Reconciling the geology of Mars with models of atmospheric evolution remains a major challenge. Martian geology is characterized by past evidence for episodic surface liquid water, and geochemistry indicating a slow and intermittent transition from wetter to drier and more oxidizing surface conditions. Here we present a model that incorporates randomized injection of reducing greenhouse gases and oxidation due to hydrogen escape to investigate the conditions responsible for these diverse observations. We find that Mars could have transitioned repeatedly from reducing (hydrogen-rich) to oxidizing (oxygen-rich) atmospheric conditions in its early history. Our model predicts a generally cold early Mars, with mean annual temperatures below 240 K. If peak reducing-gas release rates and background carbon dioxide levels are high enough, it nonetheless exhibits episodic warm intervals sufficient to degrade crater walls, form valley networks and create other fluvial/lacustrine features. Our model also predicts transient build-up of atmospheric oxygen, which can help explain the occurrence of oxidized mineral species such as manganese oxides at Gale Crater. We suggest that the apparent Noachian–Hesperian transition from phyllosilicate deposition to sulfate deposition around 3.5 billion years ago can be explained as a combined outcome of increasing planetary oxidation, decreasing groundwater availability and a waning bolide impactor flux, which dramatically slowed the remobilization and thermochemical destruction of surface sulfates. Ultimately, rapid and repeated variations in Mars’s early climate and surface chemistry would have presented both challenges and opportunities for any emergent microbial life.
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The input data to the model used to produce the plots in this paper are available on GitHub at https://github.com/wordsworthgroup/mars_redox_2021, https://github.com/wordsworthgroup/mars_redox_2021/tree/main/PCM_LBL and https://github.com/wordsworthgroup/crustal-heat, with the exception of the HITRAN data used by the line-by-line radiative–convective model and the one-dimensional regolith heating data, which are available on Zenodo at https://doi.org/10.5281/zenodo.4458673.
The stochastic atmospheric evolution model, along with other scripts to reproduce plots in the paper, is available open source on GitHub at https://github.com/wordsworthgroup/mars_redox_2021. The line-by-line radiative–convective model used to produce the climate parameterization (PCM_LBL) is available open source on GitHub at https://github.com/wordsworthgroup/mars_redox_2021/PCM_LBL. The regolith thermal evolution model is available open source on GitHub at https://github.com/wordsworthgroup/crustal-heat. The Geochemist’s Workbench is proprietary software available at https://www.gwb.com/.
Carr, M. H. & Head, J. W. Geologic history of Mars. Earth Planet. Sci. Lett. 294, 185–203 (2010).
Grotzinger, J. P. et al. A habitable fluvio-lacustrine environment at Yellowknife Bay, Gale Crater, Mars. Science 343, 1242777 (2014).
Halevy, I., Zuber, M. T. & Schrag, D. P. A sulfur dioxide climate feedback on early Mars. Science 318, 1903–1907 (2007).
Tian, F. et al. Photochemical and climate consequences of sulfur outgassing on early Mars. Earth Planet. Sci. Lett. 295, 412–418 (2010).
Toon, O. B., Segura, T. & Zahnle, K. The formation of martian river valleys by impacts. Annu. Rev. Earth Planet. Sci. 38, 303–322 (2010).
Forget, F. et al. 3D modelling of the early martian climate under a denser CO2 atmosphere: temperatures and CO2 ice clouds. Icarus 222, 81–99 (2013).
Haberle, R. M., Catling, D. C., Carr, M. H. & Zahnle, K. J. in The Atmosphere and Climate of Mars (eds Haberle, R. M. et al.) Ch. 17 (Cambridge Univ. Press, 2017).
Ramirez, R. M. & Craddock, R. A. The geological and climatological case for a warmer and wetter early Mars. Nat. Geosci. 11, 230–237 (2018).
Hoke, M. R. T., Hynek, B. M. & Tucker, G. E. Formation timescales of large martian valley networks. Earth Planet. Sci. Lett. 312, 1–12 (2011).
Bishop, J. L. et al. Surface clay formation during short-term warmer and wetter conditions on a largely cold ancient Mars. Nat. Astron. 2, 206–213 (2018).
