Sulfite–sulfide–sulfate–carbonate equilibria with applications to Mars

Abstract

Mars volcanic SO2 and H2S gas emissions are likely the dominant source of martian sulfate, and the source of sulfuric acid. Until this work, the FREZCHEM model lacked SO2 and H2S gases and associated sulfite and sulfide minerals. The specific objectives of this paper were to add these components and associated sulfite and sulfide minerals and phases into FREZCHEM, and to explore some possible roles of these chemistries on Mars. New solid phases added included the sulfites: Na2SO3·7H2O, K2SO3, (NH4)2SO3·H2O, MgSO3·6H2O, CaSO3·0.5H2O, and FeSO3·1.5H2O, and the sulfide: FeS2. The lowest eutectic of these minerals was K2SO3 (= 6.57m) at 228K. Because sulfurous acid is stronger than carbonic acid, this causes a much larger fraction of S(IV) to exist as sulfite (SO32-) at acidic to mildly alkaline pH, whereas almost none of the C is present as carbonate anion. Model calculations show that small quantities of SO2 in an early CO2-rich martian atmosphere suppressed formation of carbonates because SO2 is much more water soluble than CO2 and a stronger acid, which may be a major reason why sulfates are much more common than carbonates on Mars. Also, perhaps equally important are low temperatures that favor sulfite mineral precipitation, the oxidation of which leads to sulfate minerals. Another potentially important factor that favors sulfite/sulfide mineral formation is low pH values that cannot allow carbonate minerals, but can allow sulfide minerals such as pyrite (FeS2). The presence of pyrite, highly insoluble, would lead to sulfate minerals when oxygen becomes available in acidic environments. Major cations for both sulfites (or sulfates) and carbonates (Ca and Mg) can limit carbonates. Sulfite–sulfide volcanism on a cold, lower pH, Mars are the primary causes of high sulfate minerals (e.g., Ca and Mg sulfates), compared to volcanism on a warm, higher pH, Earth that led to more abundant carbonate minerals (e.g., Ca and Mg carbonates).