Carl A. Peters

Reappraisal of hydrocarbon biomarkers in Archean rocks

Significance The advent of oxygenic photosynthesis set the stage for the evolution of complex life on an oxygenated planet, but it is unknown when this transformative biochemistry emerged. The existing hydrocarbon biomarker record requires that oxygenic photosynthesis and eukaryotes emerged more than 300 million years before the Great Oxidation Event [∼2.4 billion years ago (Ga)]. We report that hopane and sterane concentrations measured in new ultraclean Archean drill cores from Australia are comparable to blank concentrations, yet their concentrations in the exteriors of conventionally collected cores of stratigraphic equivalence exceed blank concentrations by more than an order of magnitude due to surficial contamination. Consequently, previous hydrocarbon biomarker reports no longer provide valid evidence for the advent of oxygenic photosynthesis and eukaryotes by ∼2.7 Ga. Hopanes and steranes found in Archean rocks have been presented as key evidence supporting the early rise of oxygenic photosynthesis and eukaryotes, but the syngeneity of these hydrocarbon biomarkers is controversial. To resolve this debate, we performed a multilaboratory study of new cores from the Pilbara Craton, Australia, that were drilled and sampled using unprecedented hydrocarbon-clean protocols. Hopanes and steranes in rock extracts and hydropyrolysates from these new cores were typically at or below our femtogram detection limit, but when they were detectable, they had total hopane (<37.9 pg per gram of rock) and total sterane (<32.9 pg per gram of rock) concentrations comparable to those measured in blanks and negative control samples. In contrast, hopanes and steranes measured in the exteriors of conventionally drilled and curated rocks of stratigraphic equivalence reach concentrations of 389.5 pg per gram of rock and 1,039 pg per gram of rock, respectively. Polycyclic aromatic hydrocarbons and diamondoids, which exceed blank concentrations, exhibit individual concentrations up to 80 ng per gram of rock in rock extracts and up to 1,000 ng per gram of rock in hydropyrolysates from the ultraclean cores. These results demonstrate that previously studied Archean samples host mixtures of biomarker contaminants and indigenous overmature hydrocarbons. Therefore, existing lipid biomarker evidence cannot be invoked to support the emergence of oxygenic photosynthesis and eukaryotes by ∼2.7 billion years ago. Although suitable Proterozoic rocks exist, no currently known Archean strata lie within the appropriate thermal maturity window for syngenetic hydrocarbon biomarker preservation, so future exploration for Archean biomarkers should screen for rocks with milder thermal histories.

Focused hydrocarbon‐migration in shallow sediments of a pockmark cluster in the Niger Delta (Off Nigeria)

The Niger Delta is one of the largest hydrocarbon basin offshore Africa and it is well known for the presence of active pockmarks on the seabed. During the Guineco-MeBo cruise in 2011, long cores were taken from a pockmark cluster in order to investigate the state of its current activity. Gas hydrates, oil and pore-water were sampled for geochemical studies. The resulting dataset combined with seismic data reveal that shallow hydrocarbon migration in the upper sedimentary section was focused exclusively within the pockmarks. There is a clear tendency for gas migration within the hydrate-bearing pockmarks, and oil migration within the carbonate-rich one. This trend is interpreted as a consequence of hydrate dissolution followed by carbonate precipitation in the course of the evolution of these pockmarks. We also demonstrate that Anaerobic Oxidation of Methane (AOM) is the main process responsible for the depletion of pore-water sulfate, with depths of the Sulfate-Methane Transition Zone (SMTZ) ranging between 1.8 and 33.4 m. In addition, a numerical transport-reaction model was used to estimate the age of hydrate-layer formation from the present-day sulfate profiles. The results show that the sampled hydrate-layers were formed between 21 and 3750 years before present. Overall, this work shows the importance of fluid flow on the dynamics of pockmarks, and the investigated cluster offers new opportunities for future cross-site comparison studies. Our results imply that sudden discharges of gas can create hydrate layers within the upper sedimentary column which can affect the seafloor morphology over few decades. This article is protected by copyright. All rights reserved.