Tracing organic compounds in aerobically altered methane-derived carbonate pipes (Gulf of Cadiz, SW Iberia)

Abstract

The primary geochemical process at methane seeps is anaerobic oxidation of methane (AOM), performed by methanotrophic archaea and sulfate-reducing bacteria (SRB). The molecular fingerprints (biomarkers) of these chemosynthetic microorganisms can be preserved in carbonates formed through AOM. However, thermal maturity and aerobic degradation can change the original preserved compounds, making it difficult to establish the relation between AOM and carbonate precipitation. Here we report a study of amino acid and lipid abundances in carbonate matrices of aerobically altered pipes recovered from the seafloor of the Gulf of Cadiz (SW Iberian Peninsula). This area is characterized by a complex tectonic regime that supports numerous cold seeps. Studies so far have not determined whether the precipitation of carbonate pipes in the Gulf of Cadiz is a purely chemical process or whether microbial communities are involved. Samples from this site show signs of exposure to oxygenated waters and of aerobic alteration, such as oxidation of authigenic iron sulfides. In addition, the degradation index, calculated from the relative abundance of preserved amino acids, indicates aerobic degradation of organic matter. Although crocetane was the only lipid identified from methanotrophic archaea, the organic compounds detected (n-alkanes, regular isoprenoids and alcohols) are compatible with an origin from AOM coupled with bacterial sulfate reduction (BSR) and subsequent aerobic degradation. We establish a relation among AOM, BSR and pipe formation in the Gulf of Cadiz through three types of analysis: (1) stable carbon and oxygen isotopic composition of carbonate minerals; (2) carbonate microfabrics; and (3) mineralogical composition. Our results suggest that carbonate pipes may form through a process similar to the precipitation of vast amounts of carbonate pavements often found at cold seeps. Our approach suggests that some organic compound patterns, in combination with additional evidence of AOM and BSR, may help indicate the source of altered methane-derived carbonates commonly occurring in ancient and modern deposits.