In a paper recently published in the international peer-reviewed journal
Energy & Fuels, Dr. Robert H. Essenhigh (2009), Professor of Energy Conversion at The Ohio State University, addresses the residence time (RT) of anthropogenic CO
2 in the air. He finds that the RT for bulk atmospheric CO
2, the molecule
12CO
2, is ~5 years, in good agreement with other cited sources (Segalstad, 1998), while the RT for the trace molecule
14CO
2 is ~16 years. Both of these residence times are much shorter than what is claimed by the IPCC. The rising concentration of atmospheric CO
2 in the last century is not consistent with supply from anthropogenic sources. Such anthropogenic sources account for less than 5% of the present atmosphere, compared to the major input/output from natural sources (~95%). Hence,
anthropogenic CO2 is too small to be a significant or relevant factor in the global warming process, particularly when comparing with the far more potent greenhouse gas water vapor. The rising atmospheric CO
2 is the outcome of rising temperature rather than vice versa. Correspondingly, Dr. Essenhigh concludes that the politically driven target of capture and sequestration of carbon from combustion sources would be a major and pointless waste of physical and financial resources.
Essenhigh (2009) points out that the IPCC (Intergovernmental Panel on Climate Change) in their first report (Houghton
et al., 1990) gives an atmospheric CO
2 residence time (lifetime) of 50-200 years [as a "rough estimate"]. This estimate is confusingly given as an adjustment time for a scenario with a given anthropogenic CO
2 input, and ignores natural (sea and vegetation) CO
2 flux rates. Such estimates are analytically invalid; and they are in conflict with the more correct explanation given elsewhere in the same IPCC report: "
This means that on average it takes only a few years before a CO2 molecule in the atmosphere is taken up by plants or dissolved in the ocean".
Some 99% of the atmospheric CO
2 molecules are
12CO
2 molecules containing the stable isotope
12C (Segalstad, 1982). To calculate the RT of the bulk atmospheric CO
2 molecule
12CO
2, Essenhigh (2009) uses the IPCC data of 1990 with a total mass of carbon of 750 gigatons in the atmospheric CO
2 and a natural input/output exchange rate of 150 gigatons of carbon per year (Houghton
et al., 1990). The characteristic decay time (denoted by the Greek letter tau) is simply the former value divided by the latter value: 750 / 150 = 5 years. This is a similar value to the ~5 years found from
13C/
12C carbon isotope mass balance calculations of measured atmospheric CO
2 13C/
12C carbon isotope data by Segalstad (1992); the ~5 years obtained from CO
2 solubility data by Murray (1992); and the ~5 years derived from CO
2 chemical kinetic data by Stumm & Morgan (1970).
Revelle & Suess (1957) calculated from data for the trace atmospheric molecule
14CO
2, containing the radioactive isotope
14C, that the amount of atmospheric "
CO2 derived from industrial fuel combustion" would be only 1.2% for an atmospheric CO
2 lifetime of 5 years, and 1.73% for a CO
2 lifetime of 7 years (Segalstad, 1998). Essenhigh (2009) reviews measurements of
14C from 1963 up to 1995, and finds that the RT of atmospheric
14CO
2 is ~16 (16.3) years. He also uses the
14C data to find that the time value (exchange time) for variation of the concentration difference between the northern and southern hemispheres is ~2 (2.2) years for atmospheric
14CO
2. This result compares well with the observed hemispheric transport of volcanic debris leading to "the year without a summer" in 1816 in the northern hemisphere after the 1815 Tambora volcano cataclysmic eruption in Indonesia in 1815.
Sundquist (1985) compiled a large number of measured RTs of CO
2 found by different methods. The list, containing RTs for both
12CO
2 and
14CO
2, was expanded by Segalstad (1998), showing a total range for all reported RTs from 1 to 15 years, with most RT values ranging from 5 to 15 years. Essenhigh (2009) emphasizes that this list of measured values of RT compares well with his calculated RT of 5 years (atmospheric bulk
12CO
2) and ~16 years (atmospheric trace
14CO
2). Furthermore he points out that the annual oscillations in the measured atmospheric CO
2 levels would be impossible without a short atmospheric residence time for the CO
2 molecules.
Essenhigh (2009) suggests that the difference in atmospheric CO
2 residence times between the gaseous molecules
12CO
2 and
14CO
2 may be due to differences in the kinetic absorption and/or dissolution rates of the two different gas molecules.
With such short residence times for atmospheric CO
2, Essenhigh (2009) correctly points out that it is impossible for the anthropogenic combustion supply of CO
2 to cause the given rise in atmospheric CO
2. Consequently, a rising atmospheric CO
2 concentration must be natural. This conclusion accords with measurements of
13C/
12C carbon isotopes in atmospheric CO
2, which show a maximum of 4% anthropogenic CO
2 in the atmosphere (including any biogenic CO
2), with 96% of the atmospheric CO
2 being isotopically indistinguishable from "natural" inorganic CO
2 exchanged with and degassed from the ocean, and degassed from volcanoes and the Earth's interior (Segalstad, 1992).
