What the ∼1.4 Ga Xiamaling Formation can and cannot tell us about the mid-Proterozoic ocean

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 similar to 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 Mo-98 value of +1.7 parts per thousand. 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 Mo-98 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 similar to 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 O-2 dynamics based on rocks of any age.