In situ S‐isotope compositions of sulfate and sulfide from the 3.2 Ga Moodies Group, South Africa: A record of oxidative sulfur cycling

Sulfate minerals are rare in the Archean rock record and largely restricted to the occurrence of barite (BaSO4). The origin of this barite remains controversially debated. The mass‐independent fractionation of sulfur isotopes in these and other Archean sedimentary rocks suggests that photolysis of volcanic aerosols in an oxygen‐poor atmosphere played an important role in their formation. Here, we report on the multiple sulfur isotopic composition of sedimentary anhydrite in the ca. 3.22 Ga Moodies Group of the Barberton Greenstone Belt, southern Africa. Anhydrite occurs, together with barite and pyrite, in regionally traceable beds that formed in fluvial settings. Variable abundances of barite versus anhydrite reflect changes in sulfate enrichment by evaporitic concentration across orders of magnitude in an arid, nearshore terrestrial environment, periodically replenished by influxes of seawater. The multiple S‐isotope compositions of anhydrite and pyrite are consistent with microbial sulfate reduction. S‐isotope signatures in barite suggest an additional oxidative sulfate source probably derived from continental weathering of sulfide possibly enhanced by microbial sulfur oxidation. Although depositional environments of Moodies sulfate minerals differ strongly from marine barite deposits, their sulfur isotopic composition is similar and most likely reflects a primary isotopic signature. The data indicate that a constant input of small portions of oxidized sulfur from the continents into the ocean may have contributed to the observed long‐term increase in Δ33Ssulfate values through the Paleoarchean.Centre National de la Recherche ScientifiqueDeutsche ForschungsgemeinschaftH2020 European Research Counci

Inherited geochemical diversity of 3.4 Ga organic films from the Buck Reef Chert, South Africa

International audienceArchean rocks contain crucial information about the earliest life forms on Earth, but documenting these early stages of biological evolution remains challenging. The main issue lies in the geochemical transformations experienced by Archean organic matter through its multibillion-year geological history. Here we present spatially resolved chemical investigations conducted on 3.4 Ga organic films from the Buck Reef Chert, South Africa which indicate that they possess significantly different chemical compositions. Since these organic films allunderwent the same post-depositional geological history, this geochemical diversity is most likely inherited, reflecting original chemical differences which were not completely obliterated by subsequent burial-induced degradation processes. These results demonstrate that earlyArchean organic films carry chemical information directly related to their original molecular compositions. This paves the way for the reconstruction of the initial chemical nature of organic microfossils found in ancient rocks, provided that the geologically-induced chemicaltransformations they underwent are properly constrained

Multiple Sulfur Isotope Records of the 3.22 Ga Moodies Group, Barberton Greenstone Belt

Co-auteur étrangerInternational audienceThe Moodies Group, the uppermost unit in the Barberton Greenstone Belt (BGB) in SouthAfrica, is a ~3.7-km-thick coarse clastic succession accumulated on terrestrial-to-shallow marinesettings at around 3.22 Ga. The multiple sulfur isotopic composition of pyrite of Moodies intervalswas newly obtained to examine the influence of these depositional settings on the sulfur isotope record.Conglomerate and sandstone rocks were collected from three synclines north of the Inyoka Fault of thecentral BGB, namely, the Eureka, Dycedale, and Saddleback synclines. The sulfur isotopic compositionof pyrite was analyzed by Secondary Ion Mass Spectrometry (SIMS) for 6 samples from the threesynclines and by Isotope Ratio Mass Spectrometry (IR-MS) for 17 samples from a stratigraphic sectionin the Saddleback Syncline. The present results show a signal of mass-independent fractionation ofsulfur isotopes (S-MIF), although t-tests statistically demonstrated that the Moodies S-MIF signals(mostly 0% < D33S < +0.5%) are significantly small compared to the signal of the older Paleoarchean(3.6–3.2 Ga) records. These peculiar signatures might be related to initial deposition of detrital pyriteof juvenile origin from the surrounding intrusive (tonalite–trondhjemite–granodiorite; TTG) andfelsic volcanic rocks, and/or to secondary addition of hydrothermal sulfur during late metasomatism.Moreover, fast accumulation (~0.1–1 mm/year) of the Moodies sediments might have led to a reducedaccumulation of sulfur derived from an atmospheric source during their deposition. As a result, thesulfur isotopic composition of the sediments may have become susceptible to the secondary additionof metasomatic sulfur on a mass balance point of view. The sulfur isotopic composition of Moodiespyrite is similar to the composition of sulfides from nearby gold mines. It suggests that, after theMoodies deposition, metasomatic pyrite formation commonly occurred north of the Inyoka Fault inthe central BGB at 3.1–3.0 Ga

Intense biogeochemical iron cycling revealed in Neoarchean micropyrites from stromatolites

