Geochemical Reservoirs and Timing of Sulfur Cycling on Mars

Sulfate-dominated sedimentary deposits are widespread on the surface of Mars, which contrasts with the rarity of carbonate deposits, and indicates surface waters with chemical features drastically different from those on Earth. While the Earth's surface chemistry and climate are intimately tied to the carbon cycle, it is the sulfur cycle that most strongly influences the Martian geosystems. The presence of sulfate minerals observed from orbit and in-situ via surface exploration within sedimentary rocks and unconsolidated regolith traces a history of post-Noachian aqueous processes mediated by sulfur. These materials likely formed in water-limited aqueous conditions compared to environments indicated by clay minerals and localized carbonates that formed in surface and subsurface settings on early Mars. Constraining the timing of sulfur delivery to the Martian exosphere, as well as volcanogenic H2O is therefore central, as it combines with volcanogenic sulfur to produce acidic fluids and ice. Here, we reassess and review the Martian geochemical reservoirs of sulfur from the innermost core, to the mantle, crust, and surficial sediments. The recognized occurrences and the mineralogical features of sedimentary sulfate deposits are synthesized and summarized. Existing models of formation of sedimentary sulfate are discussed and related to weathering processes and chemical conditions of surface waters. We also review existing models of sulfur content in the Martian mantle and analyze how volcanic activities may have transferred igneous sulfur into the exosphere and evaluate the mass transfers and speciation relationships between volcanic sulfur and sedimentary sulfates. The sedimentary clay-sulfate succession can be reconciled with a continuous volcanic eruption rate throughout the Noachian-Hesperian, but a process occurring around the mid-Noachian must have profoundly changed the composition of volcanic degassing. A hypothetical increase in the oxidation state or in water content of Martian lavas or a decrease in atmospheric pressure is necessary to account for such a change in composition of volcanic gases. This would allow the pre mid-Noachian volcanic gases to be dominated by water and carbon-species but late Noachian and Hesperian volcanic gases to be sulfur-rich and characterized by high SO2 content. Interruption of early dynamo and impact ejection of the atmosphere may have decreased the atmospheric pressure during the early Noachian whereas it remains unclear how the redox state or water content of lavas could have changed. Nevertheless, volcanic emission of SO2 rich gases since the late Noachian can explain many features of Martian sulfate-rich regolith, including the mass of sulfate and the particular chemical features (i.e. acidity) of surface waters accompanying these deposits. How SO2 impacted on Mars's climate, with possible short time scale global warming and long time scale cooling effects, remains controversial. However, the ancient wet and warm era on Mars seems incompatible with elevated atmospheric sulfur dioxide because conditions favorable to volcanic SO2 degassing were most likely not in place at this time.