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’.
Iron is important in regulating the ocean carbon cycle
. Although several dissolved and particulate species participate in oceanic iron cycling, current understanding emphasizes the importance of ...complexation by organic ligands in stabilizing oceanic dissolved iron concentrations
. However, it is difficult to reconcile this view of ligands as a primary control on dissolved iron cycling with the observed size partitioning of dissolved iron species, inefficient dissolved iron regeneration at depth or the potential importance of authigenic iron phases in particulate iron observational datasets
. Here we present a new dissolved iron, ligand and particulate iron seasonal dataset from the Bermuda Atlantic Time-series Study (BATS) region. We find that upper-ocean dissolved iron dynamics were decoupled from those of ligands, which necessitates a process by which dissolved iron escapes ligand stabilization to generate a reservoir of authigenic iron particles that settle to depth. When this 'colloidal shunt' mechanism was implemented in a global-scale biogeochemical model, it reproduced both seasonal iron-cycle dynamics observations and independent global datasets when previous models failed
. Overall, we argue that the turnover of authigenic particulate iron phases must be considered alongside biological activity and ligands in controlling ocean-dissolved iron distributions and the coupling between dissolved and particulate iron pools.
Aeolian dust was collected from 2001 to 2003, as part of a longer-term study, to estimate the nutrient input to the Levantine basin from atmospheric deposition. Adsorption experiments, using dust ...samples from six individual dust storms, showed insignificant adsorption of phosphate onto dry deposited Saharan dust. Thus adsorption onto dust can be discounted as a reason for the high nitrogen:phosphorus (N:P) ratio in the deep water of the eastern basin. A single dust storm sample from the Western Mediterranean was able to adsorb some phosphate from seawater, and it is speculated that this may be linked to the action of acid aerosols on the dust during cloud formation, or to the varying chemical composition in different sources of dust.
Dry atmospheric deposition is an important net supplier of both N and P to the eastern basin. Leachable inorganic nitrogen concentrations and fluxes are higher in background (non-storm) samples than in storm samples, probably due to the smaller grain size and aerosol source. Total P is supplied naturally with the dust, as shown by the close correlation between total P and Al (
r
2
=
0.95
). However, there is a poor correlation between leachable inorganic P (LIP) and Al (
r
2
=
0.20
), which may be related to grain-size effects and/or recycling processes in the atmosphere. Even so, the supply of LIP to surface waters is greatest during dust storms due to comparatively high deposition of aerosol material. While atmospheric input of P during dust storms does not produce significant in situ increases in chlorophyll, probably due to rapid microbial grazing, it does represent an important proportion of the long-term nutrient input to the basin. This may be increasing as the frequency of dust storms increases.
Short sediment cores were collected from ∼1100m water depth at the top of Hook Ridge, a submarine volcanic edifice in the Central Basin of the Bransfield Strait, Antarctica, to assess Fe and Mn ...supply to the water column. Low-temperature hydrothermal fluids advect through these sediments and, in places, subsurface H2S is present at high enough concentrations to support abundant Sclerolinum sp., an infaunal tubeworm that hosts symbiotic thiotrophic bacteria. The water column is fully oxic, and oxygen penetration depths at all sites are 2–5cmbsf. Pore water Fe and Mn content is high within the subsurface ferruginous zone (max. 565μmolFeL−1, >3–7cmbsf)—14–18 times higher than values measured at a nearby, background site of equivalent water depth. Diffusion and advection of pore waters supply significant Fe and Mn to the surface sediment. Sequential extraction of the sediment demonstrates that there is a significant enrichment in a suite of reactive, authigenic Fe minerals in the upper 0–5cm of sediment at one site characterised by weathered crusts at the seafloor. At a site with only minor authigenic mineral surface enrichment we infer that leakage of pore water Fe and Mn from the sediment leads to enriched total dissolvable Fe and Mn in bottom waters. An Eh sensor mounted on a towed package mapped a distinct Eh signature above this coring site which is dispersed over several km at the depth of Hook Ridge. We hypothesise that the main mechanism for Fe and Mn efflux from the sediment is breach of the surface oxic layer by the abundant Sclerolinum sp., along with episodic enhancements by physical mixing and resuspension of sediment in this dynamic volcanic environment. We propose that Hook Ridge sediments are an important source of Fe and Mn to the deep waters of the Central Basin in the Bransfield Strait, where concentrations are sustained by the benthic flux, and Fe is stabilised in the water column as either colloidal phases or ligand-bound dissolved species. Entrainment of this water mass into the Drake Passage and thereby the Antarctic Circumpolar Current could provide a significant metal source to this HNLC region of the Southern Ocean if mixing and upwelling occurs before removal of this metal pool to underlying sediments. Sediment-covered volcanic ridges are common within rifted margins and may play a previously overlooked role in the global Fe cycle.
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 (T½ = 5.75 yr), which is continuously supplied to te 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 self-derived TEI fluxes to the ocean. This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.
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