Oceanic iron inputs must be traced and quantified to learn how they affect primary productivity and climate. Chemical reduction of iron in continental margin sediments provides a substantial dissolved flux to the oceans, which is isotopically lighter than the crust, and so may be distinguished in seawater from other sources, such as wind-blown dust. However, heavy iron isotopes measured in seawater have recently led to the proposition of another source of dissolved iron from ‘non-reductive’ dissolution of continental margins. Here we present the first pore water iron isotope data from a passive-tectonic and semi-arid ocean margin (South Africa), which reveals a smaller and isotopically heavier flux of dissolved iron to seawater than active-tectonic and dysoxic continental margins. These data provide in situ evidence of non-reductive iron dissolution from a continental margin, and further show that geological and hydro-climatic factors may affect the amount and isotopic composition of iron entering the ocean.

This is a repository copy of Controls on the barium isotope compositions of marine sediments.

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’.

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Pore-fl uid Fe isotopes may be a unique tracer of sediment respiration by dissimilatory Fereducing bacteria, but to date, pore-fl uid Fe isotope measurements have been restricted to continental shelf settings. Here, we present δ 56 Fe values of pore fl uids from two distinct sedimentary settings: (1) a riverine-dominated site on the northern California margin (Eel River shelf; 120 m water depth) and (2) biogenic opal-rich volcaniclastic deep-sea sediments from the Southern Ocean (north and south of the Crozet Plateau; 3000-4000 m water depth). The Fe isotope compositions of Crozet region pore fl uids are signifi cantly less fractionated (δ 56 Fe = +0.12‰ to -0.01‰) than the Eel River shelf (δ 56 Fe = -0.65‰ to -3.40‰) and previous studies of pore-fl uid Fe isotopes, relative to average igneous rocks. Our data represent the fi rst measurements of Fe isotope compositions in pore fl uids from deep-sea sediments. A comparison of pore-fl uid δ 56 Fe with the relative abundance of highly labile Fe in the reactive sedimentary Fe pool demonstrates that the composition of Fe isotopes in the pore fl uids refl ects the different extent of sedimentary Fe redox recycling between these sites.

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Continental shelves and shelf seas play a central role in the global carbon cycle. However, their importance with respect to trace element and isotope (TEI) inputs to ocean basins is less well understood. Here, we present major findings on shelf TEI biogeochemistry from the GEOTRACES programme as well as a proof of concept for a new method to estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment micronutrient fluxes and basin-scale estimates of submarine groundwater discharge. The proposed shelf flux tracer is 228-radium (T1/2 = 5.75 yr), which is continuously supplied to the shelf from coastal aquifers, sediment porewater exchange and rivers. Model-derived shelf 228Ra fluxes are combined with TEI/ 228Ra ratios to quantify ocean TEI fluxes from the western North Atlantic margin. The results from this new approach agree well with previous estimates for shelf Co, Fe, Mn and Zn inputs and exceed published estimates of atmospheric deposition by factors of approximately 3–23. Lastly, recommendations are made for additional GEOTRACES process studies and coastal margin-focused section cruises that will help refine the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes to the ocean.This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’.

Shelf sediments underlying temperate and oxic waters of the Celtic Sea (NW European Shelf) were found to have shallow oxygen penetrations depths from late spring to late summer (2.2-5.8 mm below seafloor) with the shallowest during/after the spring-bloom (mid-April to mid-May) when the organic carbon content was highest. Sediment porewater dissolved iron (dFe,\0.15 lm) mainly ([85%) consisted of Fe(II) and gradually increased from 0.4 to 15 lM at the sediment surface to *100-170 lM at about 6 cm depth. During the late spring this Fe(II) was found to be mainly present as soluble Fe(II) ([85% sFe, \0.02 lm). Sub-surface dFe(II) maxima were enriched in light isotopes (d 56 Fe -2.0 to -1.5%), which is attributed to dissimilatory iron reduction (DIR) during the bacterial decomposition of organic matter. As porewater Fe(II) was oxidised to insoluble Fe(III) in the surface sediment layer, residual Fe(II) was further enriched in light isotopes (down to -3.0%). Ferrozine-reactive Fe(II) was found in surface porewaters and in overlying core top waters, and was highest in the late spring period. Shipboard experiments showed that depletion of bottom water Responsible Editor: Martin Solan.Electronic supplementary material The online version of this article (doi:10.1007/s10533-017-0309-x) contains supplementary material, which is available to authorized users. 49-67 DOI 10.1007/s10533-017-0309-x oxygen in late spring can lead to a substantial release of Fe(II). Reoxygenation of bottom water caused this Fe(II) to be rapidly lost from solution, but residual dFe(II) and dFe(III) remained (12 and 33 nM) after [7 h. Iron(II) oxidation experiments in core top and bottom waters also showed removal from solution but at rates up to 5-times slower than predicted from theoretical reaction kinetics. These data imply the presence of ligands capable of complexing Fe(II) and supressing oxidation. The lower oxidation rate allows more time for the diffusion of Fe(II) from the sediments into the overlying water column. Modelling indicates significant diffusive fluxes of Fe(II) (on the order of 23-31 lmol m -2 day -1 ) are possible during late spring when oxygen penetration depths are shallow, and pore water Fe(II) concentrations are highest. In the water column this stabilised Fe(II) will gradually be oxidised and become part of the dFe(III) pool. Thus oxic continental shelves can supply dFe to the water column, which is enhanced during a small period of the year after phytoplankton bloom events when organic matter is transferred to the seafloor. This input is based on conservative assumptions for solute exchange (diffusion-reaction), whereas (bio)physical advection and resuspension events are likely to accelerate these solute exchanges in shelf-seas.