Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Perspective
  • Published:

Mineral alteration in water-saturated liquid CO2 on early Mars

Nature Geoscience volume 17, pages 1204–1208 (2024)Cite this article

Subjects

Abstract

Geomorphological and mineralogical evidence is consistent with aqueous activity on ancient Mars, yet explaining the presence of substantial liquid water on early Mars remains challenging. Another fluid, liquid CO2, was probably present during Martian history, at least in the subsurface, and could even have been stable at the surface under a sufficiently dense CO2-rich early atmosphere. Liquid CO2 flows have been proposed as an alternative to water to explain morphological features, but it is widely accepted that water is the fluid responsible for mineral alteration. Interestingly, however, experimental research on geologic sequestration on Earth has revealed a surprising degree of chemical reactivity between CO2 fluid and minerals if the fluid is water-saturated, as it would probably have been on Mars. The resulting alteration products — carbonates, phyllosilicates and possibly sulfates — are consistent with minerals found on Mars today. We therefore propose that the formation of some of the aqueous mineral alteration observed on the Martian surface may have been mediated by liquid CO2. Further laboratory investigations are needed to test this hypothesis.

Access through your institution
Buy or subscribe

This is a preview of subscription content, access via your institution

Access options

Access through your institution

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Accelerated carbonate formation rates in water-saturated LCO2 compared to water alone.
Fig. 2: The phase diagram of CO2 constrains the minimum partial pressure \(p_{{\mathrm{CO}}_2}\) in both the present day and on early Mars.

Similar content being viewed by others

References

  1. Kasting, J. F. CO2 condensation and the climate of early Mars. Icarus 94, 1–13 (1991).

    CAS  Google Scholar 

  2. Batalha, N. E., Kopparapu, R. K., Haqq-Misra, J. & Kasting, J. F. Climate cycling on early Mars caused by the carbonate-silicate cycle. Earth Planet. Sci. Lett. 455, 7–13 (2016).

    CAS  Google Scholar 

  3. Kite, E. S. & Conway, S. Geological evidence for multiple climate transitions on early Mars. Nat. Geosci. 17, 10–19 (2024).

    CAS  Google Scholar 

  4. 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).

    CAS  Google Scholar 

  5. Bibring, J.-P. et al. Global mineralogical and aqueous Mars history derived from OMEGA/Mars Express Data. Science 312, 400–404 (2006).

    CAS  Google Scholar 

  6. Mars at war. Nat. Geosci. 11, 219 (2018).

  7. Hoffman, N. White Mars: a new model for Mars’ surface and atmosphere based on CO2. Icarus 146, 326–342 (2000).

    CAS  Google Scholar 

  8. Stewart, S. T. & Nimmo, F. Surface runoff features on Mars: testing the carbon dioxide formation hypothesis. J. Geophys. Res. Planets 107, 7.1–7.12 (2002).

    Google Scholar 

  9. Musselwhite, D. S., Swindle, T. D. & Lunine, J. I. Liquid CO2 breakout and the formation of recent small gullies on Mars. Geophys. Res. Lett. 28, 1283–1285 (2001).

    CAS  Google Scholar 

  10. Bryan, C. R. et al. Fundamental Study of CO2-H2O-Mineral Interactions for Carbon Sequestration, with Emphasis on the Nature of the Supercritical Fluid-Mineral Interface (US Department of Energy, 2013); https://www.osti.gov/servlets/purl/1096255/

  11. Regnault, O., Lagneau, V., Catalette, H. & Schneider, H. Étude expérimentale de la réactivité du CO2 supercritique vis-à-vis de phases minérales pures. Implications pour la séquestration géologique de CO2. C. R. Geosci. 337, 1331–1339 (2005).

    CAS  Google Scholar 

  12. Regnault, O., Lagneau, V. & Schneider, H. Experimental measurement of portlandite carbonation kinetics with supercritical CO2. Chem. Geol. 265, 113–121 (2009).

    CAS  Google Scholar 

  13. Lin, H., Fujii, T., Takisawa, R., Takahashi, T. & Hashida, T. Experimental evaluation of interactions in supercritical CO2/water/rock minerals system under geologic CO2 sequestration conditions. J. Mater. Sci. 43, 2307–2315 (2008).

