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Abstract We report the formation of minerals from the tochilinite-valleriite group (TVG) during laboratory serpentinization experiments conducted at 300 and 328 °C. Minerals in the TVG are composed of a mixture of sulfide and hydroxide layers that can contain variable proportions of Fe, Mg, Cu, Ni, and other cations in both layers. Members of this group have been observed as accessory minerals in several serpentinites, and have also been observed in association with serpentine minerals in meteorites. To our knowledge, however, TVG minerals have not previously been identified as reaction products during laboratory simulation of serpentinization. The serpentinization experiments reacted olivine with artificial seawater containing 34S-labeled sulfate, with a small amount of solid FeS also added to the 300 °C experiment. In both experiments, the predominant reaction products were chrysotile serpentine, brucite, and magnetite. At 300 °C, these major products were accompanied by trace amounts of the Ni-bearing TVG member haapalaite, Ni,Fe-sulfide (likely pentlandite), and anhydrite. At 328 °C, valleriite occurs rather than haapalaite and the accompanying Ni,Fe-sulfide is proportionally more enriched in Ni. Reduction of sulfate by H2 produced during serpentinization evidently provided a source of reduced S that contributed to formation of the TVG minerals and Ni,Fe-sulfides. The results provide new constraints on the conditions that allow precipitation of tochilinite-valleriite group minerals in natural serpentinites. 

Abstract We present chemostratigraphy, biostratigraphy, and geochronology from a succession that spans the Ediacaran-Cambrian boundary in Sonora, Mexico. A sandy hematite-rich dolostone bed, which occurs 20 m above carbonates that record the nadir of the basal Cambrian carbon isotope excursion within the La Ciénega Formation, yielded a maximum depositional age of 539.40 ± 0.23 Ma using U-Pb chemical abrasion–isotope dilution–thermal ionization mass spectrometry on a population of sharply faceted volcanic zircon crystals. This bed, interpreted to contain reworked tuffaceous material, is above the last occurrences of late Ediacaran body fossils and below the first occurrence of the Cambrian trace fossil Treptichnus pedum, and so the age calibrates key markers of the Ediacaran-Cambrian boundary. The temporal coincidence of rift-related flood basalt volcanism in southern Laurentia (>250,000 km3 of basalt), a negative carbon isotope excursion, and biological turnover is consistent with a mechanistic link between the eruption of a large igneous province and end-Ediacaran extinction. 

Abstract Stratigraphic variability in the geochemistry of sedimentary rocks provides critical data for interpreting paleoenvironmental change throughout Earth history. However, the vast majority of pre-Jurassic geochemical records derive from shallow-water carbonate platforms that may not reflect global ocean chemistry. Here, we used calcium isotope ratios (δ44Ca) in conjunction with minor-element geochemistry (Sr/Ca) and field observations to explore the links among sea-level change, carbonate mineralogy, and marine diagenesis and the expression of a globally documented interval of elevated carbon isotope ratios (δ13C; Hirnantian isotopic carbon excursion [HICE]) associated with glaciation in Upper Ordovician shallow-water carbonate strata from Anticosti Island, Canada, and the Great Basin, Nevada and Utah, USA. The HICE on Anticosti is preserved in limestones with low δ44Ca and high Sr/Ca, consistent with aragonite as a major component of primary mineralogy. Great Basin strata are characterized by lateral gradients in δ44Ca and δ13C that reflect variations in the extent of early marine diagenesis across the platform. In deep-ramp settings, deposition during synglacial sea-level lowstand and subsequent postglacial flooding increased the preservation of an aragonitic signature with elevated δ13C produced in shallow-water environments. In contrast, on the mid- and inner ramp, extensive early marine diagenesis under seawater-buffered conditions muted the magnitude of the shift in δ13C. The processes documented here provide an alternative explanation for variability in a range of geochemical proxies preserved in shallow-water carbonates at other times in Earth history, and challenge the notion that these proxies necessarily record changes in the global ocean. 

Abstract The sedimentary pyrite sulfur isotope (δ³⁴S) record is an archive of ancient microbial sulfur cycling and environmental conditions. Interpretations of pyrite δ³⁴S signatures in sediments deposited in microbial mat ecosystems are based on studies of modern microbial mat porewater sulfide δ³⁴S geochemistry. Pyrite δ³⁴S values often capture δ³⁴S signatures of porewater sulfide at the location of pyrite formation. However, microbial mats are dynamic environments in which biogeochemical cycling shifts vertically on diurnal cycles. Therefore, there is a need to study how the location of pyrite formation impacts pyrite δ³⁴S patterns in these dynamic systems. Here, we present diurnal porewater sulfide δ³⁴S trends and δ³⁴S values of pyrite and iron monosulfides from Middle Island Sinkhole, Lake Huron. The sediment–water interface of this sinkhole hosts a low‐oxygen cyanobacterial mat ecosystem, which serves as a useful location to explore preservation of sedimentary pyrite δ³⁴S signatures in early Earth environments. Porewater sulfide δ³⁴S values vary by up to ~25‰ throughout the day due to light‐driven changes in surface microbial community activity that propagate downwards, affecting porewater geochemistry as deep as 7.5 cm in the sediment. Progressive consumption of the sulfate reservoir drives δ³⁴S variability, instead of variations in average cell‐specific sulfate reduction rates and/or sulfide oxidation at different depths in the sediment. The δ³⁴S values of pyrite are similar to porewater sulfide δ³⁴S values near the mat surface. We suggest that oxidative sulfur cycling and other microbial activity promote pyrite formation in and immediately adjacent to the microbial mat and that iron geochemistry limits further pyrite formation with depth in the sediment. These results imply that primary δ³⁴S signatures of pyrite deposited in organic‐rich, iron‐poor microbial mat environments capture information about microbial sulfur cycling and environmental conditions at the mat surface and are only minimally affected by deeper sedimentary processes during early diagenesis. 

Summary Nitrogen fixation, the biological conversion of N₂to NH₃, is critical to alleviating nitrogen limitation in many marine ecosystems. To date, few measurements exist of N₂fixation in deep‐sea sediments. Here, we conducted > 400 bottle incubations with sediments from methane seeps, whale falls and background sites off the western coast of the United States from 600 to 2893 m water depth to investigate the potential rates, spatial distribution and biological mediators of benthic N₂fixation. We found that N₂fixation was widespread, yet heterogeneously distributed with sediment depth at all sites. In some locations, rates exceeded previous measurements by > 10×, and provided up to 30% of the community anabolic growth requirement for nitrogen. Diazotrophic activity appeared to be inhibited by pore water ammonium: N₂fixation was only observed if incubation ammonium concentrations were ≤ 25 μM, and experimental additions of ammonium reduced diazotrophy. In seep sediments, N₂fixation was dependent on CH₄and coincident with sulphate reduction, consistent with previous work showing diazotrophy by microorganisms mediating sulphate‐coupled methane oxidation. However, the pattern of diazotrophy was different in whale‐fall and associated reference sediments, where it was largely unaffected by CH₄, suggesting catabolically different diazotrophs at these sites.