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Green sulfur bacteria biomarkers that indicate euxinia within the photic zone sometimes co-occur with evidence of contradictory depositional redox conditions, such as oxygen-requiring fossils or bioturbation. Intermittent euxinia may explain this apparent contradiction, and recent studies of modern environments show that green sulfur bacteria dwell in transiently euxinic settings. As a result, new approaches are needed to distinguish green sulfur bacteria biomarkers indicative of persistent versus intermittent euxina in ancient sedimentary samples, which this study addresses by investigating how the distribution of isorenieratene derivatives relates to depositional redox conditions. To accomplish this objective, this study focuses on two drill cores through the Upper Cretaceous Mowry Shale and the Eagle Ford Group. These drill cores are comparably thermally immature according to vitrinite reflectance data, and these formations in these cores capture a spectrum of depositional redox conditions according to multiple organic and inorganic proxies, including newly acquired iron speciation and kerogen organic sulfur data. The results presented here reveal that higher molecular weight diagenetic products of isorenieratene are preferentially preserved under persistent euxinia compared to intermittently euxinic intervals that contain isorenieratene derivatives that are shifted to lower molecular weights. Further, the total inventory of aromatic carotenoid diagenetic products contains features that can be used to identify green sulfur bacteria biomarkers from reworked petrogenic sources. Accordingly, the diagenetic fate of isorenieratene and the distribution of its diagenetic products distinguish persistent versus intermittent euxinia, which can be used to sharpen our evaluation of euxinia in the geologic record.more » « lessFree, publicly-accessible full text available February 1, 2027
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During the burial of mudstones, the associated organic matter undergoes gradual thermal maturation, a key process that can influence the reactivity of organic matter during catagenesis, the formation of hydrocarbon deposits and the chemical weathering of mudstones. Conventional methods for assessing the thermal maturity of organic matter often fail to reflect the geochemical heterogeneity between individual organic phases in mudstone samples. Here, we report an alternative, non‐destructive, surficial and micro‐scale (analytical spot size of ~ 300 nm with about 4 μm diffusion depth for micrometre‐size organic grains) method to evaluate the thermal maturity of organic matter in mudstones using the carbonKα X‐ray spectrum measured by field emission‐electron probe microanalyser (FE‐EPMA). Using this method, we observed correlations between parameter values derived from FE‐EPMA spectra, including the peak position, the peak area and the intra‐sample heterogeneity of these measurements, and independently measured vitrinite/solid bitumen reflectance for a suite of mudstones, representing different age, geological context and burial depth. With the increased values in peak area and position, we identified an increase in the carbon mass fraction of organic matter and the mean nominal oxidation state of carbon approaching zero. These trends, which are consistent with aromatisation and graphitisation, provide the rationale for using FE‐EPMA to estimate the thermal maturity of organic matter. To explore some of these trends in more detail, we employed time‐of‐flight secondary ionisation mass spectrometry, X‐ray photoelectron spectroscopy and optical reflectance measurements on a subset of samples.more » « less
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