Description: Empirical transfer functions are derived for predicting the total benthic nitrate loss(LNO3) and the net loss of dissolved inorganic nitrogen (LDIN) in marine sediments,equivalent to sedimentary denitrification. The functions are dynamic vertically integratedsediment models which require the rain rate of particulate organic carbon to the seafloor(RRPOC) and a proposed new variable(O2-NO3)bw (bottom water O2 concentration minus NO3-concentration) as the only input parameters. Applied globally to maps of RRPOC and(O2-NO3)bw on a 1° x 1° spatial resolution, the models predict a NO3- drawdown of 196 Tg yr-1 (LNO3)of which 153 – 155 Tg yr-1 is denitrified to N2 (LDIN). This is in good agreement with previous estimates using very different methods. Our approach implicitly accounts for fixed N loss via anammox, such that our findings do not support the idea that the relatively recent discovery of anammox in marine sediments might require current estimates of the global benthic marine N budget to be revised. The continental shelf (0 – 200 m) accounts for 〉50% of global LNO3 and LDIN, with slope (200 – 2000 m) and deep-sea (〉2000 m) sediments contributing ca. 30% and 20%, respectively. Denitrification in high-nitrate/low-oxygen regions such as oxygen minimum zones is significant (ca. 15 Tg N yr-1; 10% of global) despite covering only 1% of the seafloor. The data are used to estimate the net fluxes of nitrate (18 Tg N yr-1) and phosphate(27 Tg P yr-1) across the sediment-water interface. The benthic fluxes strongly deviate from Redfield composition, with globally averaged N:P, N:C and C:P values of 8.3, 0.067 and 122, respectively, indicating world-wide fixed N losses (by denitrification) relative to C and P. The transfer functions are designed to be coupled dynamically to general circulation models to better predict the feedback of sediments on pelagic nutrient cycling and dissolved O2 distributions.

Description: We present sedimentary geochemical data and in situ benthic flux measurements of dissolved inorganic nitrogen (DIN: NO3−, NO2−, NH4+) and oxygen (O2) from 7 sites with variable sand content along 18°N offshore Mauritania (NW Africa). Bottom water O2 concentrations at the shallowest station were hypoxic (42 μM) and increased to 125 μM at the deepest site (1113 m). Total oxygen uptake rates were highest on the shelf (−10.3 mmol O2 m−2 d−1) and decreased quasi-exponentially with water depth to −3.2 mmol O2 m−2 d−1. Average denitrification rates estimated from a flux balance decreased with water depth from 2.2 to 0.2 mmol N m−2 d−1. Overall, the sediments acted as net sink for DIN. Observed increases in δ15NNO3 and δ18ONO3 in the benthic chamber deployed on the shelf, characterized by muddy sand, were used to calculate apparent benthic nitrate fractionation factors of 8.0‰ (15εapp) and 14.1‰ (18εapp). Measurements of δ15NNO2 further demonstrated that the sediments acted as a source of 15N depleted NO2−. These observations were analyzed using an isotope box model that considered denitrification and nitrification of NH4+ and NO2−. The principal findings were that (i) net benthic 14N/15N fractionation (εDEN) was 12.9 ± 1.7‰, (ii) inverse fractionation during nitrite oxidation leads to an efflux of isotopically light NO2− (−22 ± 1.9‰), and (iii) direct coupling between nitrification and denitrification in the sediment is negligible. Previously reported εDEN for fine-grained sediments are much lower (4–8‰). We speculate that high benthic nitrate fractionation is driven by a combination of enhanced porewater–seawater exchange in permeable sediments and the hypoxic, high productivity environment. Although not without uncertainties, the results presented could have important implications for understanding the current state of the marine N cycle.

