Molecular signals for anaerobic methane oxidation in Black Sea seep carbonates and a microbial mat

Linked to gas seeps on the Ukrainian shelf (northwestern Black Sea), massive authigenic carbonates form as a result of anaerobic methane oxidation. Lipid distributions in these 'cold seep' carbonates and an associated microbial mat were investigated for process markers reflecting the presence and metabolic activity of distinctive methane-related biota. The samples contain free, irregular isoprenoid hydrocarbons, namely the tail-to-tail linked acyclic C-20-isoprenoid 2,6,11,15-tetra-methylhexadecane (crocetane), its C-25-homologue 2,6,10,15,19-pentamethylicosane (PMI), and several unsaturated derivatives thereof. Furthermore, specific acyclic and cyclic C-40-isoprenoids were released upon ether cleavage of the polar fraction from the carbonate. The abundance of these compounds indicates a pronounced role of particular Archaea in the biogeochemical cycling of carbon at methane seeps. Stable carbon isotopic analyses of these lipids reveal extraordinary depletions in C-13 corresponding to delta -values in the range of - 100 +/- 30 parts per thousand PDB, whereas other compounds show isotopic compositions normally observed for marine lipids (around - 30 parts per thousand PDB). The isotope data imply that the biosynthesis of the archaeal isoprenoids occurred in situ and involved the utilization of isotopically depleted, i.e, methane-derived, carbon. Apart from archaeal markers, the carbonate and the mat contain authigenic, framboidal pyrite and isotopically depleted fatty acids, namely iso-, and anteiso-branched compounds most likely derived from sulphate-reducing bacteria (SRB). The indications for a tight association of these normally competitive organisms support a model invoking a syntrophic relationship of SRB with Archaea responsible for the anaerobic oxidation of methane. The biomarker patterns obtained from the Black Sea samples were further compared to those from a Oligocene seep carbonate (Lincoln Creek Formation, WA, USA) in order to evaluate their biomarker potential for ancient settings. The prominent occurrence of isotopically light crocetane (-112 parts per thousand) and PMI (-120 parts per thousand) meets the findings for the contemporary materials. Thus, isotopically depleted isoprenoids provide diagenetically stable fingerprints for the reconstruction of carbon cycling in both, modern and ancient methane seep systems. (C) 2001 Elsevier Science B.V. All rights reserved.