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?

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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.

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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?

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November 22, 2013 2:01 pm

Bart says:
November 22, 2013 at 1:23 pm
You really could have stopped right there and said “I do not understand your equations.” It would have been a lot shorter.
Sorry, it’s late here… Agreed that it boils down to a short or long(er) tau. But an estimated e-fold decay rate of ~50 years is somewhere between the two extremes you showed. Slow enough to allow the accumulation of a part of the human emissions and fast enough to give the thight following of CO2 levels after temperature during ice ages…
No, it must simply overwhelm it. This is typical feedback system behavior.
Sorry, but that can’t be true: the human input is not zero, it is about 3% of the natural throughput. If the human input increases a threefold and the increase in the atmosphere follows that at the exact same ratio over a period of 50 years, then the natural throughput must have increased a threefold over the same period to give the same effect.

November 22, 2013 2:06 pm

Lord Monckton:
Since with Mr. Eschenbach’s help we may still have your attention, I’ll respond to a few of your comments.
Monckton of Brenchley: “[Joe Born’s] equations (3, 4) are dimensionally challenged.”
I believe you’ll find that the originals weren’t.
Monckton of Brenchley: “however, as many have pointed out, for all relevant purposes the isotopes behave identically”
If you study my work carefully, you’ll find that I have not assumed otherwise.
Monckton of Brenchley: “his model of a dynamic object is unduly static”
Although it’s true that I highly simplified things to set forth the principle, that principle does not depend on e and u’s being either constant or equal, and the fact that I did not intend such a limitation should have been evident from my following comment at JoNova’s, from which you abstracted my equations: “Also, if the emission rate p exceeds the sink rate, the total mass of atmospheric CO2 will rise until such time, if any, as the sink rate catches up, and, unless the sink rate thereafter exceeds the emission rate, the mass M will remain elevated forever.”
It’s true that I additionally set forth a thought experiment in which e and u were kept equal in order to make m a constant and therefore make Equation (3) into a linear equation whose solution could be obtained by inspection. But nothing else depended on that relationship.

Jquip
November 22, 2013 2:13 pm

Mike Jonas: ” But AFAIK Bicarbonate and Carbonate do not affect pCO2, only CO2 does.”
That’s the problem in sum. The pCO2 you’re after for Henry’s is pDIC. Remember, at one instant in time one molecule is CO2, at another it is one of the other DIC’s. Statistically, in aggregate, for any given instant in time we can expect x% of the CO2 to be bonded up as Bicarbonate and y% as Carbonate. Between instants the same ratios will hold, but it won’t be the same molecules in the same state.
With regards to partial pressure, we derive that from the moles of CO2 alone. But that doesn’t work here precisely as CO2 is getting itself merry at any given instant as one of the three DICs. And so partial pressure must be considered as the moles of DIC and not as the moles of dissolved CO2 that is — in this one and very instant CO2 — rather than one of the other conjugates. This confusion is where the claims of rate differences arise from.
If this is not understood, or is held to be wholly wrong: I shall not refute it thus ::kicks rock:: But I’ll offer you and anyone else the opportunity to construct a lab table experiment that doesn’t put a tiny adjustment on Henry’s but entirely refutes it as the most wrong-headed thing to come across the pike. It’s an opportunity for any takes to claim a Nobel Prize for showing that Henry’s isn’t just wrong, but so wrong that it’s off on the order of 1:10 in the worst possible direction — despite that we’ve been using it, experimentally with success, for ages.

clipe
November 22, 2013 2:17 pm

Wow! I cant believe I’ve read the whole thing. (so far)
Although I only understand about 10% of it, seeing my favorite Boffins thrashing out a chicken or egg question is fascinating.

bobl
November 22, 2013 2:27 pm

Lord M.
Shall we agree that the halflife of added CO2 lies somewhere between 1 and 10 years depending on the magnitude of the negative feedback response of the biosphere to a change in CO2 and how much of the annual CO2 gap (missing CO2) is caused by additional uptake.
Remember my analysis only considers delta CO2, positing that the biosphere removes 50% of any excess per annum based on the emission gap that exits the system over the year, since the excess removed is small, 50 % of emissions or about 3ppm – of the order of 0.75 percent of the total sinking capacity I think its consistent with a whole of atmosphere turnover of the order of 100 years. That the biosphere can respond to change in CO2 quickly and deeply doesn’t in my mind preclude a longer halflife for whole of atmosphere turnover. What it does suggest in my mind is that the turnover rate is being limited by the relative starvation of the biosphere for CO2, that is the sinking rate is saturated and turnover rate is not constant and should increase with CO2 level. This seems logical to me.
By the way, the estimate of a 6 percent greening 2000 – 2012 (0.5 % PA) does seem to be broadly consistent with a 0.75% increase in CO2 sinking PA providing some evidentiary support that the missing CO2 is very possibly due to increased biological uptake.

