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The 18O/16O of precipitated silica in natural environments is posited to record the temperature of the ambient environment. Measurements of 17O/16O in silica (SiO2), when paired with 18O/16O, provide an opportunity to further constrain the environmental conditions at the time of mineral precipitation and ripening. On Cenozoic timescales, siliceous frustule precipitation by diatoms has served as the primary sink of silica from the ocean. Frustule precipitation is a biologically catalyzed process from an ocean undersaturated in SiO2. Here, we measure the 17O/16O and 18O/16O in diatom frustules from semicontinuous cultures with two different diatom species and across a range of growth rates and temperatures. To further enable these measurements, we developed a laser fluorination method to reproducibly measure the triple oxygen isotope composition of silica frustules. While the δ13C of the organic matter scaled predictably with growth rate, neither the δ18O or Δ′17O of the frustule silica varied significantly with respect to variations in growth rate or species. Temperature, however, does carry a control on the product δ18O composition. Conversely, the measured Δ′17O compositions were systematically negative with respect to the corresponding theoretical equilibrium isotope prediction, consistent with other empirical work on the SiO2 system and only weakly temperature‐dependent. This isotopic offset may be caused by the silica concentrating mechanisms diatoms use to precipitate their frustules. These results are consistent with literature arguments regarding the utility of diatom δ18O in reconstructing temperature, but suggest that Δ′17O may not be a suitable temperature proxy for diatomaceous sediment. [ABSTRACT FROM AUTHOR]

Throughout most of the sedimentary record, the marine carbon cycle is interpreted as being in isotopic steady state. This is most commonly inferred via isotopic reconstructions, where two export fluxes (organic carbon and carbonate) are offset by a constant isotopic fractionation of ~25 (termed εorg-carb). Sedimentary deposits immediately overlying the Marinoan snowball Earth diamictites, however, stray from this prediction. In stratigraphic sections from the Ol Formation (Mongolia) and Sheepbed Formation (Canada), we observe a temporary excursion where the organic matter has anomalously heavy δ13C and is grossly decoupled from the carbonate δ13C. This signal may reflect the unique biogeochemical conditions that persisted in the aftermath of snowball Earth. For example, physical oceanographic modeling suggests that a strong density gradient caused the ocean to remain stratified for about 50,000 years after termination of the Marinoan snowball event, during which time the surface ocean and continental weathering consumed the large atmospheric CO2 reservoir. Further, we now better understand how δ13C records of carbonate can be post‐depostionally altered and thus be misleading. In an attempt to explain the observed carbon isotope record, we developed a model that tracks the fluxes and isotopic values of carbon between the surface ocean, deep ocean, and atmosphere. By comparing the model output to the sedimentary data, stratification alone cannot generate the anomalous observed isotopic signal. Reproducing the heavy δ13C in organic matter requires the progressively diminishing contribution of an additional anomalous source of organic matter. The exact source of this organic matter is unclear. [ABSTRACT FROM AUTHOR]

The anaerobic oxidation of methane (AOM) is a globally significant sink that regulates methane flux from sediments into the oceans and atmosphere. Here we examine mesophilic to thermophilic AOM in hydrothermal sediments recovered from the Middle Valley vent field, on the Juan de Fuca Ridge. Using continuous-flow sediment bioreactors and batch incubations, we characterized (i) the degree to which AOM contributes to net dissolved inorganic carbon flux, (ii) AOM and sulfate reduction (SR) rates as a function of temperature and (iii) the distribution and density of known anaerobic methanotrophs (ANMEs). In sediment bioreactors, inorganic carbon stable isotope mass balances results indicated that AOM accounted for between 16% and 86% of the inorganic carbon produced, underscoring the role of AOM in governing inorganic carbon flux from these sediments. At 90°C, AOM occurred in the absence of SR, demonstrating a striking decoupling of AOM from SR. An abundance of Fe(III)-bearing minerals resembling mixed valent Fe oxides, such as green rust, suggests the potential for a coupling of AOM to Fe(III) reduction in these metalliferous sediments. While SR bacteria were only observed in cooler temperature sediments, ANMEs allied to ANME-1 ribotypes, including a putative ANME-1c group, were found across all temperature regimes and represented a substantial proportion of the archaeal community. In concert, these results extend and reshape our understanding of the nature of high temperature methane biogeochemistry, providing insight into the physiology and ecology of thermophilic anaerobic methanotrophy and suggesting that AOM may play a central role in regulating biological dissolved inorganic carbon fluxes to the deep ocean from the organic-poor, metalliferous sediments of the global mid-ocean ridge hydrothermal vent system. [ABSTRACT FROM AUTHOR]

