Oxidative alteration of ferrous smectites and implications for the redox evolution of early Mars

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 suggest 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 re-exposure 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 towards 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.