Description: The eastern tropical South Pacific (ETSP) represents one of the most productive areas in the ocean that is characterized by a pronounced oxygen minimum zone (OMZ). Particulate organic matter (POM) that sinks out of the euphotic zone is supplied to the anoxic sediments and utilized by microbial communities. The degradation of POM is associated with dissolved organic matter (DOM) production and reworking. The release of recalcitrant DOM to the overlying waters may represent an important organic matter escape mechanism from remineralization within sediments but received little attention in OMZ regions so far. Here, we combine measurements of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) with DOM optical properties in the form of chromophoric (CDOM) and fluorescent (FDOM) DOM from pore waters and near-bottom waters of the ETSP off Peru. We evaluate diffusion–driven fluxes and net in situ fluxes of DOC and DON in order to investigate processes affecting DOM cycling at the sediment–water interface along a transect 12° S. To our knowledge, these are the first data for sediment release of DON and pore water CDOM and FDOM for the ETSP off Peru. Pore-water DOC and DON accumulated with increasing sediment depth, suggesting an imbalance between DOM production and remineralization within sediments. High DON accumulation resulted in very low pore water DOC / DON ratios (〉 1) which could be caused by either an "imbalance" in DOC and DON remineralization, or to the presence of an additional nitrogen source. Diffusion driven fluxes of DOC and DON exhibited high spatial variability. They varied from 0.2–0.1 mmol m−2 d−1 to 2.52–1.3 mmol m−2 d−1 and from −0.042–0.02 mmol m−2 d−1 to 3.32–1.7 mmol m−2 d−1, respectively. Generally low net in situ DOC and DON fluxes as well as steepening of spectral slope (S) of CDOM and accumulation of humic-like FDOM at the near-bottom waters over time indicated active microbial DOM utilization at the sediment–water interface, potentially stimulated by nitrate (NO3−) and nitrite (NO2−). The microbial DOC utilization rates, estimated in our study, may be sufficient to support denitrification rates of 0.2–1.4 mmol m−2 d−1, suggesting that sediment release of DOM contributes substantially to nitrogen loss processes in the ETSP off Peru.

Description: The intraseasonal evolution of physical and biogeochemical properties during a coastal trapped wave event off central Peru is analysed using data from an extensive shipboard observational programme conducted between April and June 2017, and remote sensing data. The poleward velocities in the Peru–Chile Undercurrent were highly variable and strongly intensified to above 0.5 m s−1 between the middle and end of May. This intensification was likely caused by a first-baroclinic-mode downwelling coastal trapped wave, excited by a westerly wind anomaly at the Equator and originating at about 95∘ W. Local winds along the South American coast did not impact the wave. Although there is general agreement between the observed cross-shore-depth velocity structure of the coastal trapped wave and the velocity structure of first vertical mode solution of a linear wave model, there are differences in the details of the two flow distributions. The enhanced poleward flow increased water mass advection from the equatorial current system to the study site. The resulting shorter alongshore transit times between the Equator and the coast off central Peru led to a strong increase in nitrate concentrations, less anoxic water, likely less fixed nitrogen loss to N2 and a decrease of the nitrogen deficit compared to the situation before the poleward flow intensification. This study highlights the role of changes in the alongshore advection due to coastal trapped waves for the nutrient budget and the cumulative strength of N cycling in the Peruvian oxygen minimum zone. Enhanced availability of nitrate may impact a range of pelagic and benthic elemental cycles, as it represents a major electron acceptor for organic carbon degradation during denitrification and is involved in sulfide oxidation in sediments.

