Identification of carbonate-associated sulfate (CAS) in a Noachian Martian meteorite Allan Hills 84001

Abstract

The aqueous environment and possible habitability of early Mars have been widely studied based on orbital and in situ explorations, as well as analyses of Martian meteorites. Using microscale X-ray absorption near edge structure (μ-XANES) analysis, we report the first sulfur (S) speciation of the carbonates in a Martian meteorite, Allan Hills 84001, precipitated in the 4-billion-year-old aqueous alteration on Mars. The XANES data show diagnostic signatures of oxidized sulfur in the carbonates, indicating that carbonate-associated sulfate (CAS) formed from coexisting sulfate ions (SO42−) in the aqueous fluid. A thermodynamic calculation suggests that the CAS deposited from a fluid with a moderately oxidizing to reducing and neutral to slightly alkaline pH condition. The possible sources of SO42− ions are the minor SOx species in the Noachian atmosphere and/or the supply from volcanic gas. It is concluded that considerable amounts of the atmospheric volatiles including CO2 and SOx may have been stored as alteration products (e.g., carbonates) in the Martian underground system.