Spatiotemporal redox heterogeneity and transient marine shelf oxygenation in the Mesoproterozoic ocean

Abstract

The Mesoproterozoic Era (1.6–1.0 Ga), long regarded as an interval of sluggish biotic evolution and persistently low atmospheric-oceanic oxygen levels, has become the subject of recent controversy regarding putative large-scale oxygenation events. In this study, we conducted a comprehensive investigation of redox, productivity, seawater sulfate concentrations, and hydrographic conditions for the ∼1.4–1.32-Ga Xiamaling Formation in the shallow Hougou and mid-depth Huangtugui sections in the Yanshan Basin (North China). Integrated Fe-trace metal data suggest that bottom-water redox conditions mainly underwent a three-stage secular evolution: (1) suboxic (-oxic), (2) predominantly anoxic, and (3) oxic. Integrated productivity (TOC, P/Al, and Cu-Zn-Ni enrichment factors) and depositional system (major and trace elemental enrichment patterns) data suggest varying productivity levels during deposition of the Xiamaling Formation, with high productivity fueled mainly by intense open-marine upwelling. In combination with published data from the deep Xiahuayuan and Chicheng sections, a refined stratigraphic correlation framework was developed for the Xiamaling Formation based on the basinal upwelling event and existing lithostratigraphic framework. Within this new framework, sulfur concentration and pyrite δ34S (δ34Spy) data suggest a rise in marine sulfate concentrations at ∼1.36 Ga. Furthermore, strong spatiotemporal redox heterogeneity was observed within the ∼1.4–1.32-Ga Yanshan Basin, i.e., strong bottom-water anoxia (or euxinia) in deep sections and less anoxic (even oxic) conditions in shallow sections, although all sections experienced high productivity owing to oceanic upwelling. We propose a productivity-driven shelf oxygenation model to explain this spatiotemporal redox heterogeneity within the context of eustatic changes, an upwelling event, and the rise of oceanic sulfate concentrations at ∼1.36 Ga. In this model, from initially low atmospheric oxygen levels, increasing surface productivity in shelf areas due to elevated nutrient supplies from upwelling not only intensified bottom-water anoxia through organic matter export but also stimulated expansion of the ocean-surface oxic layer through photosynthetic O2 release, contributing to the development of contrasting bottom-water redox conditions between shallow and deep sections during the upwelling event identified in this study. Our model helps reconcile conflicting observations concerning Mesoproterozoic marine redox conditions, and provides new insights into putative Mesoproterozoic oceanic oxygenation events and their relationship to the evolution of early eukaryotes.