November 22, 2013 2:40 pm

DocMartyn says:
November 22, 2013 at 12:58 pm
Okay, both hats were a little worn out, but I do follow your reasoning. Except for the last sentences:
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.

The swings of nDIC in seawater at the Bermuda’s between summer and winter (8 K difference) are around 30 μmol/kg, between 2030 and 2060 μmol/kg. Thus really, carbon availability is not an issue for biological life in seawater. See Fig. 4 in:
http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf
But the combination of temperature and biolife certainly influences the pCO2 in seawater in opposite ways. What we see at Bermuda is that pCO2 in summer is slightly above the pCO2 of the atmosphere during 2-3 months, while nDIC is at minimum. Thus temperature is the winning factor in seawater, despite the increased biological activity in summer, that a part of nDIC removed. Another part is emitted from the oceans into the atmosphere durign that period. The rest of the year the oceans near Bermuda are net absorbers for CO2 from the atmosphere.
The seasonal swings in the atmosphere are caused by land plants, which are far more abundant in the NH than in the SH where the seasonal swings are much smaller…
And if you look at the trends in Fig. 5, nDIC increases with about 10% of the increase in the atmosphere, the combination of Henry’s law and the Revelle factor still at work, despite all biological activity…

Editor
November 22, 2013 3:06 pm

Jquip – As you say, “With regards to partial pressure, we derive that from the moles of CO2 alone. But that doesn’t work here precisely“. and you refer to “a tiny adjustment on Henry’s“. In other words, the process is as I describe it, but there is a tiny variation from what could be expected from Henry’s Law and the actual CO2 concentration. A tiny variation doesn’t affect the argument.

November 22, 2013 3:07 pm

Jquip says:
November 22, 2013 at 2:13 pm
That’s the problem in sum. The pCO2 you’re after for Henry’s is pDIC.
Wait a minute, something like pDIC doesn’t exist. It is pCO2, as Henry’s law is only for the solubility of gases. As bicarbonate and carbonate are not gases, they don’t play any direct role in pCO2 or Henry’s law. But they do play a very important indirect role.
Remember, at one instant in time one molecule is CO2, at another it is one of the other DIC’s. Statistically, in aggregate, for any given instant in time we can expect x% of the CO2 to be bonded up as Bicarbonate and y% as Carbonate. Between instants the same ratios will hold, but it won’t be the same molecules in the same state.
All transformations between free CO2, bicarbonate ions and carbonate ions are equilibrium reactions dependent of pCO2 in the atmosphere at on side and H+ ions (pH) at the other side.
If pCO2(atm) is higher than pCO2(aq), then CO2 is pushed into the oceans, if it is reverse, then CO2 is pushed out of the oceans. In all cases, an 100% increase of CO2 in the atmosphere will give you a 100% increase of free CO2 in the ocean surface.
But free CO2 is less than 1% of total DIC in seawater, thus in first instance a 100% increase of CO2 in the atmosphere will increase total DIC only with 1% (that happens if the buffer was saturated).
But as we have equilibrium reactions, more CO2 in solution pushes the reactions to more bicarbonate and more carbonate ions. But that also gives more H+ ions, thus the pH lowers, pushing the equilibrium reactions back towards bicarbonate and free CO2.
The net effect is that the original 1% increase in DIC gets up further to 10% when everything is again in equilibrium. That is the Revelle factor…

Bart
November 22, 2013 3:08 pm

Ferdinand Engelbeen says:
November 22, 2013 at 2:01 pm
“If the human input increases a threefold and the increase in the atmosphere follows that at the exact same ratio over a period of 50 years, then the natural throughput must have increased a threefold over the same period to give the same effect.”
The difference between sources and sinks has to have increased threefold. But, that is only a constraint on the difference, and that difference is dynamic, as the sinks respond to source activity.

