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Title: Oxidative Alteration of Ferrous Smectites and Implications for the Redox Evolution of Early Mars: Oxidation Products of Ferrous Smectites

Abstract

Surface conditions on early Mars were likely anoxic, similar to early Earth, but the timing of the evolution to oxic conditions characteristic of contemporary Mars is unresolved. Ferrous trioctahedral smectites are the thermodynamically predicted products of anoxic basalt weathering, but orbital analyses of Noachian-aged terrains find primarily Fe 3+-bearing clay minerals. Rover-based detection of Fe 2+-bearing trioctahedral smectites at Gale Crater suggests that ferrous smectites are the unoxidized progenitors of orbitally detected ferric smectites. To assess this pathway, we conducted ambient-temperature oxidative alteration experiments on four synthetic ferrous smectites having molar Fe/(Mg + Fe) from 1.00 to 0.33. Smectite suspension in air-saturated solutions produced incomplete oxidation (24–38% Fe 3+/ΣFe). Additional smectite oxidation occurred upon reexposure to air-saturated solutions after anoxic hydrothermal recrystallization, which accelerated cation and charge redistribution in the octahedral sheet. Oxidation was accompanied by contraction of the octahedral sheet (d (060) decreased from 1.53–1.56 Å to 1.52 Å), consistent with a shift toward dioctahedral structure. Ferrous smectite oxidation by aqueous hydrogen peroxide solutions resulted in nearly complete Fe 2+ oxidation but also led to partial Fe 3+ ejection from the structure, producing nanoparticulate hematite. Reflectance spectra of oxidized smectites were characterized by (Fe 3+,Mg) 2-OH bands at 2.28–2.30more » μm, consistent with oxidative formation of dioctahedral nontronite. Accordingly, ferrous smectites are plausible precursors to observed ferric smectites on Mars, and their presence in late-Noachian sedimentary units suggests that anoxic conditions may have persisted on Mars beyond the Noachian.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [2]
  1. Temple Univ., Philadelphia, PA (United States); Washington Univ., St. Louis, MO (United States)
  2. Washington Univ., St. Louis, MO (United States)
  3. EIS Directorate, NASA Johnson Space Center, Houston TX USA
  4. Univ. of Alabama, Birmingham, AL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Aeronautic and Space Administration (NASA); USDOE
OSTI Identifier:
1417389
Alternate Identifier(s):
OSTI ID: 1411260
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Geophysical Research. Planets
Additional Journal Information:
Journal Volume: 122; Journal Issue: 12; Journal ID: ISSN 2169-9097
Publisher:
American Geophysical Union
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Mars; clay mineralogy; alteration and weathering processes; experimental mineralogy; Gale Crater

Citation Formats

Chemtob, Steven M., Nickerson, Ryan D., Morris, Richard V., Agresti, David G., and Catalano, Jeffrey G. Oxidative Alteration of Ferrous Smectites and Implications for the Redox Evolution of Early Mars: Oxidation Products of Ferrous Smectites. United States: N. p., 2017. Web. doi:10.1002/2017JE005331.
Chemtob, Steven M., Nickerson, Ryan D., Morris, Richard V., Agresti, David G., & Catalano, Jeffrey G. Oxidative Alteration of Ferrous Smectites and Implications for the Redox Evolution of Early Mars: Oxidation Products of Ferrous Smectites. United States. doi:10.1002/2017JE005331.
Chemtob, Steven M., Nickerson, Ryan D., Morris, Richard V., Agresti, David G., and Catalano, Jeffrey G. Fri . "Oxidative Alteration of Ferrous Smectites and Implications for the Redox Evolution of Early Mars: Oxidation Products of Ferrous Smectites". United States. doi:10.1002/2017JE005331. https://www.osti.gov/servlets/purl/1417389.
@article{osti_1417389,
title = {Oxidative Alteration of Ferrous Smectites and Implications for the Redox Evolution of Early Mars: Oxidation Products of Ferrous Smectites},
author = {Chemtob, Steven M. and Nickerson, Ryan D. and Morris, Richard V. and Agresti, David G. and Catalano, Jeffrey G.},
abstractNote = {Surface conditions on early Mars were likely anoxic, similar to early Earth, but the timing of the evolution to oxic conditions characteristic of contemporary Mars is unresolved. Ferrous trioctahedral smectites are the thermodynamically predicted products of anoxic basalt weathering, but orbital analyses of Noachian-aged terrains find primarily Fe3+-bearing clay minerals. Rover-based detection of Fe2+-bearing trioctahedral smectites at Gale Crater suggests that ferrous smectites are the unoxidized progenitors of orbitally detected ferric smectites. To assess this pathway, we conducted ambient-temperature oxidative alteration experiments on four synthetic ferrous smectites having molar Fe/(Mg + Fe) from 1.00 to 0.33. Smectite suspension in air-saturated solutions produced incomplete oxidation (24–38% Fe3+/ΣFe). Additional smectite oxidation occurred upon reexposure to air-saturated solutions after anoxic hydrothermal recrystallization, which accelerated cation and charge redistribution in the octahedral sheet. Oxidation was accompanied by contraction of the octahedral sheet (d(060) decreased from 1.53–1.56 Å to 1.52 Å), consistent with a shift toward dioctahedral structure. Ferrous smectite oxidation by aqueous hydrogen peroxide solutions resulted in nearly complete Fe2+ oxidation but also led to partial Fe3+ ejection from the structure, producing nanoparticulate hematite. Reflectance spectra of oxidized smectites were characterized by (Fe3+,Mg)2-OH bands at 2.28–2.30 μm, consistent with oxidative formation of dioctahedral nontronite. Accordingly, ferrous smectites are plausible precursors to observed ferric smectites on Mars, and their presence in late-Noachian sedimentary units suggests that anoxic conditions may have persisted on Mars beyond the Noachian.},
doi = {10.1002/2017JE005331},
journal = {Journal of Geophysical Research. Planets},
number = 12,
volume = 122,
place = {United States},
year = {2017},
month = {12}
}

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