    CAS  Google Scholar 

  14. Wigand, M., Kaszuba, J. P., Carey, J. W. & Hollis, W. K. Geochemical effects of CO2 sequestration on fractured wellbore cement at the cement/caprock interface. Chem. Geol. 265, 122–133 (2009).

    CAS  Google Scholar 

  15. Felmy, A. R. et al. Reaction of water-saturated supercritical CO2 with forsterite: evidence for magnesite formation at low temperatures. Geochim. Cosmochim. Acta 91, 271–282 (2012).

    CAS  Google Scholar 

  16. Placencia-Gómez, E. et al. Critical water coverage during forsterite carbonation in thin water films: activating dissolution and mass transport. Environ. Sci. Technol. 54, 6888–6899 (2020).

    Google Scholar 

  17. Jacquemet, N., Pironon, J. & Saint-Marc, J. Mineralogical changes of a well cement in various H2S-CO2(-brine) fluids at high pressure and temperature. Environ. Sci. Technol. 42, 282–288 (2008).

    CAS  Google Scholar 

  18. McGrail, B. P., Schaef, H. T., Glezakou, V.-A., Dang, L. X. & Owen, A. T. Water reactivity in the liquid and supercritical CO2 phase: has half the story been neglected? Energy Procedia 1, 3415–3419 (2009).

    CAS  Google Scholar 

  19. Mattson, E. D., Mcling, T., Smith, W. & Palmer, C. EGS rock reactions with supercritical CO2 saturated with water and water saturated with supercritical CO2. In Proc. Thirty-Eighth Workshop on Geothermal Reservoir Engineering (Curran Associates, 2013).

  20. Shao, H., Ray, J. R. & Jun, Y. S. Effects of salinity and the extent of water on supercritical CO2-induced phlogopite dissolution and secondary mineral formation. Environ. Sci. Technol. 45, 1737–1743 (2011).

    CAS  Google Scholar 

  21. Hangx, S. J. T. & Spiers, C. J. Reaction of plagioclase feldspars with CO2 under hydrothermal conditions. Chem. Geol. 265, 88–98 (2009).

    CAS  Google Scholar 

  22. Yang, Y., Ronzio, C. & Jun, Y. S. The effects of initial acetate concentration on CO2-brine-anorthite interactions under geologic CO2 sequestration conditions. Energy Environ. Sci. 4, 4596–4606 (2011).

    CAS  Google Scholar 

  23. Knauss, K. G., Johnson, J. W. & Steefel, C. I. Evaluation of the impact of CO2, co-contaminant gas, aqueous fluid and reservoir rock interactions on the geologic sequestration of CO2. Chem. Geol. 217, 339–350 (2005).

    CAS  Google Scholar 

  24. Bacon, D. H. & Murphy, E. M. Managing chemistry underground: is co-sequestration an option in selected formations? Energy Procedia 4, 4457–4464 (2011).

    CAS  Google Scholar 

  25. Bacon, D. H., Ramanathan, R., Schaef, H. T. & McGrail, B. P. Simulating geologic co-sequestration of carbon dioxide and hydrogen sulfide in a basalt formation. Int. J. Greenh. Gas Con. 21, 165–176 (2014).

    CAS  Google Scholar 

  26. Crandell, L. E., Ellis, B. R. & Peters, C. A. Dissolution potential of SO2 co-injected with CO2 in geologic sequestration. Environ. Sci. Technol. 44, 349–355 (2010).

    CAS  Google Scholar 

  27. Schaef, H. T. et al. Mineralization of basalts in the CO2-H2O-SO2-O2 system. Environ. Sci. Technol. 48, 5298–5305 (2014).

    CAS  Google Scholar 

  28. Ellis, B. R., Crandell, L. E. & Peters, C. A. Limitations for brine acidification due to SO2 co-injection in geologic carbon sequestration. Int. J. Greenh. Gas Con. 4, 575–582 (2010).

    CAS  Google Scholar 

  29. Loring, J. S. et al. In situ infrared spectroscopic study of forsterite carbonation in wet supercritical CO2. Environ. Sci. Technol. 45, 6204–6210 (2011).

    CAS  Google Scholar 

  30. Thompson, C. J., Loring, J. S., Rosso, K. M. & Wang, Z. Comparative reactivity study of forsterite and antigorite in wet supercritical CO2 by in situ infrared spectroscopy. Int. J. Greenh. Gas Con. 18, 246–255 (2013).

