Opposing authigenic controls on the isotopic signature of dissolved iron in hydrothermal plumes

Iron is a scarce but essential micronutrient in the oceans that limits primary productivity in many regions of the surface ocean. The mechanisms and rates of Fe supply to the ocean interior are still poorly understood and quantified. Iron isotope ratios of different Fe pools can potentially be used to trace sources and sinks of the global Fe biogeochemical cycle if these boundary fluxes have distinct signatures. Seafloor hydrothermal vents emit metal rich fluids from mid-ocean ridges into the deep ocean. Iron isotope ratios have the potential to be used to trace the input of hydrothermal dissolved iron to the oceans if the local controls on the fractionation of Fe isotopes during plume dispersal in the deep ocean are understood. In this study we assess the behaviour of Fe isotopes in a Southern Ocean hydrothermal plume using a sampling program of Total Dissolvable Fe (TDFe), and dissolved Fe (dFe). We demonstrate that δ56Fe values of dFe (δ56dFe) within the hydrothermal plume change dramatically during early plume dispersal, ranging from −2.39 ± 0.05‰ to −0.13 ± 0.06‰ (2 SD). The isotopic composition of TDFe (δ56TDFe) was consistently heavier than dFe values, ranging from −0.31 ± 0.03‰ to 0.78 ± 0.05‰, consistent with Fe oxyhydroxide precipitation as the plume samples age. The dFe present in the hydrothermal plume includes stabilised dFe species with potential to be transported to the deep ocean. We estimate that stable dFe exported from the plume will have a δ56Fe of −0.28 ± 0.17‰. Further, we show that the proportion of authigenic iron-sulfide and iron-oxyhydroxide minerals precipitating in the buoyant plume exert opposing controls on the resultant isotope composition of dissolved Fe passed into the neutrally buoyant plume. We show that such controls yield variable dissolved Fe isotope signatures under the authigenic conditions reported from modern vent sites elsewhere, and so ought to be considered during iron isotope reconstructions of past hydrothermalism from ocean sediment records

Radium-228 as a tracer of dissolved trace element inputs from the Peruvian continental margin

International audienceContinental margins play a central role in the composition of seawater by being an important source of trace element essentials to the functioning of the ocean ecosystems. Here, we measured long-lived radium isotopes (Ra-226, Ra-228) along a zonal transect at 12 degrees S (US GEOTRACES GP16) in the eastern tropical South Pacific Ocean. We used Ra-228 to quantify the trace element and isotope (TEI) fluxes (DMn, DFe, and DCo) delivered from the Peruvian continental i) shelf and ii) slope. First, elevated Ra-228 activities were measured in surface water over the entire transect (similar to 8500 km), evidence that the continental shelf is an important source of sediment-derived TEIs not only to coastal areas, but to central Pacific Ocean waters. Modeled Ra-228 shelf fluxes combined with water column dissolved TEI/Ra-228 ratios were used to quantify the shelf-ocean input rates (normalized to shelf-area) for DMn (3.3 x 10(3) mu mol m(-2) y(-1)), DFe (1.5 x 10(3) mu mol m(-2) y(-1)), and DCo (1.0 x 10(2) mu mol m(-2) y(-1)). Second, co-occurring plumes of Ra-228, DFe, and DMn extended over 1800 km from the margin at 1000-2500 m depth, indicative of a continental slope sediment TEI input to the intermediate water column. The Ra-228 gradient allowed us to derive an effective horizontal eddy diffusion coefficient (K-h) of 46 m(2) s(-1), which in turn permitted the calculation of slope sediment DMn (6.4 mu mol m(-2) y(-1)) and DFe (5.9 x 10(2) mu mol m(-2) y(-1)) fluxes based on their offshore concentration gradients. On the scale of the South Pacific continental margin between 0-20 degrees S, the DMn shelf flux is approximately 2-3 orders of magnitude higher than the slope flux, while the DFe shelf/slope flux is similar to 3:1. Both shelf and slope sediment derived DMn was transported over a significant distance towards the ocean interior, while DFe concentration gradients were steep, consistent with longer water column residence time for DMn as compared to DFe in marine systems. These findings highlight the importance of considering the continental slope-ocean boundary in the oceanic budgets of biologically-important trace elements