ABSTRACT Isotopic fractionations produced by biosynthetic processes are the result of networks of individual biochemical reactions that operate at differing efficiencies and with distinct fractionation factors. These reaction networks determine the magnitude and direction of the net isotopic fractionation associated with a given process. Here we examine the ways that biological reaction networks control mass-dependent isotopic fractionations of multiple sulphur isotopes. We describe how material-flow through some networks can produce characteristic multiple-sulphur-isotope signatures that differ from those produced by their constituent steps and demonstrate that experimental results with Archaeaglobus fulgidus can be evaluated using multiple sulphur isotopes in the context of previously published models for dissimilatory sulphate reduction. Our evaluation of these data is consistent with the interpretation that the dependence of sulphur isotope fractionation on external sulphate concentration is rooted in differences between the forward and reverse &formmu0; ↔ adenosine-5′-phosphosulphate (APS) ↔ &formmu1; steps. The framework provided by our analysis has the potential to evaluate the biosynthetic pathways that produce the isotopic fractionations, to isolate the primary sources of isotopic fractionations (sulphate reduction or disproportionation reactions) and to establish criteria to identify the signature of specific sulphur metabolisms in the geological record. The results highlight the new types of information that can be obtained by including measurements of δ33 S {δ33 S = [(33 S/32 S)sample /(33 S/32 S)reference - 1]*1000} with measurements of δ34 S. [ABSTRACT FROM AUTHOR]

Studies of microbial sulfate reduction have suggested that the magnitude of sulfur isotope fractionation varies with sulfate concentration. Small apparent sulfur isotope fractionations preserved in Archean rocks have been interpreted as suggesting Archean sulfate concentrations of <200 μm, while larger fractionations thereafter have been interpreted to require higher concentrations. In this work, we demonstrate that fractionation imposed by sulfate reduction can be a function of concentration over a millimolar range, but that nature of this relationship depends on the organism studied. Two sulfate-reducing bacteria grown in continuous culture with sulfate concentrations ranging from 0.1 to 6 mm showed markedly different relationships between sulfate concentration and isotope fractionation. Desulfovibrio vulgaris str. Hildenborough showed a large and relatively constant isotope fractionation (34εSO4-H2S ≅ 25‰), while fractionation by Desulfovibrio alaskensis G20 strongly correlated with sulfate concentration over the same range. Both data sets can be modeled as Michaelis–Menten (MM)-type relationships but with very different MM constants, suggesting that the fractionations imposed by these organisms are highly dependent on strain-specific factors. These data reveal complexity in the sulfate concentration–fractionation relationship. Fractionation during MSR relates to sulfate concentration but also to strain-specific physiological parameters such as the affinity for sulfate and electron donors. Previous studies have suggested that the sulfate concentration–fractionation relationship is best described with a MM fit. We present a simple model in which the MM fit with sulfate concentration and hyperbolic fit with growth rate emerge from simple physiological assumptions. As both environmental and biological factors influence the fractionation recorded in geological samples, understanding their relationship is critical to interpreting the sulfur isotope record. As the uptake machinery for both sulfate and electrons has been subject to selective pressure over Earth history, its evolution may complicate efforts to uniquely reconstruct ambient sulfate concentrations from a single sulfur isotopic composition., Earth and Planetary Sciences

A substantial body of evidence suggests that subsurface water masses in mid-Proterozoic marine basins were commonly anoxic, either euxinic (sulfidic) or ferruginous (free ferrous iron). To further document redox variations during this interval, a multiproxy geochemical and paleobiological investigation was conducted on the approximately 1000-m-thick Mesoproterozoic (Lower Riphean) Arlan Member of the Kaltasy Formation, central Russia. Iron speciation geochemistry, supported by organic geochemistry, redox-sensitive trace element abundances, and pyrite sulfur isotope values, indicates that basinal calcareous shales of the Arlan Member were deposited beneath an oxygenated water column, and consistent with this interpretation, eukaryotic microfossils are abundant in basinal facies. The Rhenium–Osmium (Re–Os) systematics of the Arlan shales yield depositional ages of 1414 ± 40 and 1427 ± 43 Ma for two horizons near the base of the succession, consistent with previously proposed correlations. The presence of free oxygen in a basinal environment adds an important end member to Proterozoic redox heterogeneity, requiring an explanation in light of previous data from time-equivalent basins. Very low total organic carbon contents in the Arlan Member are perhaps the key—oxic deep waters are more likely (under any level of atmospheric O2) in oligotrophic systems with low export production. Documentation of a full range of redox heterogeneity in subsurface waters and the existence of local redox controls indicate that no single stratigraphic section or basin can adequately capture both the mean redox profile of Proterozoic oceans and its variance at any given point in time., Earth and Planetary Sciences