    CAS  Google Scholar 

  31. Miller, Q. R. S. et al. Surface-catalyzed oxygen exchange during mineral carbonation in nanoscale water films. J. Phys. Chem. C 123, 12871–12885 (2019).

    CAS  Google Scholar 

  32. Kerisit, S. N., Mergelsberg, S. T., Thompson, C. J., White, S. K. & Loring, J. S. Thin water films enable low-temperature magnesite growth under conditions relevant to geologic carbon sequestration. Environ. Sci. Technol. 55, 12539–12548 (2021).

    CAS  Google Scholar 

  33. Li, H. et al. Water mobility in the interfacial liquid layer of ice/clay nanocomposites. Angew. Chem. Int. Ed. 60, 7697–7702 (2021).

    CAS  Google Scholar 

  34. Kite, E. S. Geologic constraints on early Mars climate. Space Sci. Rev. 215, 10 (2019).

    Google Scholar 

  35. Jakosky, B. M. The CO2 inventory on Mars. Planet. Space Sci. 175, 52–59 (2019).

    CAS  Google Scholar 

  36. Dundas, C. M. et al. The formation of gullies on Mars today. Geol. Soc. Spec. Publ. 467, 67–94 (2019).

    Google Scholar 

  37. David, E., Aharonson, O., Vos, E., Forget, F. & Schorghofer, N. The effect of ground ice redistribution on the martian paleo-CO2 cycle. In Proc. 54th Lunar and Planetary Science Conference 2806 (USRA, 2023).

  38. Wordsworth, R. D., Kerber, L., Pierrehumbert, R. T., Forget, F. & Head, J. W. Comparison of ‘warm and wet’ and ‘cold and icy’ scenarios for early Mars in a 3-D climate model. J. Geophys. Res. Planets 120, 1201–1219 (2015).

    Google Scholar 

  39. Buhler, P. B. A 510,000-year record of Mars’ climate. Geophys. Res. Lett. 50, e2022GL101752 (2023).

    Google Scholar 

  40. Alwarda, R. & Smith, I. B. Stratigraphy and volumes of the units within the massive carbon dioxide ice deposits of mars. J. Geophys. Res. Planets 126, e2020JE006767 (2021).

    CAS  Google Scholar 

  41. Putzig, N. E. et al. Three-dimensional radar imaging of structures and craters in the Martian polar caps. Icarus 308, 138–147 (2018).

    CAS  Google Scholar 

  42. Buhler, P. B. & Piqueux, S. Obliquity-driven CO2 exchange between Mars’ atmosphere, regolith and polar cap. J. Geophys. Res. Planets 126, e2020JE006759 (2021).

    CAS  Google Scholar 

  43. Soto, A., Mischna, M., Schneider, T., Lee, C. & Richardson, M. Martian atmospheric collapse: idealized GCM studies. Icarus 250, 553–569 (2015).

    CAS  Google Scholar 

  44. Mellon, M. T. Limits on the CO2 content of the martian polar deposits. Icarus 124, 268–279 (1996).

    CAS  Google Scholar 

  45. He, S. & Morse, J. W. The carbonic acid system and calcite solubility in aqueous Na-K-Ca-Mg-Cl-SO4 solutions from 0 to 90 °C. Geochim. Cosmochim. Acta 57, 3533–3554 (1993).

    CAS  Google Scholar 

  46. Haghi, R. K., Chapoy, A., Peirera, L. M. C., Yang, J. & Tohidi, B. pH of CO2 saturated water and CO2 saturated brines: experimental measurements and modelling. Int. J. Greenh. Gas Con. 66, 190–203 (2017).

    CAS  Google Scholar 

  47. Yen, A. S. et al. Multiple stages of aqueous alteration along fractures in mudstone and sandstone strata in Gale Crater, Mars. Earth Planet. Sci. Lett. 471, 186–198 (2017).

    CAS  Google Scholar 

  48. Hausrath, E. M., Ming, D. W., Rampe, E. B. & Peretyazhko, T. S. Reactive transport modeling of aqueous alteration in the Murray formation, Gale crater, Mars. ACS Earth Space Chem. 5, 424–435 (2021).

    CAS  Google Scholar 

  49. Rampe, E. B. et al. Mineralogy of an ancient lacustrine mudstone succession from the Murray formation, Gale crater, Mars. Earth Planet. Sci. Lett. 471, 172–185 (2017).

