Silicon isotope fractionation during microbial reduction of Fe(III)–Si gels under Archean seawater conditions and implications for iron formation genesis

Microbial dissimilatory iron reduction (DIR) is a deeply rooted metabolism in the Bacteria and Archaea. In the Archean and Proterozoic, the most likely electron acceptor for DIR in marine environments was Fe(III)–Si gels. It has been recently suggested that the Fe and Si cycles were coupled through sorption of aqueous Si to iron oxides/hydroxides, and through release of Si during DIR. Evidence for the close association of the Fe and Si cycles comes from banded iron formations (BIFs), which consist of alternating bands of Fe-bearing minerals and quartz (chert). Although there has been extensive study of the stable Fe isotope fractionations produced by DIR of Fe(III)–Si gels, as well as studies of stable Fe isotope fractionations in analogous abiologic systems, no studies to date have investigated stable Si isotope fractionations produced by DIR. In this study, the stable Si isotope fractionations produced by microbial reduction of Fe(III)–Si gels were investigated in simulated artificial Archean seawater (AAS), using the marine iron-reducing bacterium Desulfuromonas acetoxidans. Microbial reduction produced very large 30Si/28Si isotope fractionations between the solid and aqueous phase at ∼23 °C, where Δ30Sisolid–aqueous isotope fractionations of −3.35 ± 0.16‰ and −3.46 ± 0.09‰ were produced in two replicate experiments at 32% Fe(III) reduction (solid-phase Fe(II)/FeTotal = 0.32). This isotopic fractionation was substantially greater than that observed in two abiologic controls that had solid-phase Fe(II)/FeTotal = 0.02–0.03, which produced Δ30Sisolid–aqueous isotope fractionations of −2.83 ± 0.24‰ and −2.65 ± 0.28‰. In a companion study, the equilibrium Δ30Sisolid–aqueous isotope fractionation was determined to be −2.3‰ for solid-phase Fe(II)/FeTotal = 0. Collectively, these results highlight the importance of Fe(II) in Fe–Si gels in producing large changes in Si isotope fractionations. These results suggest that DIR should produce highly negative δ30Si values in quartz that is the product of diagenetic reactions associated with Fe–Si gels. Such Si isotope compositions would be expected to be associated with Fe-bearing minerals that contain Fe(II), indicative of reduction, such as magnetite. Support for this model comes from recent in situ Si isotope studies of oxide-facies BIFs, where quartz in magnetite-rich samples have significantly more negative δ30Si values than quartz in hematite-rich samples

Abiologic silicon isotope fractionation between aqueous Si and Fe(III)–Si gel in simulated Archean seawater: Implications for Si isotope records in Precambrian sedimentary rocks

Precambrian Si-rich sedimentary rocks, including cherts and banded iron formations (BIFs), record a >7‰ spread in 30Si/28Si ratios (δ30Si values), yet interpretation of this large variability has been hindered by the paucity of data on Si isotope exchange kinetics and equilibrium fractionation factors in systems that are pertinent to Precambrian marine conditions. Using the three-isotope method and an enriched 29Si tracer, a series of experiments were conducted to constrain Si isotope exchange kinetics and fractionation factors between amorphous Fe(III)–Si gel, a likely precursor to Precambrian jaspers and BIFs, and aqueous Si in artificial Archean seawater under anoxic conditions. Experiments were conducted at room temperature, and in the presence and absence of aqueous Fe(II) (Fe(II)aq). Results of this study demonstrate that Si solubility is significantly lower for Fe–Si gel than that of amorphous Si, indicating that seawater Si concentrations in the Precambrian may have been lower than previous estimates. The experiments reached ∼70–90% Si isotope exchange after a period of 53–126 days, and the highest extents of exchange were obtained where Fe(II)aq was present, suggesting that Fe(II)–Fe(III) electron-transfer and atom-exchange reactions catalyze Si isotope exchange through breakage of Fe–Si bonds. All experiments except one showed little change in the instantaneous solid–aqueous Si isotope fractionation factor with time, allowing extraction of equilibrium Si isotope fractionation factors through extrapolation to 100% isotope exchange. The equilibrium 30Si/28Si fractionation between Fe(III)–Si gel and aqueous Si (Δ30Sigel–aqueous) is −2.30 ± 0.25‰ (2σ) in the absence of Fe(II)aq. In the case where Fe(II)aq was present, which resulted in addition of ∼10% Fe(II) in the final solid, creating a mixed Fe(II)–Fe(III) Si gel, the equilibrium fractionation between Fe(II)–Fe(III)–Si gel and aqueous Si (Δ30Sigel–aqueous) is −3.23 ± 0.37‰ (2σ). Equilibrium Si isotope fractionation for Fe–Si gel systems is significantly larger in magnitude than estimates of a near-zero solid–aqueous fractionation factor between pure Si gel and aqueous Si, indicating a major influence of Fe atoms on Si–O bonds, and hence the isotopic properties, of Fe–Si gel. Larger Si isotope fractionation in the Fe(II)-bearing systems may be caused by incorporation of Fe(II) into the solid structure, which may further weaken Fe–Si bonds and thus change the Si isotope fractionation factor. The relatively large Si isotope fractionation for Fe–Si gel, relative to pure Si gel, provides a new explanation for the observed contrast in δ30Si values in the Precambrian BIFs and cherts, as well as an explanation for the relatively negative δ30Si values in BIFs, in contrast to previous proposals that the more negative δ30Si values in BIFs reflect hydrothermal sources of Si or sorption to Fe oxides/hydroxides