Lapotre, M. G. & Ielpi, A. The pace of fluvial meanders on Mars and implications for the western delta deposits of Jezero Crater. AGU Adv. 1, e2019AV000141 (2020).
Olsen, A. A. & Rimstidt, J. D. Using a mineral lifetime diagram to evaluate the persistence of olivine on Mars. Am. Mineral. 92, 598–602 (2007).
Ehlmann, B. L. & Edwards, C. S. Mineralogy of the martian surface. Annu. Rev. Earth Planet. Sci. 42, 291–315 (2014).
Niles, P. B. et al. Geochemistry of carbonates on Mars: implications for climate history and nature of aqueous environments. Space Sci. Rev. 174, 301–328 (2013).
Ehlmann, B. L. et al. Subsurface water and clay mineral formation during the early history of Mars. Nature 479, 53–60 (2011).
Bibring, J.-P. et al. Global mineralogical and aqueous mars history derived from OMEGA/Mars Express data. Science 312, 400–404 (2006).
Wadhwa, M. Redox state of Mars’ upper mantle and crust from Eu anomalies in shergottite pyroxenes. Science 291, 1527–1530 (2001).
Ramirez, R. M. et al. Warming early Mars with CO2 and H2. Nat. Geosci. 7, 59–63 (2014).
Wordsworth, R. et al. Transient reducing greenhouse warming on early Mars. Geophys. Res. Lett. 44, 665–671 (2017).
Lorand, J.-P. et al. The sulfur budget and sulfur isotopic composition of Martian regolith breccia NWA 7533. Meteorit. Planet. Sci. 55, 2097–2116 (2020).
Hurowitz, J. A. et al. Redox stratification of an ancient lake in Gale Crater, Mars. Science 356, eaah6849 (2017).
Lanza, N. L. et al. Oxidation of manganese in an ancient aquifer, Kimberley formation, Gale Crater, Mars. Geophys. Res. Lett. 43, 7398–7407 (2016).
Hurowitz, J. A., Fischer, W. W., Tosca, N. J. & Milliken, R. E. Origin of acidic surface waters and the evolution of atmospheric chemistry on early Mars. Nat. Geosci. 3, 323–326 (2010).
Liu, W. et al. Anoxic photogeochemical oxidation of manganese carbonate yields manganese oxide. Proc. Natl Acad. Sci. USA 117, 22698–22704 (2020).
Haberle, R. M., Zahnle, K. J., Barlow, N. G. & Steakley, K. Impact degassing of H2 on early Mars and its effect on the climate system. Geophys. Res. Lett. 46, 13355–13362 (2019).
Chassefière, E., Lasue, J., Langlais, B. & Quesnel, Y. Early Mars serpentinization-derived CH4 reservoirs, H2-induced warming and paleopressure evolution. Meteorit. Planet. Sci. 51, 2234–2245 (2016).
Tosca, N. J., Ahmed, I. A. M., Tutolo, B. M., Ashpitel, A. & Hurowitz, J. A. Magnetite authigenesis and the warming of early Mars. Nat. Geosci. 11, 635–639 (2018).
Jakosky, B. M. et al. Loss of the martian atmosphere to space: present-day loss rates determined from MAVEN observations and integrated loss through time. Icarus 351, 146–157 (2018).
Turbet, M., Boulet, C. & Karman, T. Measurements and semi-empirical calculations of CO2 + CH4 and CO2 + H2 collision-induced absorption across a wide range of wavelengths and temperatures. Application for the prediction of early Mars surface temperature. Icarus 346, 113762 (2020).
Mangold, N., Adeli, S., Conway, S., Ansan, V. & Langlais, B. A chronology of early Mars climatic evolution from impact crater degradation. J. Geophys. Res. Planets 117, E04003 (2012).
Fassett, C. I. & Head, J. W. Sequence and timing of conditions on early Mars. Icarus 211, 1204–1214 (2008).
Wordsworth, R. et al. Global modelling of the early martian climate under a denser CO2 atmosphere: water cycle and ice evolution. Icarus 222, 1–19 (2013).
Osterloo, M. M., Anderson, F. S., Hamilton, V. E. & Hynek, B. M. Geologic context of proposed chloride-bearing materials on Mars. J. Geophys. Res. Planets 115, E10012 (2010).