Description: Sediments in oxygen-depleted marine environments can be an important sink or source of bio-essential trace metals in the ocean. However, the key mechanisms controlling the release from or burial of trace metals in sediments are not exactly understood. Here, we investigate the benthic biogeochemical cycling of Fe and Cd in the oxygen minimum zone off Peru. We combine bottom water profiles, pore water profiles, as well as benthic fluxes determined from pore water profiles and in-situ from benthic chamber incubations along a depth transect at 12° S. In agreement with previous studies, both concentration-depth profiles and in-situ benthic fluxes indicate a Fe release from sediments into bottom waters. Diffusive Fe fluxes and Fe fluxes from benthic chamber incubations are roughly consistent (0.3–17.1 mmol m−2 y−1), indicating that diffusion is the main transport mechanism of dissolved Fe across the sediment-water interface. The occurrence of mats of sulfur oxidizing bacteria on the seafloor represents an important control on the spatial distribution of Fe fluxes by regulating hydrogen sulfide (H2S) concentrations and, potentially, Fe sulfide precipitation within the surface sediment. Removal of dissolved Fe after its release to anoxic bottom waters is rapid in the first 4 m away from the seafloor (half-life 〈 3 min) which hints to oxidative removal by nitrite or interaction with particles in the benthic boundary layer. Benthic flux estimates of Cd are indicative of a flux into the sediment within the oxygen minimum zone. Fluxes from benthic chamber incubations (up to 22.6 µmol m−2 y−1) exceed the diffusive fluxes (〈 1 µmol m−2 y−1) by a factor 〉 25, indicating that downward diffusion of Cd across the sediment-water interface is of subordinate importance for Cd removal from benthic chambers. As Cd removal in benthic chambers co-varies with H2S concentrations in the pore water of surface sediments, we argue that Cd removal is mediated by precipitation of CdS within the chamber. A mass balance approach, taking into account the contributions of diffusive fluxes and fluxes measured in benthic chambers as well as Cd delivery with organic material suggests that CdS precipitation in the near-bottom water could make an important contribution to the overall Cd mass accumulation in the sediment solid phase. According to our results, the solubility of trace metal sulfide minerals (Cd 〈〈 Fe) is a key-factor controlling trace metal removal and consequently the magnitude as well as the temporal and spatial heterogeneity of sedimentary fluxes. We argue that depending on their sulfide solubility, sedimentary source or sink fluxes of trace metals will change differentially as a result of declining oxygen concentrations and an associated expansion of sulfidic surface sediments. Such a trend could cause a change in the trace metal stoichiometry of upwelling water masses with potential consequences for marine ecosystems in the surface ocean.

Description: Bacterial sulfate reduction (SR) is often determined by radiotracer techniques using 35S‐labeled sulfate. In environments featuring simultaneous sulfide oxidation, SR can be underestimated due to re‐oxidation of 35S‐sulfide. Recycling of 35S‐tracer is expected to be high in sediment with low concentrations of pore‐water sulfide and high abundance of giant filamentous sulfur‐oxidizing bacteria (GFSOB). Here, we applied a sulfide‐spiking method, originally developed for water samples, to sediments along a shelf‐slope transect (72, 128, 243, 752 m water depth) traversing the Peruvian oxygen minimum zone. Sediment spiked with unlabeled sulfide prior to 35S‐sulfate injection to prevent radiotracer recycling was compared to unspiked sediment. At stations characterized by low natural sulfide and abundant GFSOB (128 and 243 m), the method revealed 1–3 times higher SR rates in spiked sediment. Spiking had no effect on SR in sediment with high natural sulfide despite presence of GFSOB (72 m). Bioturbated sediment devoid of GFSOB (752 m) showed elevated SR in spiked samples, likely from artificial introduction of sulfidic conditions. Sulfide oxidation rates at the 128 and 243 m station, derived from the difference in SR between spiked and unspiked sediment, approximated rates of dissimilatory nitrate reduction to ammonium by GFSOB. Gross SR contributed considerably to benthic dissolved inorganic carbon fluxes at the three shallowest station, confirming that SR is an important process for benthic carbon respirations within the oxygen minimum zone. We recommend to further explore the spiking method to capture SR in sediment featuring low sulfide concentrations and high sulfur cycling by GFSOB.