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Inhibition of carbonate synthesis in acidic oceans on early Mars

Abstract

Several lines of evidence have recently reinforced the hypothesis that an ocean existed on early Mars1,2,3,4,5,6,7. Carbonates are accordingly expected to have formed from oceanic sedimentation of carbon dioxide from the ancient martian atmosphere7,8. But spectral imaging of the martian surface has revealed the presence of only a small amount of carbonate, widely distributed in the martian dust9. Here we examine the feasibility of carbonate synthesis in ancient martian oceans using aqueous equilibrium calculations. We show that partial pressures of atmospheric carbon dioxide in the range 0.8–4 bar, in the presence of up to 13.5 mM sulphate and 0.8 mM iron in sea water8, result in an acidic oceanic environment with a pH of less than 6.2. This precludes the formation of siderite, usually expected to be the first major carbonate mineral to precipitate8. We conclude that extensive interaction between an atmosphere dominated by carbon dioxide and a lasting sulphate- and iron-enriched acidic ocean on early Mars is a plausible explanation for the observed absence of carbonates.

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Figure 1: Stability boundaries of siderite and minnesotaite (under reducing conditions) and acidic solutions and haematite (under oxidizing conditions) on early Mars.
Figure 2: Evolution of the acidic martian environment over time.
Figure 3: Schematic representation of atmosphere–land–ocean interactions generating acidic environments in early Mars.

References

  1. Clifford, S. M. & Parker, T. J. The evolution of the martian hydrosphere: Implications for the fate of a primordial ocean and the current state of the northern plains. Icarus 154, 40–79 (2001)

    ADS  CAS  Article  Google Scholar 

  2. Phillips, R. J. et al. Ancient geodynamics and global-scale hydrology on Mars. Science 291, 2587–2591 (2001)

    ADS  CAS  Article  Google Scholar 

  3. Dohm, J. M. et al. Ancient drainage basin of the Tharsis region, Mars: Potential source for outflow channel systems and putative oceans or paleolakes. J. Geophys. Res. 106, 32943–32958 (2001)

    ADS  Article  Google Scholar 

  4. Craddock, R. A. & Howard, A. D. The case for rainfall on a warm, wet early Mars. J. Geophys. Res. 107, doi:10.1029/2001JE001505 (2002)

  5. Fairén, A. G. et al. Episodic flood inundations of the northern plains of Mars. Icarus 165, 53–67 (2003)

    ADS  Article  Google Scholar 

  6. Malin, M. C. & Edgett, K. S. Evidence for persistent flow and aqueous sedimentation on early Mars. Science 302, 1931–1934 (2003)

    ADS  CAS  Article  Google Scholar 

  7. Moore, J. M. Blueberry fields for ever. Nature 428, 711–712 (2004)

    ADS  CAS  Article  Google Scholar 

  8. Catling, D. C. A chemical model for evaporites on early Mars: Possible sedimentary tracers of the early climate and implications for exploration. J. Geophys. Res. 104, 16453–16469 (1999)

    ADS  CAS  Article  Google Scholar 

  9. Bandfield, J. L., Glotch, T. D. & Christensen, P. R. Spectroscopic identification of carbonate minerals in the martian dust. Science 301, 1084–1087 (2003)

    ADS  CAS  Article  Google Scholar 

  10. Carr, M. H. & Head, J. W. Oceans on Mars: An assessment of the observational evidence and possible fate. J. Geophys. Res. 108, doi:10.1029/2002JE001963 (2003)

  11. Kirkland, L. E., Herr, K. C. & Adams, P. M. Infrared stealthy surfaces: Why TES and THEMIS may miss some substantial mineral deposits on Mars and implications for remote sensing of planetary surfaces. J. Geophys. Res. 108, doi:10.1029/2003JE002105 (2003)

  12. Huguenin, R. L. J. The formation of goethite and hydrated clay minerals on Mars. J. Geophys. Res. 79, 3895–3905 (1974)

    ADS  CAS  Article  Google Scholar 

  13. Mukhin, L. M., Koscheev, A. P., Dikov, Yu. P., Huth, J. & Wänke, H. Experimental simulations of the photo-decomposition of carbonates and sulphates on Mars. Nature 379, 141–143 (1996)

    ADS  CAS  Article  Google Scholar 

  14. Clark, B. C. On the non-observability of carbonates on Mars. 5th Mars Conf. Abstr. 6214 (Lunar and Planetary Institute, Houston, Texas, 1999).