Jquip
November 22, 2013 3:18 pm

Ferdinand: “The swings of nDIC in seawater at the Bermuda’s between summer and winter (8 K difference) are around 30 μmol/kg, between 2030 and 2060 μmol/kg. ”
This is not responsive to DocMartyn’s statements about atmospheric CO2 concentrations. You can corrobaration of his statements as to that here: http://www.esrl.noaa.gov/gmd/ccgg/trends/global.html

Jquip
November 22, 2013 3:27 pm

Ferdinand: “All transformations between free CO2, bicarbonate ions and carbonate ions are equilibrium reactions dependent of pCO2 in the atmosphere at on side and H+ ions (pH) at the other side.”
Ah, no. This is a complete misunderstanding. And I’ll say the same thing to you as I said to Mike Jonas: Grab the Nobel Prize and produce an experiment that demonstrates it. This is not some queerly confounding construction such as the whole of the climate — it is something as simple as what can be trivially constructed on a lab table.
And if there’s any validity — proper empiricism — behind what you’re stating then you don’t get the Nobel Prize, but you do know how to link every reader of this thread to the lab-table experiment they can do themselves. If it has not been properly validated by experiment then: Shut up. Go design it and win the Nobel Prize. But if you’re not interested in international fame and glory then you need to get your head around the semantics of Henry’s that reduce the problem to partial pressure and why that is invalid when we’re speaking of the volatile equlibrium of CO2 as one of its various conjugates at any given instsant in time.

November 22, 2013 3:28 pm

Gunga Din says:
November 22, 2013 at 12:36 pm
So the “yes” is that it’s assumed there is no carbon14 in fossil fuels?
Fossil fuels haven’t been tested for it?

radiocarbon dating needed corrections for the years from 1870 on and later, due to the “thinning” of the normal production rate of 14C in the atmosphere by the use of fossil fuels.
The difference anyway is used today to calculate the biogenic fraction of fuels:
http://www.rug.nl/research/isotope-research/projects/biogenic-carbon-determination
and
http://www.rug.nl/research/isotope-research/projects/sannemeasurements.pdf

November 22, 2013 3:37 pm

Bart says:
November 22, 2013 at 3:08 pm
The difference between sources and sinks has to have increased threefold. But, that is only a constraint on the difference, and that difference is dynamic, as the sinks respond to source activity
As there is no difference in sink rate for “human” CO2 and “natural” CO2, only an increase of the natural emissions at the same rate as the human emissions will give the same result…

Bart
November 22, 2013 4:07 pm

Ferdinand Engelbeen says:
November 22, 2013 at 3:37 pm
“As there is no difference in sink rate for “human” CO2 and “natural” CO2, only an increase of the natural emissions at the same rate as the human emissions will give the same result…”
Incorrect. Total sinks expand in response to increased forcing from either source. If natural forcing is dominant, then dominant sink expansion will be in response to natural forcing.

Bart
November 22, 2013 4:09 pm

I am disappointed that nobody, especially Willis, has commented on my post here. I think it clears up a lot of confusion regarding the 14C results using a simple analogy.

Pippen Kool
November 22, 2013 4:19 pm

If you follow the long line of links from the link at the top of Monckton’s post you get to an article by Solomon et al in PNAS in 2008. They do many things in the paper, but they have estimates of the the amount of future conc’s of CO2 in the atmosphere. Needless to say, the decreases do not match Monckton’s. The reason is that Monckton is looking at an isotope that is not in equilibrium with the CO2 in the fixed carbon; his isotope goes into a very large pool of carbon, much much larger than the CO2 in the atmosphere (afterall, which is measured in ppm). So of course it’s quickly diluted, never to be seen again at measureable amounts.
The IPCC is not interested in the residence time of individual molecules of CO2, they are interested in the resisdence time of the high CO2 levels….These will someday in the long future go down as they are absorbed into the oceans (not good, actually). And this is measured in 1000 year half lives. Not 12 or what ever Monckton’s half life is. (hmmm, should I reword that…nah)
The point is that Monckton’s calculations has nothing to do with the IPCCs worries and they are completely silly. Apples and oranges.
And BYW, I really like Hans Erren’s analogy, it is perfect. I was going to use one with blue dye in tide pools, but his is better.