Description: Oxygen minimum zones (OMZs) represent key regions for nitrogen (N) turnover in the water column as well as in the sediments. However, the redox dependent source-sink function of sediments for reactive nitrogen (NO3- + NO2- + NH4+) is not well established. To address this issue, we studied benthic nitrogen cycling under different bottom water oxygen concentrations along a transect traversing the Peruvian OMZ at 11°S. In situ fluxes of nitrogen species across the sediment-water interface were measured using benthic landers and the sediment geochemistry was analyzed in recovered multi-core samples. The fieldwork was conducted through (80 - 400 m water depth) and beyond (700 - 1000 m water depth) the extension of the OMZ. The relative importance of different processes in the benthic nitrogen cycle was investigated using a 1D reaction-transport model tuned to the measured data. The reaction network included the release of ammonium during organic matter mineralization, nitrification and heterotrophic denitrification, as well as anammox. Nitrite was explicitly included in the model as an independent variable. Dissimilatory nitrate reduction to ammonium (DNRA) was also considered where mats of large sulfur bacteria were observed during towed camera deployments (~ 80 - 300 m depth). The model was able to simulate the following features of the benthic N cycle determined from the in situ lander deployments: (i) at the upper fringe of the OMZ (~ 80 - 250 m), the sediments acted as a source of reactive nitrogen due to enhanced ammonium release, (ii) at the lower fringe of the OMZ (300 - 400 m), there was a net uptake of reactive nitrogen of up to ~ 1.9 mmol N m-2 d-1 , and (iii) below the OMZ, reactive nitrogen fluxes into the sediments were low (≤ 0.5 mmol N m-2 d-1 ). The model further predicted that denitrification was the major control on N2 production along the entire transect whereas anammox played a minor role (≤ 10%). At the upper fringe of the OMZ, DNRA was driving ammonium release and determined whether the sediments were a net source or sink for reactive nitrogen species. In contrast, at the lower fringe of the OMZ organic carbon mineralization was the dominant process releasing ammonium. The relative importance of DNRA versus organic carbon mineralization for ammonium release varied systematically between these two end-members along the studied transect.

Description: The benthic nitrogen (N) cycle is highly dynamic and diverse due to the strong redox gradients occurring in marine surface sediments and the variety of oxidation states accessible to nitrogen. Since N is a limiting nutrient for biological productivity, fluxes of nitrogenous species across the sediment-water interface may strongly affect the biogeochemistry of nitrogen, carbon and phosphorus in the oceanic water column. In particular, as a major sink for fixed N in the marine environment, benthic denitrification has a profound impact on the availability of bioavailable N in the oceans. Consequently, an understanding of N cycling in marine sediments is of major importance for constraining the global marine nitrogen budget and quantifying benthic-pelagic feedbacks. The thesis addresses benthic N turnover on local and global scales with a special focus on oxygen minimum zones where strong lateral redox gradients lead to unique and highly interesting interactions in N cycling.

Description: This study investigates the biogeochemical processes that control the benthic fluxes of dissolved nitrogen (N) species in Boknis Eck - a 28 m deep site in the Eckernförde Bay (southwestern Baltic Sea). Bottom water oxygen concentrations (O2-BW) fluctuate greatly over the year at Boknis Eck, being well-oxygenated in winter and experiencing severe bottom water hypoxia and even anoxia in late summer. The present communication addresses the winter situation (February 2010). Fluxes of ammonium (NH4+), nitrate (NO3-) and nitrite (NO2-) were simulated using a benthic model that accounted for transport andbiogeochemical reactions and constrained with ex situ flux measurements and sediment geochemical analysis. The sediments were a net sink for NO3- (-0.35 mmol m-2 d-1 of NO3-), of which 75% was ascribed to dissimilatory reduction of nitrate to ammonium (DNRA) by sulfide oxidizing bacteria, and 25% to NO3- reduction to NO2- by denitrifying microorganisms. NH4+ fluxes were high (1.74 mmol m-2d-1 of NH4+), mainly due to the degradation of organic nitrogen, and directed out of the sediment. NO2-fluxes were negligible. The sediments in Boknis Eck are, therefore, a net source of dissolved inorganic nitrogen(DIN = NO3- + NO2- + NH4+) during winter. This is in large part due to bioirrigation, which accounts for 76% of the benthic efflux of NH4+, thus reducing the capacity for nitrification of NH4+. The combined rate of fixed N loss by denitrification and anammox was estimated at 0.08 mmol m-2 d-1 of N2, which is at the lower end of previously reported values. A systematic sensitivity analysis revealed that denitrification and anammox respond strongly and positively to the concentration of NO3- in the bottomwater (NO3-BW).Higher O2-BW decreases DNRA and denitrification but stimulates both anammox and the contribution ofanammox to total N2 production (%Ramx). A complete mechanistic explanation of these findings is provided. Our analysis indicates that nitrification is the geochemical driving force behind the observed correlation between %Ramx and water depth in the seminal study of Dalsgaard et al. (2005). Despite remaining uncertainties, the results provide a general mechanistic framework for interpreting the existing knowledge of N-turnover processes and fluxes in continental margin sediments, as well as predicting the types of environment where these reactions are expected to occur prominently.

