Timing and Characterization of the Change in the Redox State of Uranium in Precambrian Surface Environments: A Proxy for the Oxidation State of the Atmosphere

The redox-sensitive geochemical behavior of uranium permits the use of Th/U ratios as a geochemical proxy for the oxidation state of the atmosphere and oceans during sedimentary processes. Due to the effects of post-depositional uranium mobility on Th/U ratios during events involving oxygenated fluids, direct measurements of Th/U ratios are often misleading, but the whole rock Pb isotope composition may be used to determine a sample’s apparent time-integrated Th/U ratio (κa) and the timing associated with the onset of the U-Th-Pb geochemistry. Rare earth element (REE) concentrations were determined by isotope dilution mass spectrometry to evaluate the influence of multiple provenance components and potential mobility of Th, U, and Pb during post-depositional processes on the Th/U ratio. The Pb isotope compositions and REE concentrations were determined for six Paleoproterozoic sedimentary sequences, which were the focus of previous studies involving the timing of the rise of atmospheric oxygen. The Mount McRae Shale, Huronian Supergroup, and Zaonezhskaya Formation have been interpreted as experiencing post-depositional alteration (perhaps associated with orogenic events) due to Pb-Pb ages that are younger than the likely depositional age and observed fractionation of REE in chondrite normalized REE patterns and interelement REE ratios (e.g. La/Nd, La/Yb, Eu/Eu*). Similar geochemical proxies have been interpreted as sedimentary geochemical features of the Timeball Hill Formation, Hotazel Formation, and Sengoma Argillite Formation. This study of Paleoproterozoic sedimentary units constrains the onset of U-Th decoupling, most likely due to the onset of oxidative weathering conditions, began by 2.32 Ga, the latest. INDEX WORDS: Pb isotopes, Rare earth elements, Th/U ratios, Time-integrated, Atmospheric evolution, Oxygen content of the atmosphere, U-Th decoupling TIMING AND CHARACTERIZATION OF THE CHANGE IN THE REDOX STATE OF URANIUM IN PRECAMBRIAN SURFACE ENVIRONMENTS: A PROXY FOR THE OXIDATION STATE OF THE ATMOSPHERE