ALBERT

Description: Mesoscale eddies play a major role in controlling ocean biogeochemistry. By impacting nutrient availability and water column ventilation, they are of critical importance for oceanic primary production. In the eastern tropical South Pacific Ocean off Peru, where a large and persistent oxygen deficient zone is present, mesoscale processes have been reported to occur frequently. However, investigations on their biological activity are mostly based on model simulations, and direct measurements of carbon and dinitrogen (N2) fixation are scarce. We examined an open ocean cyclonic eddy and two anticyclonic mode water eddies: a coastal one and an open ocean one in the waters off Peru along a section at 16° S in austral summer 2012. Molecular data and bioassay incubations point towards a difference between the active diazotrophic communities present in the cyclonic eddy and the anticyclonic mode water eddies. In the cyclonic eddy, highest rates of N2 fixation were measured in surface waters but no N2 fixation signal was detected at intermediate water depths. In contrast, both anticyclonic mode water eddies showed pronounced maxima in N2 fixation below the euphotic zone as evidenced by rate measurements and geochemical data. N2 fixation and carbon (C) fixation were higher in the young coastal mode water eddy compared to the older offshore mode water eddy. A co-occurrence between N2 fixation and biogenic N2, an indicator for N loss, indicated a link between N loss and N2 fixation in the mode water eddies, which was not observed for the cyclonic eddy. The comparison of two consecutive surveys of the coastal mode water eddy in November and December 2012 revealed also a reduction of N2 and C fixation at intermediate depths along with a reduction in chlorophyll by half, mirroring an aging effect in this eddy. Our data indicate an important role for anticyclonic mode water eddies in stimulating N2 fixation and thus supplying N offshore.

Description: Highlights • Very high rates of dissimilatory nitrate reduction to ammonium by Thioploca. • Non-steady state model predicts Thioploca survival on intracellular nitrate reservoir. • Ammonium release by Thioploca may be coupled to pelagic N loss by anammox. • Thioploca may contribute to anammox long after bottom water nitrate disappearance. • Model indicates that benthic foraminifera account for 90% of benthic N2 production. Abstract Benthic N cycling in the Peruvian oxygen minimum zone (OMZ) was investigated at ten stations along 12oS from the middle shelf (74 m) to the upper slope (1024 m) using in situ flux measurements, sediment biogeochemistry and modelling. Middle shelf sediments were covered by mats of the filamentous bacteria Thioploca spp. and contained a large ‘hidden’ pool of nitrate that was not detectable in the porewater. This was attributed to a biological nitrate reservoir stored within the bacteria to oxidize sulfide to sulfate during ‘dissimilatory nitrate reduction to ammonium’ (DNRA). The extremely high rates of DNRA on the shelf (15.6 mmol m-2 d-1 of N), determined using an empirical steady-state model, could easily supply all the ammonium requirements for anammox in the water column. The model further showed that denitrification by foraminifera may account for 90% of N2 production at the lower edge of the OMZ. At the time of sampling, dissolved oxygen was below detection limit down to 400 m and the water body overlying the shelf had stagnated, resulting in complete depletion of nitrate and nitrite. A decrease in the biological nitrate pool was observed on the shelf during fieldwork concomitant with a rise in porewater sulfide levels in surface sediments to 2 mM. Using a non-steady state model to simulate this natural anoxia experiment, these observations were shown to be consistent with Thioploca surviving on a dwindling intracellular nitrate reservoir to survive the stagnation period. The model shows that sediments hosting Thioploca are able to maintain high ammonium fluxes for many weeks following stagnation, potentially sustaining pelagic N loss by anammox. In contrast, sulfide emissions remain low, reducing the economic risk to the Peruvian fishery by toxic sulfide plume development.

Description: Stable isotopes (15,14N, 18,16O) of dissolved inorganic nitrogen (N) were measured in sediment porewaters and benthic flux chambers across the Peruvian oxygen minimum zone (OMZ) from 74 to 1000 m water depth. Sediments at all locations were net consumers of bottom water NO3−. In waters shallower than 400 m, this sink was largely attributed to dissimilatory nitrate reduction to ammonium (DNRA) by filamentous nitrate-storing bacteria (Marithioploca and Beggiatoa) and to denitrification by foraminifera. The apparent N isotope effect of benthic NO3− loss (15εapp) was 7.4 ± 0.7‰ at microbial mat sites and 2.5 ± 0.9‰ at the lower fringe of the OMZ (400 m) where foraminifera were abundant. The OMZ sediments were a source of 15N-enriched NO2− (28.9 to 65.5‰) and NH4+ (19.4–20.5‰) to the bottom water. Model simulations generally support a previous hypothesis attributing the 15NH4+ enrichment to a coupling between DNRA and anammox (termed DAX) using biologically-stored NO3− from Marithioploca and NH4+ from the porewater. The model predicts that 40% of NO3− that is actively transported into the sediment by Marithioploca is reduced to N2 by this pathway. DAX enhances N2 fluxes by a factor of 2–3 and accounts for 70% of fixed N loss to N2. Moreover, because most of the ambient porewater NH4+ is generated by DNRA, up to two-thirds of biologically-transported NO3− could end up being lost to N2. This challenges the premise that Marithioploca-dominated sediments tend to conserve fixed N. By limiting the flux of 15NH4+ back to the ocean, DAX also tends to decrease benthic N fractionation. Tracking the fate of NH4+ once it leaves the sediment is critical for understanding how the benthos contributes to N isotope signals in the water column.