Quantifying drivers of chemical disequilibrium: theory and application to methane in the Earth's atmosphere
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Abstract
Abstract. It has long been observed that Earth's atmosphere is uniquely far from its thermochemical equilibrium state in terms of its chemical composition. Studying this state of disequilibrium is important both for understanding the role that life plays in the Earth system, and for its potential role in the detection of life on exoplanets. Here we present a methodology for assessing the strength of the biogeochemical cycling processes that drive disequilibrium in planetary atmospheres. We apply it to the simultaneous presence of CH4 and O2 in Earth's atmosphere, which has long been suggested as a sign of life that could be detected remotely. Using a simplified model, we identify that the most important property to quantify is not the distance from equilibrium, but the power required to drive it. A weak driving force can maintain a high degree of disequilibrium if the residence times of the compounds involved are long; but if the disequilibrium is high and the kinetics fast, we can conclude that the disequilibrium must be driven by a substantial source of energy. Applying this to Earth's atmosphere, we show that the biotically generated portion of the power required to maintain the methane–oxygen disequilibrium is around 0.67 TW, although the uncertainty in this figure is about 10% due to uncertainty in the global CH4 production. Compared to the chemical energy generated by the biota by photosynthesis, 0.67 TW represents only a very small fraction and, perhaps surprisingly, is of a comparable magnitude to abiotically driven geochemical processes at the Earth's surface. We discuss the implications of this new approach, both in terms of enhancing our understanding of the Earth system, and in terms of its impact on the possible detection of distant photosynthetic biospheres.
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The modern O2-CH4 redox couple is a compelling disequilibrium biosignature because of the short kinetic lifetime (~10 years) of methane in Earth's atmosphere.
“The modern O2-CH4 redox couple is widely believed to be a compelling disequilibrium biosignature because of the short kinetic lifetime (~10 years) of methane in Earth’s atmosphere (21, 22)”
From Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life (2018) · cites this paper as [22]
Atmospheric disequilibria are the product of the generation of free energy balanced by the dissipation of free energy.
“In general, atmospheric disequilibria are the product of the generation of free energy balanced by the dissipation of free energy.”
From Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life (2018) · cites this paper as [22]
A large thermodynamic disequilibrium could be the consequence of either a high free energy generation rate or a low dissipation rate.
“A large thermodynamic disequilibrium could be the consequence of either a high free energy generation rate or a low dissipation rate (22).”
From Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life (2018) · cites this paper as [22]
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Cites
Biogeochemistry: an Analysis of Global Change
(1991) · Elsevier eBooks · doi:10.1016/c2012-0-01654-7 · Cited by 3,444 · see citing works
Atmospheric homeostasis by and for the biosphere: the gaia hypothesis
Lovelock, J. E., & Margulis, L. (1974) · Tellus · doi:10.3402/tellusa.v26i1-2.9731 · Cited by 1,325 · see citing works
A search for life on Earth from the Galileo spacecraft
Sagan, C., Thompson, W. R., Carlson, R., Gurnett, D., & Hord, C. (1993) · Nature · doi:10.1038/365715a0 · Cited by 507 · see citing works
Moses, J. I., Visscher, C., Fortney, J. J., Showman, A. P., Lewis, N. K., Griffith, C. A., Klippenstein, S. J., Shabram, M., Friedson, A. J., Marley, M. S., et al. (2011) · The Astrophysical Journal · doi:10.1088/0004-637x/737/1/15 · Cited by 491 · see citing works
The Minimum Entropy Production Principle
Jaynes, E. (1980) · Annual Review of Physical Chemistry · doi:10.1146/annurev.pc.31.100180.003051 · Cited by 456 · see citing works
A Physical Basis for Life Detection Experiments
LOVELOCK, J. E. (1965) · Nature · doi:10.1038/207568a0 · Cited by 446 · see citing works
Introduction to Atmospheric Chemistry
Hobbs, P. V. (2000) · Cambridge University Press eBooks · doi:10.1017/cbo9780511808913 · Cited by 357 · see citing works
A coupled atmosphere–ecosystem model of the early Archean Earth
KHARECHA, P., KASTING, J., & SIEFERT, J. (2005) · Geobiology · doi:10.1111/j.1472-4669.2005.00049.x · Cited by 321 · see citing works
Lenton, T. M. (1998) · Nature · doi:10.1038/28792 · Cited by 302 · see citing works
Rise of atmospheric oxygen and the “upside‐down” Archean mantle
Kump, L. R., Kasting, J. F., & Barley, M. (2001) · Geochemistry Geophysics Geosystems · doi:10.1029/2000gc000114 · Cited by 186 · see citing works
QUENCHING OF CARBON MONOXIDE AND METHANE IN THE ATMOSPHERES OF COOL BROWN DWARFS AND HOT JUPITERS
Visscher, C., & Moses, J. I. (2011) · The Astrophysical Journal · doi:10.1088/0004-637x/738/1/72 · Cited by 183 · see citing works
Carbon Monoxide on Jupiter and Implications for Atmospheric Convection
Prinn, R. G., & Barshay, S. S. (1977) · Science · doi:10.1126/science.198.4321.1031 · Cited by 170 · see citing works
Life, hierarchy, and the thermodynamic machinery of planet Earth.
