Formation of seep carbonates along the makran convergent margin, northern Arabian sea and a molecular and isotopic approach to constrain the carbon isotopic composition of parent methane Formation of seep carbonates along the makran convergent margin, northern Arabian sea and a molecular and isotopic approach to constrain the carbon isotopic composition of parent methane, Chemical Geology (2015),
AbstractAuthigenic carbonate deposits have been sampled with the remotely operated vehicle 'MARUM-QUEST 4000 m' from five methane seeps between 731 and 1823 m water depth along the convergent Makran continental margin, offshore Pakistan (northern Arabian Sea).Two seeps on the upper slope are located within the oxygen minimum zone (OMZ; ca. 100 to 1100 m water depth), the other sites are situated in oxygenated water below the OMZ (below 1100 m water depth). The carbonate deposits vary with regard to their spatial extent,sedimentary fabrics, and associated seep fauna: Within the OMZ, carbonates are spatially restricted and associated with microbial mats, whereas in the oxygenated zone below the OMZ extensive carbonate crusts are exposed on the seafloor with abundant metazoans (bathymodiolin mussels, tube worms, galatheid crabs). Aragonite and Mg-calcite are the dominant carbonate minerals, forming common early diagenetic microcrystalline cement and clotted to radial-fibrous cement. The δ 18 O carbonate values range from 1.3 to 4.2‰ V-PDB, indicating carbonate precipitation at ambient bottom-water temperature in shallow sediment depth. Extremely low δ 13 C carbonate values (as low −54.6‰ V-PDB) point to anaerobic oxidation of methane (AOM) as trigger for carbonate precipitation, with biogenic methane as dominant carbon source. Prevalence of biogenic methane in the seepage gas is corroborated by δ 13 C methane values ranging from −70.3 to −66.7‰ V-PDB, and also by back-calculationsconsidering δ 13 C methane values of carbonate and incorporated lipid biomarkers. These calculations (Δδ 13 C methane-carbonate , Δδ 13 C ANME-methane , Δδ 13 C MOX-methane ) prove to be useful to assess the carbon stable isotope composition of seeping methane if this has not been determined in the first place; such an approach represents a useful tool to reconstruct fluid composition of ancient seeps. AOM is also revealed by lipid biomarkers of anaerobic methane oxidizing archaea such as crocetane, pentamethylicosane (PMI), and sn2-hydroxyarchaeol strongly depleted in 13 C (δ 13 C values as low as −127‰ V-PDB). Biomarkers of sulphatereducing bacteria are also abundant, showing slightly less negative δ 13 C values, but still significantly 13 C-depleted (average values as low as −101‰). Other bacterial biomarkers, such as bacteriohopanepolyols (BHPs), hopanols, and hopanoic acids are detected in most carbonates, but are particularly common in seep carbonates from the non-OMZ sites. The BHP patterns of these carbonates and their low δ 13 C values resemble patterns of aerobic methanotrophic bacteria. In the shallower OMZ sites, BHPs revealed much lowe...