Description: We present iron (Fe) concentration and Fe isotope data for a sediment core transect across the Peru upwelling area, which hosts one of the ocean’s most pronounced oxygen minimum zones (OMZs). The lateral progression of total Fe to aluminum ratios (FeT/Al) across the continental margin indicates that sediments within the OMZ are depleted in Fe whereas sediments below the OMZ are enriched in Fe relative to the lithogenic background. Rates of Fe loss within the OMZ, as inferred from FeT/Al ratios and sedimentation rates, are in agreement with benthic flux data that were calculated from pore water concentration gradients. The mass of Fe lost from sediments within the OMZ is within the same order of magnitude as the mass of Fe accumulating below the OMZ. Taken together, our data are in agreement with a shuttle scenario where Fe is reductively remobilized from sediments within the OMZ, laterally transported within the anoxic water column and re-precipitated within the more oxic water below the OMZ. Sediments within the OMZ have increased 56Fe/54Fe isotope ratios relative to the lithogenic background, which is consistent with the general notion of benthic release of dissolved Fe with a relatively low 56Fe/54Fe isotope ratio. The Fe isotope ratios increase across the margin and the highest values coincide with the greatest Fe enrichment in sediments below the OMZ. The apparent mismatch in isotope composition between the Fe that is released within the OMZ and Fe that is re-precipitated below the OMZ implies that only a fraction of the sediment-derived Fe is retained near-shore whereas another fraction is transported further offshore. We suggest that a similar open-marine shuttle is likely to operate along many ocean margins. The observed sedimentary fingerprint of the open-marine Fe shuttle differs from a related transport mechanism in isolated euxinic basins (e.g., the Black Sea) where the laterally supplied, reactive Fe is quantitatively captured within the basin sediments. We suggest that our findings are useful to identify OMZ-type Fe cycling in the geological record.

Description: The isotope composition of reactive iron (Fe) in marine sediments and sedimentary rocks is a promising tool for identifying Fe sources and sinks across ocean basins. In addition to cross-basinal Fe redistribution, which can modify Fe isotope signatures, Fe minerals also undergo diagenetic redistribution during burial. The isotope fractionation associated with this redistribution does not affect the bulk isotope composition, but complicates the identification of mineral-specific isotope signatures. Here, we present new Fe isotope data for Peru margin sediments and revisit previously published data for sediments from the California margin to unravel the impact of early diagenesis on Fe isotope compositions of individual Fe pools. Sediments from oxic California margin sites are dominated by terrigenous Fe supply with Fe release from sediments having a negligible influence on the solid phase Fe isotope composition. The highly reactive Fe pool (sum of Fe bound to (oxyhydr)oxide, carbonate, monosulfide and pyrite) of these sediments has a light isotope composition relative to the bulk crust, which is consistent with earlier studies showing that continental weathering shifts the isotope composition of Fe (oxyhydr)oxides to lighter values. Ferruginous sedimentswithin the Peruvian oxygen minimumzone are depleted in Fe relative to the lithogenic background, which we attribute to extensive Fe release to the water column. The remaining highly reactive Fe pool has a heavier isotope composition compared to California margin sediments. This observation is in agreement with the general notion of an isotopically light benthic Fe efflux. Most of the reactive Fe delivered and retained in the sediment is transferred into authigenic mineral phases within the topmost 10 to 20 cm of the sediments. We observe a first-order relationship between the extent of pyritization of Fe monosulfide and the isotope composition of authigenic pyrite. With increasing pyritization, the isotope composition of authigenic pyrite approaches the isotope composition of the highly reactive Fe pool. We argue that the isotope composition of authigenic pyrite or other Fe minerals that may undergo pyritization may only be used to trace water column sources or sinks if the extent of pyritization is separately evaluated and either close to 100% or 0%. Alternatively, one may calculate the isotope composition of the highly reactive Fe pool, thereby avoiding isotope effects due to internal diagenetic redistribution. In depositional settings with high Fe but lowsulfide concentrations, source and sink signatures in the isotope composition of the highly reactive Fe pool may be compromised by sequestration of Fe within authigenic silicate minerals. Authigenic silicate minerals appear to be an important burial phase for reactive Fe below the Peruvian oxygen minimum zone.