Kleidon, A. (2010) · Physics of Life Reviews · doi:10.1016/j.plrev.2010.10.002 · Cited by 169 · see citing works
Self-citationCarbon Monoxide on Jupiter and Implications for Atmospheric Convection
Prinn, R. G., & Barshay, S. S. (1977) · Science · doi:10.1126/science.198.4321.1031-a · Cited by 168 · see citing works
Abiotic formation of O2and O3in high-CO2terrestrial atmospheres
Segura, A., Meadows, V. S., Kasting, J. F., Crisp, D., & Cohen, M. (2007) · Astronomy and Astrophysics · doi:10.1051/0004-6361:20066663 · Cited by 156 · see citing works
Thermodynamics and the recognition of alien biospheres
Lovelock, J. E. (1975) · Proceedings of the Royal Society B Biological Sciences · doi:10.1098/rspb.1975.0051 · Cited by 155 · see citing works
HIGH METALLICITY AND NON-EQUILIBRIUM CHEMISTRY IN THE DAYSIDE ATMOSPHERE OF HOT-NEPTUNE GJ 436b
Madhusudhan, N., & Seager, S. (2011) · The Astrophysical Journal · doi:10.1088/0004-637x/729/1/41 · Cited by 139 · see citing works
The Alkaline Solution to the Emergence of Life: Energy, Entropy and Early Evolution
Russell, M. J. (2007) · Acta Biotheoretica · doi:10.1007/s10441-007-9018-5 · Cited by 126 · see citing works
Signs of Life: Criterion-System of Exobiology
Lederberg, J. (1965) · Nature · doi:10.1038/207009a0 · Cited by 123 · see citing works
COMPOSITIONS OF HOT SUPER-EARTH ATMOSPHERES: EXPLORING KEPLER CANDIDATES
Miguel, Y., Kaltenegger, L., Fegley, B., et al. (2011) · The Astrophysical Journal Letters · doi:10.1088/2041-8205/742/2/l19 · Cited by 120 · see citing works
Kleidon, A., Zehe, E., Ehret, U., & Scherer, U. (2013) · Hydrology and earth system sciences · doi:10.5194/hess-17-225-2013 · Cited by 112 · see citing works
Self-citationVisscher, C., Moses, J. I., & Saslow, S. A. (2010) · Icarus · doi:10.1016/j.icarus.2010.03.029 · Cited by 107 · see citing works
A layer of ozone detected in the nightside upper atmosphere of Venus
Montmessin, F., Bertaux, J., Lefèvre, F., Marcq, E., Belyaev, D. A., Gérard, J., Korablev, O., Fedorova, A. A., Sarago, V., & Vandaele, A. C. (2011) · Icarus · doi:10.1016/j.icarus.2011.08.010 · Cited by 102 · see citing works
Kleidon, A. (2012) · Philosophical Transactions of the Royal Society A Mathematical Physical and Engineering Sciences · doi:10.1098/rsta.2011.0316 · Cited by 101 · see citing works
Self-citationA PHOTOCHEMICAL MODEL FOR THE CARBON-RICH PLANET WASP-12b
Kopparapu, R. K., Kasting, J. F., & Zahnle, K. J. (2011) · The Astrophysical Journal · doi:10.1088/0004-637x/745/1/77 · Cited by 93 · see citing works
Introduction to Atmospheric Chemistry
(2017) · Princeton University Press eBooks · doi:10.2307/j.ctvc77ddr.10 · Cited by 92 · see citing works
Quenching of carbon monoxide and methane in the atmospheres of cool brown dwarfs and hot jupitersPreprint
Visscher, C., & Moses, J. I. (2011) · Cited by 74 · see citing works
Thermodynamic Equilibria in Planetary Atmospheres
Lippincott, E. R., Eck, R. V., Dayhoff, M. O., & Sagan, C. (1967) · The Astrophysical Journal · doi:10.1086/149051 · Cited by 73 · see citing works
High Metallicity and Non-Equilibrium Chemistry in the Dayside Atmosphere of Hot-Neptune Gj 436b
Madhusudhan, N., & Seager, S. (2011) · DSpace@MIT (Massachusetts Institute of Technology) · Cited by 71 · see citing works
Kleidon, A. (2012) · MPG.PuRe (Max Planck Society) · Cited by 62 · see citing works
Self-citationATMOSPHERIC CHEMISTRY OF VENUS-LIKE EXOPLANETS
Schaefer, L., & Fegley, B. (2011) · The Astrophysical Journal · doi:10.1088/0004-637x/729/1/6 · Cited by 58 · see citing works
Methane emissions from Earth’s degassing: Implications for Mars
