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  1. Abstract

    Despite a surge of recent work, the evolution of mid‐Proterozoic oceanic–atmospheric redox remains heavily debated. Constraining the dynamics of Proterozoic redox evolution is essential to determine the role, if any, that anoxia played in protracting the development of eukaryotic diversity. We present a multiproxy suite of high‐resolution geochemical measurements from a drill core capturing the ~1.4 Ga Xiamaling Formation, North China Craton. Specifically, we analyzed major and trace element concentrations, sulfur and molybdenum isotopes, and iron speciation not only to better understand the local redox conditions but also to establish how relevant our data are to understanding the contemporaneous global ocean. Our results suggest that throughout deposition of the Xiamaling Formation, the basin experienced varying degrees of isolation from the global ocean. During deposition of the lower organic‐rich shales (130–85 m depth), the basin was extremely restricted, and the reservoirs of sulfate and trace metals were drawn down almost completely. Above a depth of 85 m, shales were deposited in dominantly euxinic waters that more closely resembled a marine system and thus potentially bear signatures of coeval seawater. In the most highly enriched sample from this upper interval, the concentration of molybdenum is 51 ppm with a δ98Mo value of +1.7‰. Concentrations of Mo and other redox‐sensitive elements in our samples are consistent with a deep ocean that was largely anoxic on a global scale. Our maximum δ98Mo value, in contrast, is high compared to published mid‐Proterozoic data. This high value raises the possibility that the Earth's surface environments were transiently more oxygenated at ~1.4 Ga compared to preceding or postdating times. More broadly, this study demonstrates the importance of integrating all available data when attempting to reconstruct surface O2dynamics based on rocks of any age.

     
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  2. Abstract

    Records of the Ediacaran carbon cycle (635–541 million years ago) include the Shuram excursion (SE), the largest negative carbonate carbon isotope excursion in Earth history (down to −12‰). The nature of this excursion remains enigmatic given the difficulties of interpreting a perceived extreme global decrease in the δ13C of seawater dissolved inorganic carbon. Here, we present carbonate and organic carbon isotope (δ13Ccarband δ13Corg) records from the Ediacaran Doushantuo Formation along a proximal‐to‐distal transect across the Yangtze Platform of South China as a test of the spatial variation of theSE. Contrary to expectations, our results show that the magnitude and morphology of this excursion and its relationship with coexisting δ13Corgare highly heterogeneous across the platform. Integrated geochemical, mineralogical, petrographic, and stratigraphic evidence indicates that theSEis a primary marine signature. Data compilations demonstrate that theSEwas also accompanied globally by parallel negative shifts of δ34S of carbonate‐associated sulfate (CAS) and increased87Sr/86Sr ratio and coastalCASconcentration, suggesting elevated continental weathering and coastal marine sulfate concentration during theSE. In light of these observations, we propose a heterogeneous oxidation model to explain the high spatial heterogeneity of theSEand coexisting δ13Corgrecords of the Doushantuo, with likely relevance to theSEin other regions. In this model, we infer continued marine redox stratification through theSEbut with increased availability of oxidants (e.g., O2and sulfate) limited to marginal near‐surface marine environments. Oxidation of limited spatiotemporal extent provides a mechanism to drive heterogeneous oxidation of subsurface reduced carbon mostly in shelf areas. Regardless of the mechanism driving theSE, future models must consider the evidence for spatial heterogeneity in δ13C presented in this study.

     
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