    CAS  Google Scholar 

  50. Bristow, T. F. et al. Brine-driven destruction of clay minerals in Gale crater, Mars. Science 373, 198–204 (2021).

    CAS  Google Scholar 

  51. Treiman, A. H. et al. Manganese-iron phosphate nodules at the Groken site, Gale crater, Mars. Minerals 13, 1122 (2023).

    CAS  Google Scholar 

  52. Rampe, E. B. et al. Mineralogy of Vera Rubin ridge from the Mars Science Laboratory CheMin instrument. J. Geophys. Res. Planets 125, e2019JE006306 (2020).

    CAS  Google Scholar 

Download references

Acknowledgements

A portion of this work was conducted at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration (80NM0018D0004).

Author information

Authors and Affiliations

  1. MIT Haystack Observatory, Westford, MA, USA

    Michael H. Hecht

  2. Department of Earth Science & Engineering, Imperial College London, London, UK

    Samuel Krevor, Mark A. Sephton & Samuel P. Kounaves

  3. Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA

    Albert S. Yen, Michael A. Mischna & Max Coleman

  4. Plancius Research, Severna Park, MD, USA

    Adrian J. Brown

  5. University of Alberta, Edmonton, Alberta, Canada

    Nicolas Randazzo

  6. Department of Chemistry, Tufts University, Medford, MA, USA

    Samuel P. Kounaves

  7. Carnegie Institute for Science, Washington, DC, USA

    Andrew Steele

  8. Arizona State University, Tempe, AZ, USA

    James W. Rice Jr

  9. York University, Toronto, Ontario, Canada

    Isaac B. Smith

  10. Planetary Science Institute, Lakewood, CO, USA

    Isaac B. Smith

  11. Queensland University of Technology, Brisbane, Queensland, Australia

    David Flannery

  12. Johnson Space Center, Houston, TX, USA

    Marc Fries

Authors
  1. Michael H. Hecht
    View author publications

    You can also search for this author inPubMed Google Scholar

  2. Samuel Krevor
    View author publications

    You can also search for this author inPubMed Google Scholar

  3. Albert S. Yen
    View author publications

    You can also search for this author inPubMed Google Scholar

  4. Adrian J. Brown
    View author publications

    You can also search for this author inPubMed Google Scholar

  5. Nicolas Randazzo
    View author publications

    You can also search for this author inPubMed Google Scholar

  6. Michael A. Mischna
    View author publications

    You can also search for this author inPubMed Google Scholar

  7. Mark A. Sephton
    View author publications

    You can also search for this author inPubMed Google Scholar

  8. Samuel P. Kounaves
    View author publications

    You can also search for this author inPubMed Google Scholar

  9. Andrew Steele
    View author publications

    You can also search for this author inPubMed Google Scholar

  10. James W. Rice Jr
    View author publications

    You can also search for this author inPubMed Google Scholar

  11. Isaac B. Smith
    View author publications

    You can also search for this author inPubMed Google Scholar

  12. Max Coleman
    View author publications

    You can also search for this author inPubMed Google Scholar

  13. David Flannery
    View author publications

    You can also search for this author inPubMed Google Scholar

  14. Marc Fries
    View author publications

    You can also search for this author inPubMed Google Scholar

Contributions

M.H.H. conceived the study and led the writing effort. Specific author contributions include S. Krevor to the sequestration literature review, I.B.S. to the LCO2 scenario thermophysics, M.M. to the early climate considerations, M.C. and M.S. to the relevance to astrobiology and organics preservation, S. Kounaves to the geochemical considerations, A.S.Y. and D.F. to establishing the relevance to Martian mineralogy, N.R. to the writing and analysis, J.W.R. to implications for Martian geomorphology, and M.F. to understanding Martian volatile evolution. A.S., A.J.B. and several other authors contributed to writing and review of the manuscript.

Corresponding author

Correspondence to Michael H. Hecht.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Geoscience thanks Paul Niles and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Tamara Goldin, in collaboration with the Nature Geoscience team.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Hecht, M.H., Krevor, S., Yen, A.S. et al. Mineral alteration in water-saturated liquid CO2 on early Mars. Nat. Geosci. 17, 1204–1208 (2024). https://doi.org/10.1038/s41561-024-01576-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41561-024-01576-1

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing