willis: “The IPCC, on the other hand, uses the “Bern Model“, which I understand and have done the calculations for, but which I find unphysical and unbelievable.”
The only good information I can dig up on the Bern model is that it is used as a reservoir model where detritus (decomposition) and plants are used as reservoirs. However, this is impermissible. CO2 uptake by plant life is not a factor of differences in pressure between CO2 external to the plant, and the carbon already sequestered by the plant. Decomposition is just an edge case of aerobic life. Which certainly does consume plant carbon and emit CO2 by respiration. But, once again, this does not occur on pressure differences between the plant carbon sequestered in the animal and the partial pressure of CO2. So it is absolutely correct to state that it is unphysical in this regard. Strictly, it is violating the considerations necessary for a reservoir model. As a secondary consideration it is utilizing estimations of aerobic life, but ignoring the rest wholly and arbitrarily without justification.
How significant that is to results is a wholly different question. But if the sum total of plant and animal life is significant to our interests, then quite strictly Bern is out of bounds for use. And if it is significant, then certainly the notion that there is a constant e-folding time is out of bounds as well. And that makes a distinct problem if we are estimating emitted CO2 versus sunk CO2 on the idea that the e-folding time is constant and that we have a valid reservoir model. As to whether or not that is the case, I could hardly say at this point.

Editor
November 22, 2013 12:45 pm

Lord Monckton, John Whitman above references your comments in your most interesting previous post:

WUWT Guest Post ‘Towards a theory of climate’ by Christopher Monckton of Brenchley
“. . .
First, I [Christopher Monckton] asked [Murry Salby] whether the rapid, exponential decay in carbon-14 over the six decades following the atmospheric nuclear bomb tests had any bearing on his research. He said that the decay curve for carbon-14 indicated a mean CO2 atmospheric residence time far below the several hundred years assumed in certain quarters.
. . .”

This is a clear indication of the conflation I am referring to. The problem is that the term “residence time” is being used for both turnover time and for e-folding time.
The bomb-test 14C data applies only and solely to the turnover time, which is how long an individual CO2 molecule hangs out in the atmosphere before being absorbed somewhere at the surface. Since the bomb tests “tagged” individual molecules, we could see how long those molecules stayed airborne before being absorbed somewhere at the surface.
Unfortunately, the bomb-test data can tell us absolutely nothing about the e-folding time, which is the time constant of the natural exponential decay in atmospheric concentration of a pulse of CO2 emitted into the atmosphere. This is the “several hundred years” you refer to. The e-folding time has nothing to do with the airborne lifetime of your average CO2 molecule. That’s turnover time, a separate question.
Instead, the e-folding time is how long it takes the CO2 concentration to decay after the emission of a concentration-changing pulse … and that is not related to how long an individual CO2 molecule stays aloft. How long a CO2 molecule stays airborne is turnover time, as measured by bomb-test 14C. The “several hundred years” you reference is e-folding time, not turnover time.
All the best to you,
w.

November 22, 2013 12:58 pm

Bart says:
November 22, 2013 at 10:31 am
This is beside the point. I do not agree with your analysis, which is heavily influenced by the erroneous “mass balance” argument.
No, it is quite essential and has nothing to do with the mass balance argument. Your reasoning starts with:
1) dCO2/dt = (CO2eq – CO2)/tau + a*H
But that is already a wrong start: the sinks don’t make any differentiation between CO2 from humans and from nature, thus there is no “fixed” amount of human emissions that resides somewhat longer in the atmosphere. The real uptake is:
1) dCO2/dt = (CO2eq – (CO2+H))/tau
And the decay rate depends of the difference between total CO2 and CO2eq at one side and tau.
WIth a fast decay rate, total CO2 will decay fast to CO2eq and vv.
But we see that CO2 is increasing over time at a rate about halve of the increase of H
Thus either H is the cause of the increase of CO2 or as Bart and Salby says, tau is huge and a natural increase in circulation causes the increase in total CO2, thereby dwarfing H.
But then, the increase in the natural circulation must follow the increase in H at exactly the same ratio over the past 50 years of accurate measurements. Which implies that the threefold increase of H over time is mimicked by a threefold increase in all natural emissions (and therefore natural absorbances) over the same period.
For which there is no proof, to the contrary:
– there is no such change in decay rate of 14C, which should be diluted much faster over time
– the same for the 13C/12C ratio: no change in dilution.
– there is no threefold decrease in the estimated residence time, even a slight increase over the most recent ones.