Description: Iron (Fe) is a key element in the global ocean’s biogeochemical framework because of its essential role in numerous biological processes. A poorly studied link in the oceanic Fe cycle is the reductive release of Fe from sediments in oxygen depleted ocean regions - the oxygen minimum zones (OMZs). Changing rates of Fe release from OMZ sediments may have the potential to modulate ocean fertility which has far-reaching implications considering the high amplitude oxygen fluctuations throughout earth history as well as the ongoing ocean deoxygenation projected for the near future. In order to explore spatial and temporal trends of Fe cycling in OMZs, we present here Fe isotope and speciation data for surface sediments from a transect across the Peruvian upwelling area, one of the most pronounced OMZs of the modern ocean. Because of continuous dissimilatory Fe reduction and diffusive loss across the benthic boundary, sediments within the OMZ are strongly depleted in reactive Fe components, and the little reactive Fe left behind has a heavy isotope composition. In contrast, surface sediments below the OMZ are enriched in reactive Fe, with the majority being present as Fe oxides with comparably light isotope composition. This lateral pattern of Fe depletion and enrichment indicates that Fe released from sediments within the OMZ is reoxidized and precipitated at the oxycline. First-order calculations suggest that the amount of Fe mobilized within the OMZ and that accumulated at the boundaries are largely balanced. Therefore, benthic Fe fluxes in OMZs should be carefully evaluated prior to incorporation into global models, as much of the initially released Fe may be reprecipitated prior to vertical or offshore transport. First XRF core scanning results for partly laminated piston cores from the OMZ boundaries reveal downcore oscillations in the content of reactive Fe and redox-sensitive trace metals that are attributed to past changes in OMZ extension. Ongoing work on these cores will focus on their dating and the downcore investigation of Fe and trace metal records in order to better understand past Fe cycling within the Peruvian OMZ and potential interactions with climate variability.

Description: 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.

Description: The ratio of atmosphere-derived 10 Be to continent-derived 9 Be 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 9 Be transfer through the land-ocean interface. The riverine dissolved load alone is insufficient to close the marine 9 Be budget, largely due to substantial removal of riverine 9 Be 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 9 Be 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.

Description: Author Posting. © The Oceanography Society, 2012. This article is posted here by permission of The Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 25, no. 3 (2012): 40-53, doi:10.5670/oceanog.2012.73.

Description: In search of an explanation for some of the greenest waters ever seen in coastal Antarctica and their possible link to some of the fastest melting glaciers and declining summer sea ice, the Amundsen Sea Polynya International Research Expedition (ASPIRE) challenged the capabilities of the US Antarctic Program and RVIB Nathaniel B. Palmer during Austral summer 2010–2011. We were well rewarded by both an extraordinary research platform and a truly remarkable oceanic setting. Here we provide further insights into the key questions that motivated our sampling approach during ASPIRE and present some preliminary findings, while highlighting the value of the Palmer for accomplishing complex, multifaceted oceanographic research in such a challenging environment.

Description: This project was funded by the National Science Foundation Office of Polar Programs, Antarctic Organisms and Ecosystems (ANT-0839069 to PY, ANT-0838995 to RS, ANT-0838975 to SS, ANT-0838995 to OS, ANT- 0944727 to KA, and ANT-0839012 to Hugh Ducklow), and the Swedish Research Council (Grant 2008-6430 to SB and LR), with logistic support from the Swedish Polar Research Secretariat and Raytheon Polar Services.

Description: Continental shelf sediments are a major source of iron (Fe) for phytoplankton in surface waters. In this study, we investigate the mechanisms that control release of Fe from shelf sediments and its lateral transport (shuttling) in oxic and hypoxic waters on the northwestern Black Sea shelf. We find that at two coastal stations near the outflow of the Danube river high input of organic matterdrives strong reductive dissolution of Fe(oxyhydr)oxides (henceforth termed Fe oxides) in surface sediments, supporting high rates of Fe release to oxygenated bottom waters (∼0.36 mmol m-2d-1).We suggest that bioirrigation plays a key role in the release of Fe from these sediments. At four stations further offshore organic matter deposition is lower resulting in limited mobilization of Fe2+in the sediment and low benthic fluxes of Fe (〈0.07 mmol m-2d-1). Lateral transport of Fe from the coastal zone towards the deep basin mostly takes place in colloidal and/or particulate form (〉0.2μm) in the lower part of the water column, likely through repeated deposition and resuspension of Fe oxides from surface sediments. Using synchrotron-based X-ray spectroscopy and sequential chemical extractions, we demonstrate that the suspended matter and surface sediments are enriched in easily reducible Fe oxides (mostly ferrihydrite) and Fe associated with clay. The mobilization of Fe in the coastal zone and subsequent lateral transport of these Fe-bearing particles results in higher ratios of Fe/Al in surface sediments at outer shelf stations (ca. 1.2 to 2 wt% wt%-1) than at coastal stations (ca. 0.5 to 0.9 wt% wt%-1). However, below the sediment surface layer Fe/Al ratios are similar at all stations indicating limited burial of the laterally transported Fe. Our results highlight the critical role of organic matter input, associated biological activity and riverine Fe input as drivers of Fe shuttling on continental shelves. We also show that in shelf areas where sediments receive low inputs of organic matter, physical transport controls the ultimate fate of the shuttled Fe.