November 22, 2013 4:29 pm

Jquip says:
November 22, 2013 at 3:27 pm
The solubility of CO2 at 1 bar in fresh water at 20°C is 1.7 g/l or a DIC of 0.46 g/l
The solubility of sodium bicarbonate in fresh water at 20°C is 90 g/l or a DIC of 12.8 g/l
or an 28-fold.
The difference between the two solutions:
– at 1 bar the CO2-only solution is completely in equilibrium and Henry’s law works. The Revelle factor isn’t relevant here as there is no buffer present and the solution is slightly acidic.
– the bicarbonate solution still is not saturated with CO2 and no CO2 escapes from the solution. If one applies 1 bar CO2 pressure, more CO2 will get into solution. Until the pCO2 of the solution also gets 1 bar. That is at about 0.46 g/l free CO2 DIC to satisfy Henry’s law. As free CO2 is less than 1% of DIC, total DIC then may reach 46 g/l. The Revelle factor in this case is very low and a 100% change in CO2 above the solution will give about a 100% increase in DIC. The solution is slightly alkaline.
In both cases DIC exists in all three forms: free CO2, bicarbonate and carbonate. But the ratio between them is completely different.
In CO2-only 99% is free CO2, the rest is bicarbonate and hardly any carbonate
In the bicarbonate solution, 1% is free CO2, most is bicarbonate and some is carbonate
Thus Henry’s law shows how much CO2 resides in solution as free CO2 for a given temperature and CO2 pressure in the atmosphere with or without buffer capacity, regardless of pH.
In the case of fresh water that is all CO2 that gets in the water
In the case of the bicarbonate solution, far more CO2 gets in the water but then is transformed to bicarbonate and carbonate. That is the Revelle factor.
Now slowly add acetic acid to the bicarbonate solution. In first instance, nothing happens. Then at a certain moment CO2 bubbles start to form and continu to bubble up until very little CO2 is left in solution. During the whole time DIC decreases, the Revelle factor increases, but Henry’s law remains intact at all times as until the last moment the same amount of free CO2 is present in solution for the same CO2 pressure in the atmosphere above it.

November 22, 2013 4:35 pm

Bart says:
November 22, 2013 at 4:07 pm
Incorrect. Total sinks expand in response to increased forcing from either source. If natural forcing is dominant, then dominant sink expansion will be in response to natural forcing.
Let us formulate it different: Natural forcings are dominant, thus human emissions follow the same fate as the natural emissions. As we see that both human emissions and the net sink rate increased about threefold over 50 years time, that means that the natural emissions also increased a threefold over time.

Bart
November 22, 2013 4:37 pm

Pippen Kool says:
November 22, 2013 at 4:19 pm
“The point is that Monckton’s calculations has nothing to do with the IPCCs worries and they are completely silly. Apples and oranges.”
Only if you assume weak sink activity.

Pippen Kool
November 22, 2013 4:38 pm

The other thing about this discussion is that reminds of an argument I had with three engineers from Dow Chemical many years ago on a long bike ride. My question was what was the speed of the top of a bicycle wheel relative to the speed of the bike. They were going into calculations and pi R square and sin tan and diameter and on and on and they could not really answer the question. And they didn’t believe it when I finally told them the answer but what’s new…
But you don’t need math to answer that question anymore that you need it for Monckton’s question. The math seems like it’s used just to obfuscate.

November 22, 2013 4:39 pm

Pippen Kool says:
November 22, 2013 at 4:19 pm
And this is measured in 1000 year half lives.
And that is nonsense for the foreseeable long future. The current decay rate is ~50 years e-fold time. There is no saturation of the deep oceans in sight, neither of vegetation (which is an unlimited sink).

DocMartyn
November 22, 2013 4:43 pm

Ferdinand, Bermuda is well studied because of the hotels, beeches and off hours activity.
There the carbon cycle is highly constrained, as their is nowhere to go.
The land plant hypothesis I don’t buy, the positioning is wrong for matching to land chlorophyll.
I suspect marine over land, I am not wed to it, but I am skeptical.

Bart
November 22, 2013 4:44 pm

Ferdinand Engelbeen says:
November 22, 2013 at 4:35 pm
You are mixing models. You are comparing one essentially without dynamic feedback, that with direct accumulation of human inputs, to one with strong dynamic feedback, that in which human inputs are quickly sequestered and natural forcing dominates.

Bart
November 22, 2013 4:48 pm

Pippen Kool says:
November 22, 2013 at 4:38 pm
2V

Bart
November 22, 2013 4:49 pm

Sorry, 1V relative to bike.

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