DocMartyn
November 22, 2013 12:58 pm

Ferdinand, take off you chemistry hat for a moment and put a biology hat on.
You state, “The only relative important carbon flux is by dead bio material dropping out of the surface layer”.
Now let us do some numbers.
The total marine biotic carbon mass is about 2 GtC.
The flux of carbon through this 2 GtC is 55 GtC per year.
The 55 GtC is converted to CO2 in the upper 5 m, or into dead matter or into fecal matter.
Dead matter and fecal matter fall, on average, at something like 200 m per day.
A fraction dead matter and fecal matter is intercepted on the way down, along all the depths, and is converted to CO2/CH4. Some fraction of dead organic carbon is mineralized, and joins the 15,000,000 GtC of Kerogens down there already.
If CO2 was non-atmospheric and only existed as an aquatic species, as CO2/DIC, we know what the profile would look like, it would be much the same as phosphate;
http://homepage.smc.edu/grippo_alessandro/Oxygen.jpg
So phosphate is denuded at the surface, where photosynthesis is active. Organism take it up and it goes down in excreta and dead creature.
Phosphate diffuses upward and sideways into areas where biotic productivity is high. With carbon the atmosphere provides an extra dimension of transport, CO2/DIC at the surface in areas of low biotic productivity and can be transferred to areas where CO2/DIC is low.
The swings in the Keeling Curve show that atmospheric CO2 is a buffer for the marine surface, so when it is summer over the productive ares, CO2 goes down, and when it is winter, the atmospheric CO2 goes up.
Nothing to do with Henry’s Law at all.

Nick Stokes
November 22, 2013 1:03 pm

Bart says: November 22, 2013 at 10:31 am
“Nick Stokes says: November 21, 2013 at 7:36 pm
‘They say the plant reservoir has diminished by 15 Gtons C. They aren’t sure that it’s down – the range is -45 to +15.’
Basically, what you are saying here is, they haven’t really got a clue.”

Not at all. They are saying that the amount of vegetation has changed very little. They think there is a little less, but it could be a little more.
What they are saying, with great confidence, is that vegetation has not absorbed any significant part of the 400 Gt C that we have burnt. So where has it gone?

DocMartyn
November 22, 2013 1:07 pm

” Willis Eschenbach
The largest migration on earth (in tonnes of living creatures) is the nightly migration of billions of sea creatures from their daytime depths of around 200-400 metres up to near the surface where they feed, and then back down to the deep ocean again.”
Willis, after they, they descend, digest and defecate.
Note also that averaging over days the concentrations of biological’s, with respect to depth, ignores daily movements of predator and pray.

November 22, 2013 1:11 pm

John Whitman: “Your calm and civil response on one of those other threads to being called a troll is a classic.”
Thank you for the kind words. In Lord M’s defense, though, I have to confess that as an uncredentialed dilettante I had resorted to being (only slightly) provocative in order to make sure the issue got his full attention. He is a valuable asset, and it’s worth a little effort to prevent his persistence in that error from compromising his effectiveness.

Bart
November 22, 2013 1:16 pm

Willis Eschenbach says:
November 22, 2013 at 12:45 pm
“Unfortunately, the bomb-test data can tell us absolutely nothing about the e-folding time, which is the time constant of the natural exponential decay in atmospheric concentration of a pulse of CO2 emitted into the atmosphere. This is the “several hundred years” you refer to. The e-folding time has nothing to do with the airborne lifetime of your average CO2 molecule. That’s turnover time, a separate question. “
Not necessarily so. Consider this analogy.
We have a bucket of water. It has an inflow from a hose, and an outflow from a hole or drain in the bottom. The rates of the two are balanced so that a particular level of water has been established in the steady state.
Now, we add a little blue dye at the surface. This blue dye will diffuse throughout the bucket over time. We measure the blueness of the top cm or so (assume the bucket is several cm deep). The blueness of the water will decrease over a timeline associated with the rate of diffusion, which bears little relation to the rate at which water is flowing out of the drain.
So far, so good, and in perfect accord with what you have stated. BUT, there is a hidden assumption here. That assumption is that the drain is weak, and the rate of outflow is slow relative to the diffusion.
If the drain is powerful, and the rate of inflow proportionately also powerful in order to establish the steady state level, then the draining of fluid in general will dominate the diffusion process, and the rate at which the blueness of the upper cm decreases will be reflective of the rate at which all the water drains away.
So, the question before us is, as always, is our “drain” weak, or powerful? If Salby is correct, and I am convinced that he is, then the “drain” is powerful, and it is quite likely that your turnover time and e-folding time are approximately the same.

