Microstructure-specific carbon isotopic signatures of organic matter from similar to 3.5 Ga cherts of the Pilbara Craton support a biologic origin

The similar to 3.5 Ga Dresser Formation from the North Pole Dome of the Pilbara Craton (Western Australia) contains some of the oldest evidence for life on Earth. Here, we present a detailed study of microstructure specific carbon isotopic composition of organic matter (OM) preserved in Dresser Formation bedded cherts and hydrothermal chert vein using in situ Secondary-Ion Mass Spectrometry (SIMS). The OM in these rocks occurs mainly as clots that, together with minor fine OM layers and laminae, are considered primary textures formed prior to host rock lithification. Other than rare OM-rich stylolites, no evidence was found for later OM migration beyond the micrometer scale. Average delta C-13(OM) values in specific microstructural types range between -33.6%. and -25.7%.. No correlation is seen between measured delta C-13 values and H/C ratios in the studied OM microstructures. This lack of correlation and the low metamorphic grade of the rocks studied argue against significant modification of OM isotopic composition by later metamorphic alteration. It is thus concluded that the range of delta C-13 values found in the samples represents primary OM isotopic variability. Within some individual samples variable delta C-13(OM) values are correlated with specific microstructural types. This observation is not consistent with solely abiotic OM formation via Fisher-Tropsch type reactions. When compared with associated delta C-13(ankerite) values, average delta C-13(OM) values indicate C isotopic fractionation [Delta C-13(Ank-OM)] of 25-33 parts per thousand, which translates to dissolved CO2-OM isotopic fractionation [Delta C-13(CO2-OM)] of 20-30 parts per thousand. This range of delta C-13(CO2-OM) is consistent with enzymatic C fixation via the Calvin cycle utilized by photoautotrophs and the reductive acetyl-CoA pathway utilized by chemolithoautotrophs. Photosynthetic OM formation is supported by the relatively shallow water depth inferred for the Dresser environment and the restricted occurrence of stromatolites to shallow water deposits in this unit, whereas chemolithosynthesis is supported by the abundance of OM in sub-seafloor hydrothermal chert veins. The range of delta C-13(OM) values observed in the samples may therefore represent the remains of different organisms utilizing different C-fixation pathways. Other biologic effects, such as the growth rate and density of microbial communities, and further heterotrophic overprinting of the autotrophic biomass may have also contributed to the observed range of delta C-13(OM) values. (C) 2016 Elsevier B.V. All rights reserved.