Hynek, B. M., Osterloo, M. K. & Kierein-Young, K. S. Late-stage formation of martian chloride salts through ponding and evaporation. Geology 43, 787–790 (2015).
McLennan, S. M. et al. Provenance and diagenesis of the evaporite-bearing Burns formation, Meridiani Planum, Mars. Earth Planet. Sci. Lett. 240, 95–121 (2005).
Halevy, I. & Head, J. W. Episodic warming of early Mars by punctuated volcanism. Nat. Geosci. 7, 865–868 (2014).
Gaillard, F., Michalski, J., Berger, G., McLennan, S. M. & Scaillet, B. Geochemical reservoirs and timing of sulfur cycling on Mars. Space Sci. Rev. 174, 251–300 (2013).
Wade, J., Dyck, B., Palin, R. M., Moore, J. D. P. & Smye, A. J. The divergent fates of primitive hydrospheric water on Earth and Mars. Nature 552, 391–394 (2017).
Milliken, R. E., Fischer, W. W. & Hurowitz, J. A. Missing salts on early Mars. Geophys. Res. Lett. 36, L11202 (2009).
Zolotov, M. Y. & Mironenko, M. V. Chemical models for martian weathering profiles: insights into formation of layered phyllosilicate and sulfate deposits. Icarus 275, 203–220 (2016).
Sholes, S. F., Smith, M. L., Claire, M. W., Zahnle, K. J. & Catling, D. C. Anoxic atmospheres on Mars driven by volcanism: implications for past environments and life. Icarus 290, 46–62 (2017).
Segura, T. L., Toon, O. B., Colaprete, A. & Zahnle, K. Environmental effects of large impacts on Mars. Science 298, 1977–1980 (2002).
Steakley, K., Murphy, J., Kahre, M., Haberle, R. & Kling, A. Testing the impact heating hypothesis for early Mars with a 3-D global climate model. Icarus 330, 169–188 (2019).
Palumbo, A. M. & Head, J. W. Impact cratering as a cause of climate change, surface alteration, and resurfacing during the early history of Mars. Meteorit. Planet. Sci. 54, 687–725 (2018).
Turbet, M. et al. The environmental effects of very large bolide impacts on early Mars explored with a hierarchy of numerical models. Meteorit. Planet. Sci. 54, 687–725 (2018).
Mitra, K., Moreland, E. L. & Catalano, J. G. Capacity of chlorate to oxidize ferrous iron: implications for iron oxide formation on Mars. Minerals 10, 729 (2020).
Fegley, B., Zolotov, M. Y. & Lodders, K. The oxidation state of the lower atmosphere and surface of Venus. Icarus 125, 416–439 (1997).
Wordsworth, R. D. Atmospheric nitrogen evolution on Earth and Venus. Earth Planet. Sci. Lett. 447, 103–111 (2016).
Niemann, H. B. et al. The abundances of constituents of Titanas atmosphere from the GCMS instrument on the Huygens probe. Nature 438, 779–784 (2005).
Wordsworth, R., Schaefer, L. & Fischer, R. Redox evolution via gravitational differentiation on low-mass planets: implications for abiotic oxygen, water loss, and habitability. Astron. J. 155, 195 (2018).
Tremaine, S. & Dones, L. On the statistical distribution of massive impactors. Icarus 106, 335–341 (1993).
Werner, S. C. & Tanaka, K. L. Redefinition of the crater-density and absolute-age boundaries for the chronostratigraphic system of Mars. Icarus 215, 603–607 (2011).
Mason, B. G., Pyle, D. M. & Oppenheimer, C. The size and frequency of the largest explosive eruptions on Earth. Bull. Volcanol. 66, 735–748 (2004).
Cannavò, F. & Nunnari, G. On a possible unified scaling law for volcanic eruption durations. Sci. Rep. 6, 22289 (2016).
Grott, M., Morschhauser, A., Breuer, D. & Hauber, E. Volcanic outgassing of CO2 and H2O on Mars. Earth Planet. Sci. Lett. 308, 391–400 (2011).