  15. Baker, V. R. Water and the Martian landscape. Nature 412, 228–236 (2001)

    ADS  CAS  Article  Google Scholar 

  16. Head, J. W. III, Kreslavsky, M. A. & Pratt, S. Northern lowlands of Mars: Evidence for wide-spread volcanic flooding and tectonic deformation in the Hesperian Period. J. Geophys. Res. 107, doi:10.1029/2000JE001445 (2002)

  17. Bhattacharyya, A. & Friedman, G. M. Modern Carbonate Environments (Hutchinson Ross, Stroudsburg, Pennsylvania, 1983)

    Google Scholar 

  18. Brain, D. A. & Jakosky, B. M. Atmospheric loss since the onset of the martian geologic record: Combined role of impact erosion and sputtering. J. Geophys. Res. 103, 22689–22694 (1998)

    ADS  CAS  Article  Google Scholar 

  19. Squyres, S. W. & Kasting, J. F. Early Mars: How warm and how wet? Science 265, 744–749 (1994)

    ADS  CAS  Article  Google Scholar 

  20. Forget, F. & Pierrehumbert, R. T. Warming early Mars with carbon dioxide clouds that scatter infrared radiation. Science 278, 1273–1276 (1997)

    ADS  CAS  Article  Google Scholar 

  21. Melosh, H. J. & Vickery, A. M. Impact erosion of the primordial atmosphere of Mars. Nature 338, 487–489 (1989)

    ADS  CAS  Article  Google Scholar 

  22. Barley, M. E., Pickard, A. L. & Sylvester, P. J. Emplacement of a large igneous province as possible cause of banded iron formation 2.45 billion years ago. Nature 385, 55–58 (1997)

    ADS  CAS  Article  Google Scholar 

  23. Russell, M. J. & Hall, A. J. The emergence of life from iron monosulphide bubbles at a submarine hydrothermal redox and pH front. J. Geol. Soc. 154, 377–402 (1997)

    ADS  CAS  Article  Google Scholar 

  24. Holland, H. D. The oceans: A possible source of iron in iron-formations. Econ. Geol. 68, 1169–1172 (1973)

    CAS  Article  Google Scholar 

  25. Zuber, M. T. The crust and mantle of Mars. Nature 412, 220–227 (2001)

    ADS  CAS  Article  Google Scholar 

  26. Schaefer, M. W. Aqueous geochemistry on early Mars. Geochim. Cosmochim. Acta 57, 4619–4625 (1993)

    ADS  CAS  Article  Google Scholar 

  27. Burns, R. G. Ferric sulfates on Mars. J. Geophys. Res. 92, 570–574 (1987)

    ADS  Article  Google Scholar 

  28. Fernández-Remolar, D. et al. The Tinto river, an extreme acidic environment under control of iron, as an analog of the Terra Meridiani hematite site of Mars. Planet. Space Sci. 52, 239–248 (2003)

    ADS  Article  Google Scholar 

  29. Johnson, J. W., Oelkers, E. H. & Helgeson, H. C. SUPCRT92: A software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bars and 0° to 1000 °C. (Earth Sciences Department, Lawrence Livermore Laboratory, 1991).

  30. Bruland, K. W. in Chemical Oceanography 8 (eds Riley, J. P. & Chester, R.) 157–220 (Academic, London, 1983)

    Book  Google Scholar 

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Acknowledgements

Special acknowledgements to the MER team, as their compelling evidence probing the acidity of martian palaeoenvironments was unfolded while our work was in progress, and resulted in adjustments in our model following our initial submitted draft. We also thank S. Clifford, I. Fairchild and J. Kasting for comments and suggestions that refined and focused this paper.

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Correspondence to Alberto G. Fairén.

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Fairén, A., Fernández-Remolar, D., Dohm, J. et al. Inhibition of carbonate synthesis in acidic oceans on early Mars. Nature 431, 423–426 (2004). https://doi.org/10.1038/nature02911

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