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Barium (Ba) isotopes are a promising new tracer for riverine freshwater input to the ocean and marine biogeochemical cycling. However, many processes that affect Ba cycling at continental margins have not yet been investigated with respect to Ba isotope fractionation. Here, we present a comprehensive data set of Ba concentration and isotope data for water column, pore water and sediment samples from Kiel Bight, a seasonally stratified and hypoxic fjord in the southwestern Baltic Sea. The surface water Ba concentration and Ba isotope inventory of the water column can generally be explained by mixing of riverine freshwater and Atlantic seawater. However, the deep-water below the seasonal pycnocline (10 - 15 m water depth) is characterized by a pronounced positive Ba concentration anomaly (up to 915 nM) that is accompanied by a δ138Ba of ~+0.25 ‰, which is lighter than expected from the seawater-freshwater mixing line (Ba: 77 nM, δ138Ba: +0.32 ‰ at a salinity of 18). Pore water profiles indicate a Ba flux across the sediment-water interface, which contributes to the enrichment in isotopically light Ba in the deep-water. Pore waters of surface sediments and deep-waters are oversaturated with respect to barite. Therefore, barite dissolution is unlikely to account for the benthic Ba flux. Water column Ba concentrations closely correlate with those of the nutrients phosphate and silica, which are removed from surface waters by biological processes and recycled from the sediment by diffusion across the sediment-water interface. As nutrient-to-Ba ratios differ among sites and from those observed in open-marine systems, we propose that Ba is removed from surface waters by adsorption onto biogenic particles (rather than assimilation) and regenerated within surface sediments upon organic matter degradation. Pore water data for subsurface sediments in Kiel Bight indicate preferential transfer of isotopically heavy Ba into an authigenic phase during early diagenesis. Quantifying the burial flux associated with this authigenic Ba phase along continental margins could potentially help to settle the isotopic imbalance between known Ba source and sink fluxes in the ocean.

Biogeochemically reactive iron (Fe) species in marine sediments play an important role in the global carbon cycle. Primary productivity in as much as half of the world's ocean is controlled by the availability of Fe (Boyd & Ellwood, 2010;Tagliabue et al., 2017). Reductive dissolution of Fe oxide minerals in anoxic marine sediments coupled to transport of dissolved Fe (Fe 2+ ) across the sediment-water interface represents an important source of bioavailable Fe to the ocean (

Surface sediments of the coastal mud belt in the Benguela Upwelling System (BUS) off Namibia host extensive communities of chemotrophic large sulfur bacteria (LSB) of the family Beggiatoaceae such as Thiomargarita spp. and Candidatus Maribeggiatoa spp. In order to understand the role of these bacteria in N and P cycling, biogeochemical data from three sites in the mud belt were simulated with a biogeochemical model including LSB catabolic pathways. Organic carbon remineralization was dominated by the reduction of sulfate to hydrogen sulfide (5.0–7.7 mmol C m−2 d−1). At the two stations where LSB were observed, produced hydrogen sulfide was almost completely oxidized by LSB using nitrate as the electron acceptor. Modeled rates of nitrate reduction to N2 by LSB were over two times higher than nitrate reduction to ammonium. This points toward a potential negative feedback by LSB on primary production. Furthermore, loss of fixed N strongly enriched the benthic fluxes in P relative to N. Although the model included intracellular polyphosphate accumulation by LSB and subsequent breakdown to phosphate, a clear link between polyphosphate dynamics and hydroxyapatite precipitation and burial could not be clearly substantiated. This is partly due to simplifying assumptions in the model and analytical uncertainties in distinguishing between authigenic hydroxyapatite and allochthonous hydroxyapatite (e.g., fish bones), both of which are major components of particulate P in the BUS. Our modeling suggests a significant control of LSB on benthic N and P fluxes to the water column. Given the extensive coverage of LSB on the shelf (>30,000 km2), more accurate forecasts of nutrient cycling and primary production in the BUS necessitate a closer inspection of benthic P sources and sinks in the mud belt and a clearer understanding of the controls on the end product of nitrate reduction by LSB.

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