Sleep, N. H. & Zahnle, K. Carbon dioxide cycling and implications for climate on ancient Earth. J. Geophys. Res. 106, 1373–1400 (2001).
Papale, P. Global time-size distribution of volcanic eruptions on Earth. Sci. Rep. 8, 6838 (2018).
Zahnle, K., Pollack, J. B., Grinspoon, D. & Dones, L. Impact-generated atmospheres over Titan, Ganymede, and Callisto. Icarus 95, 1–23 (1992).
McCubbin, F. M. et al. Hydrous melting of the martian mantle produced both depleted and enriched shergottites. Geology 40, 683–686 (2012).
Herd, C. D. The oxygen fugacity of olivine-phyric martian basalts and the components within the mantle and crust of Mars. Meteorit. Planet. Sci. 38, 1793–1805 (2003).
Phillips, R. J. et al. Ancient geodynamics and global-scale hydrology on Mars. Science 291, 2587–2591 (2001).
Chassefière, E., Langlais, B., Quesnel, Y. & Leblanc, F. The fate of early Mars’ lost water: the role of serpentinization. J. Geophys. Res. Planets 118, 1123–1134 (2013).
Batalha, N., Domagal-Goldman, S. D., Ramirez, R. & Kasting, J. F. Testing the early Mars H2–CO2 greenhouse hypothesis with a 1-D photochemical model. Icarus 258, 337–349 (2015).
Tarnas, J. D. et al. Radiolytic H2 production on Noachian Mars: implications for habitability and atmospheric warming. Earth Planet. Sci. Lett. 502, 133–145 (2018).
Etiope, G., Ehlmann, B. L. & Schoell, M. Low temperature production and exhalation of methane from serpentinized rocks on Earth: a potential analog for methane production on Mars. Icarus 224, 276–285 (2013).
Lasue, J., Quesnel, Y., Langlais, B. & Chassefière, E. Methane storage capacity of the early martian cryosphere. Icarus 260, 205–214 (2015).
Chamberlain, J. W. & Hunten, D. M. Theory of Planetary Atmospheres. An Introduction to Their Physics and Chemistry (Academic Press, 1987).
Heavens, N. et al. Hydrogen escape from Mars enhanced by deep convection in dust storms. Nat. Astron. 2, 126–132 (2018).
Donahue, T. M. Evolution of water reservoirs on Mars from D/H ratios in the atmosphere and crust. Nature 374, 432–434 (1995).
Villanueva, G. L. et al. Strong water isotopic anomalies in the martian atmosphere: probing current and ancient reservoirs. Science 348, 218–221 (2015).
Heard, A. & Kite, E. S. A probabilistic case for a large missing carbon sink on Mars after 3.5 billion years ago. Earth Planet. Sci. Lett. 531, 116001 (2020).
Mahaffy, P. R. et al. The imprint of atmospheric evolution in the D/H of Hesperian clay minerals on Mars. Science 347, 412–414 (2015).
Lunine, J. I., Chambers, J., Morbidelli, A. & Leshin, L. A. The origin of water on Mars. Icarus 165, 1–8 (2003).
Kurokawa, H. et al. Evolution of water reservoirs on Mars: constraints from hydrogen isotopes in martian meteorites. Earth Planet. Sci. Lett. 394, 179–185 (2014).
Yung, Y. L. et al. HDO in the martian atmosphere: implications for the abundance of crustal water. Icarus 76, 146–159 (1988).
Krasnopolsky, V. A., Mumma, M. J. & Gladstone, G. R. Detection of atomic deuterium in the upper atmosphere of Mars. Science 280, 1576–1580 (1998).
Carr, M. H. & Head, J. W. Martian surface/near-surface water inventory: sources, sinks, and changes with time. Geophys. Res. Lett. 42, 726–732 (2015).
Brain, D. A. et al. The spatial distribution of planetary ion fluxes near Mars observed by MAVEN. Geophys. Res. Lett. 42, 9142–9148 (2015).
Lillis, R. J. et al. Characterizing atmospheric escape from Mars today and through time, with MAVEN. Space Sci. Rev. 195, 357–422 (2015).
Jakosky, B. M., Pepin, R. O., Johnson, R. E. & Fox, J. L. Mars atmospheric loss and isotopic fractionation by solar-wind-induced sputtering and photochemical escape. Icarus 111, 271–288 (1994).
