Microscopic sulfides with low 34 S/ 32 S ratios in marine sulfate deposits from the 3490-million-yearold Dresser Formation, Australia, have been interpreted as evidence for the presence of early sulfate-reducing organisms on Earth. We show that these microscopic sulfides have a mass-independently fractionated sulfur isotopic anomaly (Δ 33 S) that differs from that of their host sulfate (barite). These microscopic sulfides could not have been produced by sulfate-reducing microbes, nor by abiologic processes that involve reduction of sulfate. Instead, we interpret the combined negative δ 34 S and positive Δ 33 S signature of these microscopic sulfides as evidence for the early existence of organisms that disproportionate elemental sulfur.
International audienceNitrogen isotope compositions in sedimentary rocks (d(15)N(sed)) are routinely used for reconstructing Cenozoic N-biogeochemical cycling and are also being increasingly applied to understanding the evolution of ancient environments. Here we review the existing knowledge and rationale behind the use of d(15)N(sed) as a proxy for the Precambrian N-biogeochemical cycle with the aims of (i) identifying the major uncertainties that affect analyses and interpretation of nitrogen isotopes in ancient sedimentary rocks, (ii) developing a framework for interpreting the Precambrian d(15)N(sed) record, (iii) testing this framework against a database of Precambrian d(15)N(sed) values compiled from the literature, and (iv) identifying avenues of focused research that should increase confidence in interpreting Precambrian d(15)N(sed) data. This review highlights the intrinsic complexity of the d(15)N(sed) proxy and the significant effort that remains to realize its potential. Specifically, it is crucial to gain a better understanding of how and when diagenesis and metamorphism affect the d(15)N of bulk and kerogen-bound nitrogen. Ultimately, more data are required to apply statistics to interpreting d(15)N(sed) variability within given geological time intervals. Finally, numerical modeling of the d(15)N(sed) variability expected in different environments under varying redox scenarios is necessary to establish a predictive template for interpreting the ancient nitrogen isotope record. In spite of the challenges facing the application of this proxy to the Precambrian, the existing d(15)N(sed) record shows several features possibly related to the stepwise oxygenation of the surface environment, underlining the potential for nitrogen isotopes to reveal clues about the evolution of early Earth
Microbialites are widespread in modern and fossil hypersaline environments, where they provide a unique sedimentary archive. Authigenic mineral precipitation in modern microbialites results from a complex interplay between microbial metabolisms, organic matrices and environmental parameters. Here, we combined mineralogical and microscopic analyses with measurements of metabolic activity in order to characterise the mineralisation of microbial mats forming microbialites in the Great Salt Lake (Utah, USA). Our results show that the mineralisation process takes place in three steps progressing along geochemical gradients produced through microbial activity. First, a poorly crystallized Mg-Si phase precipitates on alveolar extracellular organic matrix due to a rise of the pH in the zone of active oxygenic photosynthesis. Second, aragonite patches nucleate in close proximity to sulfate reduction hotspots, as a result of the degradation of cyanobacteria and extracellular organic matrix mediated by, among others, sulfate reducing bacteria. A final step consists of partial replacement of aragonite by dolomite, possibly in neutral to slightly acidic porewater. This might occur due to dissolution-precipitation reactions when the most recalcitrant part of the organic matrix is degraded. The mineralisation pathways proposed here provide pivotal insight for the interpretation of microbial processes in past hypersaline environments.
The Great Oxidation Event (GOE) has been defined as the time interval when sufficient atmospheric oxygen accumulated to prevent the generation and preservation of mass-independent fractionation of sulphur isotopes (MIF-S) in sedimentary rocks. Existing correlations suggest that the GOE was rapid and globally synchronous. Here we apply sulphur isotope analysis of diagenetic sulphides combined with U-Pb and Re-Os geochronology to document the sulphur cycle evolution in Western Australia spanning the GOE. Our data indicate that, from ~2.45 Gyr to beyond 2.31 Gyr, MIF-S was preserved in sulphides punctuated by several episodes of MIF-S disappearance. These results establish the MIF-S record as asynchronous between South Africa, North America and Australia, argue for regional-scale modulation of MIF-S memory effects due to oxidative weathering after the onset of the GOE, and suggest that the current paradigm of placing the GOE at 2.33–2.32 Ga based on the last occurrence of MIF-S in South Africa should be re-evaluated.