November 22, 2013 1:19 pm

Rob: “Equation 3 is not dimensionally correct. e14e has units of ([m]/[t])^2. LHS is in units of [m]/[t]”
My original equation corresponding to Equation (4), too, was rendered “dimensionally challenged” in hte way I described above in connection with Equation (3): the cosmogenic carbon-14 fraction c should replace the carbon-14 mass e14.

Bart
November 22, 2013 1:23 pm

Ferdinand Engelbeen says:
November 22, 2013 at 12:58 pm
“But that is already a wrong start: the sinks don’t make any differentiation between CO2 from humans and from nature…”
You really could have stopped right there and said “I do not understand your equations.” It would have been a lot shorter.
“Thus either H is the cause of the increase of CO2 or as Bart and Salby says, tau is huge…”
For fast response, tau is small. But, you have already conceded that the “mass balance” argument depends on the response time. And, arguing that the response time is slow because the mass balance says it must be is a circular argument.
“But then, the increase in the natural circulation must follow the increase in H at exactly the same ratio over the past 50 years of accurate measurements. “
No, it must simply overwhelm it. This is typical feedback system behavior.
Nick Stokes says:
November 22, 2013 at 1:03 pm
“…the range is -45 to +15…”
So, it could have increased by a factor of 3, according to their calculations? Am I reading this wrong?
“What they are saying, with great confidence…”
95%? Do you have any idea what my level of confidence is in their levels of confidence?

November 22, 2013 1:24 pm

Willis Eschenbach says:
November 22, 2013 at 12:05 pm
Since they are eating at or near the surface, and then returning to the depths each night, the nightly migration is one of the generally overlooked transport pathways in the full carbon cycle, although there is some research in that area.
Thanks for that interesting info! Should make it as “dead and alive” material dropping out of the surface layer… Seems that BATS is involved, should have given a follow-up with more information by now…

Editor
November 22, 2013 1:45 pm

Ferdinand Engelbeen – I suspected that we were at cross purposes but couldn’t put my finger on it. Now I have it (I think!). When I said that the Revelle Effect meant that the ocean could take up 10 times as much CO2, I was talking about quantity, and I used the unit “ton” in my example. You are talking about percentage: “an increase of 30% CO2 in the atmosphere gives an increase of 3% in total carbon (DIC) in the ocean surface layer“. Also, where I am talking about the surface layer, meaning the physical layer next to the atmosphere, you are talking about the ‘mixed layer’ which excludes things like upwellings and downwellings. You say “only ~0.5 GtC/yr is absorbed by the ocean’s mixed layer,[..] and ~3 GtC by the deep oceans“. Using those numbers, my argument is that 3.5 GtC is absorbed from the atmosphere by the physical surface layer, and 3.5 GtC of that then goes on to the deep. The reason I use the physical surface layer, not the ‘mixed layer’ is that the processes which cause CO2 to transfer between atmosphere and ocean cannot distinguish between the ‘mixed layer’ and the other bits – all it sees is the physical surface layer. CO2 cannot jump from the atmosphere into the deep without going through the physical ocean surface layer.
So my argument stands. To make sure we are now clear on this, I’ll restate the mechanism:
— Ocean uptake (say) of CO2 is driven primarily by pCO2 difference between physical ocean surface and atmosphere (Henry’s Law).
— When CO2 is absorbed, pCO2 in the physical ocean surface layer goes up and in the atmosphere goes down, as they ‘aim’ for balance.
— Once in the physical ocean surface, most of the CO2 then undergoes chemical change.
— This reduces pCO2 in the physical ocean surface, thus allowing more CO2 to be absorbed.
Jquip – As I trust the above makes clear, there is no deviation from Henry’s Law, in fact it is crucial to the equation. It also agrees entirely with your statement that “CO2, Bicarbonate and Carbonate are freely transposable to one another“. But AFAIK Bicarbonate and Carbonate do not affect pCO2, only CO2 does. I have been quite careful to distinguish between CO2 and C in my comments, and hopefully I haven’t mixed them up anywhere, eg,: “there is an ongoing transfer of C from the surface layer to the deep” and “THC is not the only mechanism by which CO2 or C gets from the surface layer to the deep ocean“. Note also that (a) the rate of uptake by the ocean may be quite different to ‘pure’ Henry’s Law because of the Revelle Effect, and (b) when the ocean emits CO2, the Revelle Effect acts as a multiplier there too.

Editor
November 22, 2013 1:47 pm

Correction : 3 GtC of that then goes on to the deep

1 4 5 6 7 8 12