Oldest known biomarkers provide evidence for phototrophic green and purple sulfur bacteria in the 1.73 Ga Wollogorang Formation, northern Australia

Discovery of mid-Proterozoic (1.8 – 0.8 billion years ago, Ga) indigenous biomarkers is a challenge, since biologically informative molecules of such antiquity are commonly destroyed by metamorphism or overprinted by drilling fluids and other anthropogenic petroleum products. The previously oldest biomarkers were reported from the 1.64 Ga Barney Creek Formation in the McArthur Basin, northern Australian. In this study, we present the discovery of clearly indigenous biomarker molecules from carbonaceous shales of the 1.73 Ga Wollogorang Formation in the southern McArthur Basin, extending the biomarker record back in time by ~90 million years. The extracted hydrocarbons illustrate typical mid-Proterozoic signatures with a large unresolved complex mixture, high methyl-alkane/n-alkane ratios and absence of eukaryotic steranes. Also below detection limits were acyclic isoprenoids, saturated carotenoid derivatives, bacterial hopanes and aromatic hopanoids and steroids. Detected, however, were continuous homologous series (C13-C22) of 2,3,4- and 2,3,6-trimethyl aryl isoprenoids (AI). These breakdown products of aromatic carotenoids are the oldest known biogenic molecules, revealing the activity of phototrophic green (Chlorobiaceae) and purple sulphur bacteria (Chromatiaceae). The compounds provide evidence for at least temporary, very shallow (less than ~20 m) stratification of the McArthur Basin 1.73 Ga ago, supporting models of pervasive anoxic conditions in mid-Proterozoic basins.