Metabolomic Biomarkers Differentiate Soy Sauce Freshness under Conditions of Accelerated Storage

Naturally fermented soy sauce is one of the few globally valued food condiments. It is complex in its substrate, manufacturing processes, and chemical profile of salts and organic compounds, resulting from spontaneous, enzymatic and biochemical reactions. The overall chemical character of soy sauce has a few rivals relative to its chemical and bioactive complexity. Resulting from this complexity are unique sensory attributes contributing to the characteristic soy sauce flavor as well as potentiating other sensory sensations. Soy sauce is susceptible to deterioration after bottling during storage. This work examined soy sauces over an eight-month period using descriptive sensory methods and the discovery of metabolomic biomarkers with high resolution mass spectrometry, wherein samples were derivatized to enable volatility and identification of polar analytes. While several thousand metabolites were detected, only organic acids, amino acids, and various glycosylated metabolites were statistically defensible biomarkers of storage time. The relationships between sensory and metabolomic data were assessed using Kendall rank-based correlations to generate Kendall Tau correlation coefficients. A second approach filtered the data based on correlation significance and grouped molecules based on hierarchical clustering. Mass spectrometry analyses discovered several thousand unique analyte peaks with relevant changes denoted as significant relative to the fresh samples using volcano depictions of p values versus changes in compound abundances. We present a metabolomic approach for the analysis of complex food systems capable of differentiating a quantifiable extrinsic variable, which is, in this case, storage time with a correlation coefficient of 0.99. We further demonstrate that changes in soy sauce resulting from storage are characterized by sensory decreases in fruity/grape and nutty/sesame aroma and increases in methional/potato aroma and astringent attributes with concomitant changes in the concentrations of several key biomarkers

Coenzyme Q biosynthetic proteins assemble in a substrate-dependent manner into domains at ER-mitochondria contacts.

Coenzyme Q (CoQ) lipids are ancient electron carriers that, in eukaryotes, function in the mitochondrial respiratory chain. In mitochondria, CoQ lipids are built by an inner membrane-associated, multicomponent, biosynthetic pathway via successive steps of isoprenyl tail polymerization, 4-hydroxybenzoate head-to-tail attachment, and head modification, resulting in the production of CoQ. In yeast, we discovered that head-modifying CoQ pathway components selectively colocalize to multiple resolvable domains in vivo, representing supramolecular assemblies. In cells engineered with conditional ON or OFF CoQ pathways, domains were strictly correlated with CoQ production and substrate flux, respectively, indicating that CoQ lipid intermediates are required for domain formation. Mitochondrial CoQ domains were also observed in human cells, underscoring their conserved functional importance. CoQ domains within cells were highly enriched adjacent to ER-mitochondria contact sites. Together, our data suggest that CoQ domains function to facilitate substrate accessibility for processive and efficient CoQ production and distribution in cells