Evidence for archaeal methanogenesis within veins at the onshore serpentinite-hosted Chimaera seeps, Turkey

Abstract Serpentinite-hosted ecosystems are potential sites where life may first have evolved on Earth. Serpentinization reactions produce strongly reducing and highly alkaline fluids that are typified by high concentrations of molecular hydrogen (H 2 ) and methane (CH 4 ), which can be used as an energy source by chemosynthetic life. Low-temperature serpentinization at slow-spreading mid-ocean ridges provides an ideal environment for rich microbial communities. Similar environments have also been discovered on land, where present-day low temperature serpentinization occurs during the circulation of groundwater through exposed ophiolites, triggering the production of CH 4 and H 2 , as well as the precipitation of secondary carbonate minerals. The rock samples analyzed here are from the Chimaera seeps in Turkey, representing serpentinized peridotites that are cross-cut by veins composed of brucite and hydromagnesite. Hydromagnesite features a mean δ 13 C value of −19.8‰ caused by kinetic isotope fractionation during air-groundwater exchange of CO 2 , followed by CO 2 hydroxylation to bicarbonate within the groundwater. Geochemical modeling revealed that mixing of Mg- and Ca-rich groundwaters is required for hydromagnesite formation at the expense of brucite. Within the carbonate-hydroxide veins the lipid biomarkers pentamethylicosane (PMI) and squalane with δ 13 C values of +10‰ and +14‰, respectively, and unsaturated derivatives thereof were identified. Archaeol, sn2 -hydroxyarchaeol, and sn3 -hydroxyarchaeol are other prominent archaeal biomarkers in the veins, also revealing high δ 13 C values from +6 to +13‰. These isotope patterns combined with the absence of crocetane – a biomarker for methanotrophic archaea – reveal that the microbial communities of the Chimaera seeps performed methanogenesis from a CO 2 -limited pool rather than methanotrophy. Moreover, bacterial dialkyl glycerol diethers (DAGEs) with unusually high δ 13 C values (−9 to −2‰) and minor monoalkyl glycerol monoethers (MAGEs) were identified, suggesting that bacterial sulfate reduction is also active at the Chimaera site. This study reveals that archaeal methanogenesis and bacterial sulfate reduction may be prominent at onshore peridotite-hosted sites, and that biogenic CH 4 may contribute to abiotic CH 4 emissions from terrestrial seeps.