Chassefière, E. & Leblanc, F. Mars atmospheric escape and evolution; interaction with the solar wind. Planet. Space Sci. 52, 1039–1058 (2004).
Lammer, H. et al. Outgassing history and escape of the martian atmosphere and water inventory. Space Sci. Rev. 174, 113–154 (2013).
Lillis, R. J. et al. Photochemical escape of oxygen from Mars: first results from MAVEN in situ data. J. Geophys. Res. Space Phys. 122, 3815–3836 (2017).
Jakosky, B. M. The CO2 inventory on Mars. Planet. Space Sci. 175, 52–59 (2019).
Kite, E. S., Williams, J.-P., Lucas, A. & Aharonson, O. Low palaeopressure of the martian atmosphere estimated from the size distribution of ancient craters. Nat. Geosci. 7, 335–339 (2014).
Hu, R., Kass, D. M., Ehlmann, B. L. & Yung, Y. L. Tracing the fate of carbon and the atmospheric evolution of Mars. Nat. Commun. 6, 10003 (2015).
Burns, R. G. & Fisher, D. S. Rates of oxidative weathering on the surface of Mars. J. Geophys. Res. Planets 98, 3365–3372 (1993).
Haberle, R. M. et al. On the possibility of liquid water on present-day Mars. J. Geophys. Res. Planets 106, 23317–23326 (2001).
McEwen, A. S. et al. Recurring slope lineae in equatorial regions of Mars. Nat. Geosci. 7, 53–58 (2014).
Huguenin, R. L. Photostimulated oxidation of magnetite: 1. Kinetics and alteration phase identification. J. Geophys. Res. 78, 8481–8493 (1973).
Wordsworth, R., Forget, F. & Eymet, V. Infrared collision-induced and far-line absorption in dense CO2 atmospheres. Icarus 210, 992–997 (2010).
Ding, F. & Wordsworth, R. D. A new line-by-line general circulation model for simulations of diverse planetary atmospheres: initial validation and application to the exoplanet GJ 1132b. Astrophys. J. 878, 117 (2019).
Gough, D. O. in Physics of Solar Variations (ed. Domingo, V.) 21–34 (Springer, 1981).
Minton, D. A. & Malhotra, R. Assessing the massive young Sun hypothesis to solve the warm young Earth puzzle. Astrophys. J. 660, 1700–1706 (2007).
Clifford, S. M. A model for the hydrologic and climatic behavior of water on Mars. J. Geophys. Res. 98, 10973–11016 (1993).
Hu, H. & Argyropoulos, S. A. Mathematical modelling of solidification and melting: a review. Model. Simul. Mater. Sci. Eng. 4, 371–396 (1996).
Truche, L. et al. Experimental reduction of aqueous sulphate by hydrogen under hydrothermal conditions: implication for the nuclear waste storage. Geochim. Cosmochim. Acta 73, 4824–4835 (2009).
Hem, J. D. Rates of manganese oxidation in aqueous systems. Geochim. Cosmochim. Acta 45, 1369–1374 (1981).
Morgan, J. J. Kinetics of reaction between O2 and Mn(ii) species in aqueous solutions. Geochim. Cosmochim. Acta 69, 35–48 (2005).
Linstrom, P. J. & Mallard, W. G. The NIST Chemistry WebBook: a chemical data resource on the internet. J. Chem. Eng. Data 46, 1059–1063 (2001).
R.W. thanks D. Johnston, K. Loftus, Y. Sekine and K. Zahnle for discussions. We thank N. Lanza for helpful comments on an earlier version of the manuscript. Funding: R.W. and M.B. acknowledge funding from NSF CAREER award AST-1847120 and NASA/VPL grant UWSC10439. J.H. acknowledges support from the Simons Collaboration on the Origin of Life.
The authors declare no competing interests.
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Wordsworth, R., Knoll, A.H., Hurowitz, J. et al. A coupled model of episodic warming, oxidation and geochemical transitions on early Mars. Nat. Geosci. 14, 127–132 (2021). https://doi.org/10.1038/s41561-021-00701-8
Nature Geoscience (2021)