ALBERT

Description: Chromium (Cr) isotope fractionation is sensitive to redox changes and the Cr isotopic composition (δ53Cr) of sedimentary rocks has been used to reconstruct marine redox conditions and atmospheric oxygenation in the past. However, little is known about the behaviour of chromium isotopes across modern marine redox boundaries. We investigated Cr concentrations and δ53Cr variations in seawater and sediment across the Peruvian oxygen minimum zone (OMZ) to provide a better understanding of Cr cycling in the ocean. We found that seawater δ53Cr values ranged from 0.02 ± 0.16‰ to 0.59 ± 0.11‰ (2SD) and sediment values from 0.31 ± 0.07 to 0.92 ± 0.12‰. Neither Cr concentrations nor δ53Cr values in the water column revealed significant shifts across the oxic-anoxic boundaries. Instead, processes that operate at a local scale, such as Cr scavenging by Fe-rich particles and Cr release from reducing sediments, are identified as the main controls on Cr concentrations and isotope compositions in the water column. The δ53Cr values of sediments deposited in permanently anoxic waters (0.77 ± 0.19‰, n = 5) are significantly different from the δ53Cr values of sediments deposited in oxic bottom waters (0.46 ± 0.19‰, n = 4). This suggests that sediment Cr concentrations and δ53Cr values are to some extent influenced by water column redox (e.g. reductive dissolution and transport of Fe oxides) and/or early diagenetic (e.g. redistribution of Cr during phosphogenesis) processes as well as biologic activity. Our data demonstrate that local scale water column redox gradients and sediment exchange can lead to a large range of δ53Cr values in sediments, comparable to the range found in the entire geologic record to date. Given the increasing prominence of Cr isotope measurements in constraining atmospheric oxygenation in deep time, we argue that the processes influencing Cr cycling under different conditions and from the water column to the sediment need to be better resolved to verify the utility of such measurements as paleoenvironmental proxies.

Description: Uranium isotopes (δ238U values) in ancient sedimentary rocks (shales, carbonate rocks) are widely used as a tool to reconstruct paleo-redox conditions, but the behaviour of U isotopes under modern non-sulfidic anoxic vs. oxic conditions remains poorly constrained. We present U concentration and isotope data for modern sediments from the Peruvian margin, a highly productive open ocean environment with a range of redox conditions. To investigate U in different host fractions of the sediment (reactive, silicate, and HNO3-soluble fraction), we conducted a series of sequential extractions. Detrital-corrected authigenic U isotope compositions (δ238Uauth) in sediments deposited beneath an oxic water column show little deviation from the dissolved seawater U source, while anoxically deposited sediments have δ238Uauth values that are up to 0.4‰ heavier compared to seawater δ238U. Under anoxic, non-euxinic conditions, the U isotope offset between sediment and seawater is larger compared with oxic, but significantly smaller when compared with euxinic conditions from the literature. The results from sequential extractions show that the reactive sediment fraction records more pronounced differences in δ238Ureactive than δ238Uauth values depending on the oxidation state of the overlying water column. Furthermore, we found a strong correlation between total organic carbon (TOC) and both U concentrations (Uauth) and δ238Uauth values (R2 = 0.70 and 0.94, respectively) at the persistently anoxic site that we examined. These correlations can be caused by several processes including U isotope fractionation during microbially-mediated U reduction at the sediment-water interface (diffusive U input), during sorption onto and/or incorporation into organic matter in the water column (particulate U input) and diagenetic redistribution of U, or a combination of these processes. Our data show that several factors can influence δ238U values including oxidation state of U, the presence or absence of hydrogen sulfide and organic matter. These findings add new constraints to the degree of U isotope fractionation associated with U incorporation into sediments in different low-oxygen environments, thus aiding in interpretation of ancient paleo-redox conditions from U isotope data.