International audienceIron isotope compositions of sedimentary pyrites (FeS2) are used to constrain the redox evolution of the Precambrian ocean and early Fe-based metabolisms such as Dissimilatory Iron Reduction (DIR). Sedimentary pyrites can record biotic and abiotic iron reduction, which have similar ranges of Fe isotopic fractionation, as well as post-depositional histories and metamorphic overprints that can modify Fe isotope compositions. However, some exceptionally well-preserved sedimentary records, such as the stromatolite-bearing Tumbiana Formation (ca. 2.7 Ga, Western Australia) have been proven to retain primary information on Early Neoarchean microbial ecosystems and associated metabolic pathways. Here, we present in situ Fe isotope measurements of micropyrites included in four stromatolites from the Tumbiana Formation in order to assess iron respiration metabolism using Fe isotope signatures. A set of 142 micropyrites has been analyzed in three lamina types, i.e. micritic, organic-rich and fenestral laminae, by Secondary Ion Mass Spectrometry (SIMS), using a Hyperion radio-frequency plasma source. The diversity of laminae is attributed to specific depositional environments, leading to the formation of Type 1 (micritic laminae) and Type 2 (organic-rich laminae) and early diagenetic effects (Type 3, fenestral laminae). Type 1 and 2 laminae preserved comparable δ56Fe ranges, respectively from −1.76‰ to +4.15‰ and from −1.54‰ to +4.44‰. Type 3 laminae recorded a similar range, although slightly more negative δ56Fe values between −2.20‰ and +2.65‰. Globally, our data show a large range of δ56Fe values, from −2.20‰ to +4.44‰, with a unimodal distribution that differs from the bimodal distribution previously reported in the Tumbiana stromatolites. Such a large range and unimodal distribution cannot be explained by a unique process (e.g., biotic/abiotic Fe reduction or pyrite formation only controlled by the precipitation rate). It rather could reflect a two-step iron cycling process in the sediment pore water including i) partial Fe oxidation forming Fe(OH)3 with positive δ56Fe values followed by ii) partial, possibly microbially induced, Fe reduction leading to Fe2+ availability for pyrite formation by sulfate reducers carrying both negative δ56Fe and δ34S signatures. In this model, the buildup and subsequent reduction through time of a residual Fe(OH)3 reservoir arising from the activity of methanotrophs, can explain the strongly positive δ56FeFe(OH)3 values up to 4‰. These results indicate that Archean microbial mats have been the site of the interaction of several closely linked biogeochemical cycles involving Fe, S and C

High‐spatial‐resolution measurements of iron isotopes in pyrites by secondary ion mass spectrometry using the new Hyperion‐II radio‐frequency plasma source

International audienceIron isotopic signatures in pyrites are considered as a good proxy to reconstruct paleoenvironmental and local redox conditions. However, the investigation of micro-pyrites less than 20µm in size has been limited by the evaluable analytical techniques. The development of the new brighter radio-frequency plasma ion source (Hyperion-II source) enhances the spatial resolution by increasing the beam density 10 times compared with the Duoplasmatron source.Here we present high-spatial-resolution measurements of iron isotopes in pyrites using a 3 nA–3 μm primary 16O− beam on two Cameca IMS 1280-HR2 ion microprobe instruments equipped with Hyperion sources at CRPG-IPNT (France) and at SwissSIMS (Switzerland). We tested analytical effects, such as topography and crystal orientation, that could induce analytical biases perceptible through variations of the instrumental mass fractionation (IMF).Results: The δ56Fe reproducibility for the Balmat pyrite standard is ±0.25‰ (2 standard deviations) and the typical individual internal error is ±0.10‰(2 standard errors). The sensitivity on 56Fe+ was 1.2 × 107 cps/nA/ppm or better. Tests on Balmat pyrites revealed that neither the crystal orientation nor channeling effects seem to significantly influence the IMF. Different pyrite standards (Balmat and SpainCR) were used to test the accuracy of the measurements. Indium mounts must be carefully prepared with a sample topography less than 2 μm, which was checked using an interferometric microscope. Such a topography is negligible for introducing change in the IMF. This new source increases the spatial resolution while maintaining the high precision of analyses and the overall stability of the measurements compared with the previous Duoplasmatron source.Conclusions: A reliable method was developed for performing accurate and highresolution measurements of micrometric pyrites. The investigation of sedimentary micro-pyrites will improve our understanding of the processes and environmental conditions during pyrite precipitation, including the contribution of primary (microbial activities or abiotic reactions) and secondary (diagenesis and/or hydrothermal fluid circulation) signatures

Surface Analysis by Secondary Ion Mass Spectrometry (SIMS): Principles and Applications from Swiss laboratories

Secondary Ion Mass Spectrometry (SIMS) extracts chemical, elemental, or isotopic information about a localized area of a solid target by performing mass spectrometry on secondary ions sputtered from its surface by the impact of a beam of charged particles. This primary beam sputters ionized atoms and small molecules (as well as many neutral particles) from the upper few nanometers of the sample surface. The physical basis of SIMS has been applied to a large range of applications utilizing instruments optimized with different types of mass analyzer, either dynamic SIMS with a double focusing mass spectrometer or static SIMS with a Time of Flight (TOF) analyzer. Here, we present a short review of the principles and major applications of three different SIMS instruments located in Switzerland