Dominance of benthic fluxes in the oceanic beryllium budget and implications for paleo-denudation records.

The ratio of atmosphere-derived 10Be to continent-derived 9Be in marine sediments has been used to probe the long-term relationship between continental denudation and climate. However, its application is complicated by uncertainty in 9Be transfer through the land-ocean interface. The riverine dissolved load alone is insufficient to close the marine 9Be budget, largely due to substantial removal of riverine 9Be to continental margin sediments. We focus on the ultimate fate of this latter Be. We present sediment pore-water Be profiles from diverse continental margin environments to quantify the diagenetic Be release to the ocean. Our results suggest that pore-water Be cycling is mainly controlled by particulate supply and Mn-Fe cycling, leading to higher benthic fluxes on shelves. Benthic fluxes may help close the 9Be budget and are at least comparable to, or higher (~2-fold) than, the riverine dissolved input. These observations demand a revised model framework, which considers the potentially dominant benthic source, to robustly interpret marine Be isotopic records.

Lead Sources to the Amundsen Sea, West Antarctica.

The global prevalence of industrial lead (Pb) contamination was exemplified decades ago by the predominance of anthropogenic Pb in samples of Antarctic surface ice and in Southern Ocean surface waters. Decreases in environmental Pb contamination corresponding with the near-global phase-out of leaded automobile gasoline beginning in the 1970s have since been observed. Measurements of Pb concentration in snow and ice core samples from Antarctica show that recent fluxes of industrial Pb to Antarctica have similarly declined. Here, we present measurements of Pb concentrations and isotopic compositions in seawater and surface sediments from the Amundsen Sea continental shelf including the Amundsen Sea Polynya. Both sets of measurements show that most (∼60-95%) of the Pb at our sites, at the time of sampling, is natural in source: that is, derived from the weathering of Antarctic continental rocks. These fluxes of natural Pb then become entrained into polynya waters either from sediment resuspension or from the transport of sediment-laden glacial melt waters to the polynya.

Quantifying trace element and isotope fluxes at the ocean-sediment boundary: a review.

Quantifying fluxes of trace elements and their isotopes (TEIs) at the ocean's sediment-water boundary is a pre-eminent challenge to understand their role in the present, past and future ocean. There are multiple processes that drive the uptake and release of TEIs, and properties that determine their rates are unevenly distributed (e.g. sediment composition, redox conditions and (bio)physical dynamics). These factors complicate our efforts to find, measure and extrapolate TEI fluxes across ocean basins. GEOTRACES observations are unveiling the oceanic distributions of many TEIs for the first time. These data evidence the influence of the sediment-water boundary on many TEI cycles, and underline the fact that our knowledge of the source-sink fluxes that sustain oceanic distributions is largely missing. Present flux measurements provide low spatial coverage and only part of the empirical basis needed to predict TEI flux variations. Many of the advances and present challenges facing TEI flux measurements are linked to process studies that collect sediment cores, pore waters, sinking material or seawater in close contact with sediments. However, such sampling has not routinely been viable on GEOTRACES expeditions. In this article, we recommend approaches to address these issues: firstly, with an interrogation of emergent data using isotopic mass-balance and inverse modelling techniques; and secondly, by innovating pursuits of direct TEI flux measurements. We exemplify the value of GEOTRACES data with a new inverse model estimate of benthic Al flux in the North Atlantic Ocean. Furthermore, we review viable flux measurement techniques tailored to the sediment-water boundary. We propose that such activities are aimed at regions that intersect the GEOTRACES Science Plan on the basis of seven criteria that may influence TEI fluxes: sediment provenance, composition, organic carbon supply, redox conditions, sedimentation rate, bathymetry and the benthic nepheloid inventory.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Sulfur isotopes track the global extent and dynamics of euxinia during Cretaceous Oceanic Anoxic Event 2.

The Mesozoic Era is characterized by numerous oceanic anoxic events (OAEs) that are diagnostically expressed by widespread marine organic-carbon burial and coeval carbon-isotope excursions. Here we present coupled high-resolution carbon- and sulfur-isotope data from four European OAE 2 sections spanning the Cenomanian-Turonian boundary that show roughly parallel positive excursions. Significantly, however, the interval of peak magnitude for carbon isotopes precedes that of sulfur isotopes with an estimated offset of a few hundred thousand years. Based on geochemical box modeling of organic-carbon and pyrite burial, the sulfur-isotope excursion can be generated by transiently increasing the marine burial rate of pyrite precipitated under euxinic (i.e., anoxic and sulfidic) water-column conditions. To replicate the observed isotopic offset, the model requires that enhanced levels of organic-carbon and pyrite burial continued a few hundred thousand years after peak organic-carbon burial, but that their isotope records responded differently due to dramatically different residence times for dissolved inorganic carbon and sulfate in seawater. The significant inference is that euxinia persisted post-OAE, but with its global extent dwindling over this time period. The model further suggests that only ~5% of the global seafloor area was overlain by euxinic bottom waters during OAE 2. Although this figure is ~30× greater than the small euxinic fraction present today (~0.15%), the result challenges previous suggestions that one of the best-documented OAEs was defined by globally pervasive euxinic deep waters. Our results place important controls instead on local conditions and point to the difficulty in sustaining whole-ocean euxinia.