Millimeter-scale concentration gradients of hydrocarbons in Archean shales: Live-oil escape or fingerprint of contamination?

Archean shales from the Pilbara in Western Australia contain biomarkers that have been interpreted as evidence for the existence of cyanobacteria and eukaryotes 2.7 billion years (Ga) ago, with far reaching implications for the evolution of Earth’s early biosphere. To re-evaluate the provenance of the biomarkers, this study determined the spatial distribution of hydrocarbons in the original drill core material. Rock samples were cut into millimeter-thick slices, and the molecular content of each slice was analyzed. In core from the Hamersley Group (∼2.5 Ga), C<13 alkanes had gradually increasing concentrations from the surfaces to the center of the rock while the abundance of steranes, hopanes and C15+ alkanes decreased with distance from the outer surfaces. In samples from the Fortescue Group (∼2.7 Ga), hydrocarbons were overwhelmingly concentrated on rock surfaces.Two mechanisms are proposed that may have caused the inhomogeneous distribution: diffusion of petroleum products into the rock (contamination model), and leaching of indigenous hydrocarbons out of host shales driven by pressure release after drilling (‘live-oil’ effect). To test these models, the hydrocarbon distributions in the Archean shales are compared with artificially contaminated rocks as well as younger mudstones where leaching of live-oil had been observed.The results show that chromatographic phenomena associated with live-oil escape and contaminant diffusion have strong effects on molecular ratios and maturity parameters, potentially with broad implications for oil-source rock correlation studies and paleoenvironmental interpretations.For the Archean shales, the live-oil effect is consistent with some of the observed patterns, but only the contamination model fully explains the complex chromatographic fingerprints. Therefore, the biomarkers in the Pilbara samples have an anthropogenic origin, and previous conclusions about the origin of eukaryotes and oxygenic photosynthesis based on these samples are not valid.However, the study also identified indigenous molecules. The spatial distribution of particular aromatic hydrocarbons suggests they are syngenetic. Although devoid of biological information, these aromatics now represent the oldest known clearly-indigenous terrestrial liquid hydrocarbons.