Etiope, G., Oehler, D., & Allen, C. (2011) · Planetary and Space Science · doi:10.1016/j.pss.2010.06.003 · Cited by 52 · see citing works
Dyke, J. G., Gans, F., & Kleidon, A. (2011) · Earth System Dynamics · doi:10.5194/esd-2-139-2011 · Cited by 35 · see citing works
Self-citationThermodynamics of Steady States
Tykodi, R. J., & Nossal, R. (1968) · Physics Today · doi:10.1063/1.3034942 · Cited by 29 · see citing works
ATMOSPHERIC CHEMISTRY OF VENUS-LIKE EXOPLANETS
Schaefer, L., & Fegley, B. (2011) · Cited by 23 · see citing works
Vertical Transports by Plumes within the Moderately Convective Marine Atmospheric Surface Layer
Mason, R. A., Shirer, H. N., Wells, R., & Young, G. S. (2002) · Journal of the Atmospheric Sciences · doi:10.1175/1520-0469(2002)059 · Cited by 5 · see citing works
Walker, J. C. G. (1980) · The handbook of environmental chemistry · doi:10.1007/978-3-540-38516-5_5 · Cited by 5 · see citing works
Flagged first, then by citations
Research works printed but not linked: 3
- Atkins, P. W.: Physical Chemistry, 5th Edn., Oxford University Press, 1994.
- Ehhalt, D. M., Prather, M., Dentener, F., Derwent, R., Dlugokencky, E., Holland, E., Isaksen, I., Katima, J., Kirchhoff, V., Matson, P., Midgley, P., and Wang, M.: Atmospheric Chemistry and Green- house Gases, in: Climate Change 2001: The Scientific Basis. Contribution of Working Group I to the Third Assessment Re- port of the Intergovernmental Panel on Climate Change, edited by: Houghton, J. T., Ding, Y., Griggs, D. J., Noguer, M., van der Linden, P. J., Dai, X., Maskell, K., and Johnson, C. A., Cam- bridge University Press, Cambridge, UK and New York, NY, USA, 881 pp., 2001.
- Kondepudi, D. and Prigogine, I.: Modern Thermodynamics, Wiley, 1996.
Cited by
Sorted by citations
Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life
Krissansen-Totton, J., Olson, S., & Catling, D. C. (2018) · Science Advances · doi:10.1126/sciadv.aao5747 · Cited by 177 · see citing works
Thermodynamic Foundations of the Earth System
Kleidon, A. (2016) · doi:10.1017/cbo9781139342742 · Cited by 133 · see citing works
Self-citationOn Detecting Biospheres from Chemical Thermodynamic Disequilibrium in Planetary Atmospheres
Krissansen-Totton, J., Bergsman, D. S., & Catling, D. C. (2016) · Astrobiology · doi:10.1089/ast.2015.1327 · Cited by 132 · see citing works
- Authors
- Simoncini, E., Virgo, N., & Kleidon, A.
- Affiliations
- Arcetri Astrophysical Observatory (IT)
- Max Planck Institute for Biogeochemistry (DE)
- Venue
- Earth System Dynamics
- Publisher
- Copernicus GmbH
- Published
- 2013-09-11
- Volume
- 4
- Issue
- 2
- Pages
- 317-331
- ISSN
- 2190-4979 (ISSN-L)
- 2190-4987
- OpenAlex
- W2159925295
- Cited by
- 30
- References
- 37
- Citations by year
- 2024: 2 · 2023: 3 · 2022: 2 · 2021: 1 · 2020: 3 · 2019: 1 · 2018: 9 · 2017: 5 · 2016: 3 · 2014: 1
- FWCI
- 0.87
- Type
- journal article
- Language
- en
- Open access
- gold
- doi.org
- Licence
- Locations
- Earth System Dynamics (publishedVersion, cc-by)
- DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
- MPG.PuRe (Max Planck Society) (submittedVersion, other-oa)
- Funders
- Helmholtz-Gemeinschaft
- Topics
- Physical Sciences › Earth and Planetary Sciences › Atmospheric Science › Earth Systems and Cosmic Evolution
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Space Science and Extraterrestrial Life
- Physical Sciences › Environmental Science › Global and Planetary Change › Atmospheric and Environmental Gas Dynamics
- Keywords
- Earth's atmosphere, biogeochemical cycles, biosignatures, residence time, methane production, life detection
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