An Anaerobic Microbial Community Mediates Epigenetic Native Sulfur and Carbonate Formation During Replacement of Messinian Gypsum at Monte Palco, Sicily

The microbially mediated replacement of sulfate-bearing evaporites by authigenic carbonate and native sulfur under anoxic conditions is poorly understood. Sulfur-bearing carbonates from the Monte Palco ridge (Sicily) replacing Messinian gypsum were therefore studied to better characterize the involved microorganisms. The lack of (1) sedimentary bedding, (2) lamination, and (3) significant water-column-derived lipid biomarkers in the secondary carbonates implies replacement after gypsum deposition (epigenesis). Allochthonous clasts from the older Calcare di Base and the younger Trubi Formation within these carbonates further evidence epigenetic formation. The sulfur-bearing carbonates are significantly ¹³C-depleted (δ¹³C as low as -51‰), identifying methane as a major carbon source. The ¹⁸O-enrichment of the carbonates (δ¹⁸O as high as 5.4‰) probably reflects precipitation from ¹⁸O-enriched fluids transported along adjacent faults or precipitation in a closed system with very little water. Native sulfur with variable ³⁴S-enrichment (δ³⁴S as high as 18.9‰), a relatively small maximum offset (12.3‰) between the sulfate source (gypsum) and native sulfur, and high δ³⁴S values of carbonate-associated sulfate (as high as 61.1‰) suggest a high conversion to native sulfur in a (semi-)closed system, with insignificant sulfate removal. Anaerobic methanotrophic archaea (ANME) apparently affiliated with the ANME-1 clade mediated secondary mineral formation as evidenced by the biomarker inventory, which contains abundant ¹³C-depleted isoprenoids including sn3-hydroxyarchaeol as the sole hydroxyarchaeol isomer and glycerol dibiphytanyl glycerol tetraethers (GDGTs). A series of various, tentatively identified ¹³C-depleted non-isoprenoidal dialkyl glycerol diethers (DAGEs), 10me-C₁₆ fatty acid, hydroxy C₁₆ fatty acids, and cyclopropyl-C_17:0ω7,8 fatty acid agree with sulfate-reducing bacteria participating in the anaerobic oxidation of methane. Specific conditions during gypsum replacement, unlike those at marine methane seeps, are reflected by the occurrence of ¹³C-depleted lipids such as lycopane, 9me-C₁₇ fatty acid, and novel DAGEs. As a response to a confined environment probably characterized by high sulfate concentrations, sulfidic conditions, and elevated salinity, ANMEs and sulfate-reducing bacteria apparently adapted their membrane compositions to cope with such stressors.