Essenhigh (2009) discusses alternative ways of expressing residence time, like fill time, decay time, e-fold time, turnover time, lifetime, and so on, and whether the Earth system carbon cycle is in dynamic equilibrium or non-equilibrium status. He concludes (like Segalstad, 1998) that the residence time is a robust parameter independent of the status of equilibrium, and that alternative expressions of the residence time give corresponding values.
It is important to compare Essenhigh's (2009) results with a recently published paper in PNAS by Solomon
et al. (2009), the first author of which (Susan Solomon) co-chairs the IPCC Working Group One, the part of the IPCC that deals with physical climate science. This paper was published after Essenhigh had submitted his manuscript to Energy & Fuels.
The message of Solomon
et al. (2009) is that there is an irreversible climate change due to the assimilation of CO
2 in the atmosphere, solely due to anthropogenic CO
2 emissions. From quantified scenarios of anthropogenic increases in atmospheric CO
2, their implication is that the CO
2 level flattens out asymptotically towards infinity, giving a residence time of more than 1000 years (without offering a definition or discussion of residence time or isotopic differences): "a quasi-equilibrium amount of CO
2 is expected to be retained in the atmosphere by the end of the millennium that is surprisingly large: typically ~40% of the peak concentration enhancement over preindustrial values (~280 ppmv)". The authors' Fig. 1, i.a. shows a peak level at 1200 ppmv atmospheric CO
2 in the year 2100, levelling off to an almost steady level of ~800 ppmv in the year 3000. It is not known how their 40% estimate was derived.
Solomon
et al. (2009) go on to say that "this can be easily understood on the basis of the observed instantaneous airborne fraction (AF
peak) of ~50% of anthropogenic carbon emissions retained during their build-up in the atmosphere, together with well-established ocean chemistry and physics that require ~20% of the emitted carbon to remain in the atmosphere on thousand-year timescales [quasi-equilibrium airborne fraction (AF
equil), determined largely by the Revelle factor governing the long-term partitioning of carbon between the ocean and atmosphere/biosphere system]".
Solomon
et al. (2009) have obviously not seriously considered the paper by Segalstad (1998), who addresses the 50% "missing sink" error of the IPCC and shows that the Revelle evasion "buffer" factor is ideologically defined from an assumed model (atmospheric anthropogenic CO
2 increase) and an assumed pre-industrial value for the CO
2 level, in conflict with the chemical
Henry's Law governing the fast ~1:50 equilibrium partitioning of CO
2 between gas (air) and fluid (ocean) at the Earth's average surface temperature. This CO
2 partitioning factor is strongly dependent on temperature because of the temperature-dependent retrograde aqueous solubility of CO
2, which facilitates fast degassing of dissolved CO
2 from a heated fluid phase (ocean), similar to what we experience from a heated carbonated drink.
Consequently, the IPCC's and Solomon
et al.'s (2009) non-realistic carbon cycle modelling and misconception of the way the geochemistry of CO
2 works simply defy reality, and would make it impossible for breweries to make the carbonated beer or soda "pop" that many of us enjoy (Segalstad, 1998).
So why is the correct estimate of the atmospheric residence time of CO
2 so important? The IPCC has constructed an artificial model where they claim that the natural CO
2 input/output is in static balance, and that all CO
2 additions from anthropogenic carbon combustion being added to the atmospheric pool will stay there almost indefinitely. This means that with an anthropogenic atmospheric CO
2 residence time of 50 - 200 years (Houghton, 1990) or near infinite (Solomon
et al., 2009), there is still a 50% error (nicknamed the "missing sink") in the IPCC's model, because the measured rise in the atmospheric CO
2 level is just half of that expected from the amount of anthropogenic CO
2 supplied to the atmosphere; and carbon isotope measurements invalidate the IPCC's model (Segalstad, 1992; Segalstad, 1998).
The correct evaluation of the CO
2 residence time -- giving values of about 5 years for the bulk of the atmospheric CO
2 molecules, as per Essenhigh's (2009) reasoning and numerous measurements with different methods -- tells us that the real world's CO
2 is part of a dynamic (i.e. non-static) system, where about one fifth of the atmospheric CO
2 pool is exchanged every year between different sources and sinks, due to relatively fast equilibria and temperature-dependent CO
2 partitioning governed by the chemical Henry's Law (Segalstad 1992; Segalstad, 1996; Segalstad, 1998).
Knowledge of the correct timing of the whereabouts of CO
2 in the air is
essential to a correct understanding of the way nature works and the extent of anthropogenic modulation of, or impact upon, natural processes. Concerning the Earth's carbon cycle, the anthropogenic contribution and its influence are so small and negligible that our resources would be much better spent on other
real challenges that are facing mankind.
Tom V. Segalstad
Associate Professor of Resource and Environmental Geology
The University of Oslo, Norway
Personal web page:
www.CO2web.infoReferences
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