Description: Benthic nitrogen (N) cycling was investigated at six stations along a transect traversing the Peruvian oxygen minimum zone (OMZ) at 11 °S. An extensive dataset including porewater concentration profiles and in situ benthic fluxes of nitrate (NO3–), nitrite (NO2–) and ammonium (NH4+) was used to constrain a 1–D reaction–transport model designed to simulate and interpret the measured data at each station. Simulated rates of nitrification, denitrification, anammox and dissimilatory nitrate reduction to ammonium (DNRA) by filamentous large sulfur bacteria (e.g. Beggiatoa and Thioploca) were highly variable throughout the OMZ yet clear trends were discernible. On the shelf and upper slope (80 – 260 m water depth) where extensive areas of bacterial mats were present, DNRA dominated total N turnover (less-than-or-equals, slant 2.9 mmol N m–2 d–1) and accounted for greater-or-equal, slanted 65 % of NO3– + NO2– uptake by the sediments from the bottom water. Nonetheless, these sediments did not represent a major sink for dissolved inorganic nitrogen (DIN = NO3– + NO2– + NH4+) since DNRA reduces NO3– and, potentially NO2–, to NH4+. Consequently, the shelf and upper slope sediments were recycling sites for DIN due to relatively low rates of denitrification and high rates of ammonium release from DNRA and ammonification of organic matter. This finding contrasts with the current opinion that sediments underlying OMZs are a strong sink for DIN. Only at greater water depths (300 – 1000 m) did the sediments become a net sink for DIN. Here, denitrification was the major process (less-than-or-equals, slant 2 mmol N m–2 d–1) and removed 55 – 73 % of NO3– and NO2– taken up by the sediments, with DNRA and anammox accounting for the remaining fraction. Anammox was of minor importance on the shelf and upper slope yet contributed up to 62 % to total N2 production at the 1000 m station. The results indicate that the partitioning of oxidized N (NO3–, NO2–) into DNRA or denitrification is a key factor determining the role of marine sediments as DIN sinks or recycling sites. Consequently, high measured benthic uptake rates of oxidized N within OMZs do not necessarily indicate a loss of fixed N from the marine environment.

Description: Benthic fluxes of dissolved ferrous iron (Fe2+) and phosphate (TPO4) were quantified by in situ benthic chamber incubations and pore-water profiles along a depth transect (11°S, 80–1000 m) across the Peruvian oxygen minimum zone (OMZ). Bottom-water O2 levels were 〈 2 µmol L-1 down to 500-m water depth, and increased to ~40 µmol L-1 at 1000 m. Fe2+ fluxes were highest on the shallow shelf (maximum 316 mmol m-2 yr-1), moderate (15.4 mmol m-2 yr-1) between 250 m and 600 m, and negligible at deeper stations. In the persistent OMZ core, continuous reduction of Fe oxyhydroxides results in depletion of sedimentary Fe :Al ratios. TPO4 fluxes were high (maximum 292 mmol m-2 yr-1) throughout the shelf and the OMZ core in association with high organic carbon degradation rates. Ratios between organic carbon degradation and TPO4 flux indicate excess release of P over C when compared to Redfield stoichiometry. Most likely, this is caused by preferential P release from organic matter, dissolution of fish debris, and/or P release from microbial mat communities, while Fe oxyhydroxides can only be inferred as a major P source on the shallow shelf. The benthic fluxes presented here are among the highest reported from similar, oxygen-depleted environments and highlight the importance of sediments underlying anoxic water bodies as nutrient sources to the ocean. The shelf is particularly important as the periodic passage of coastal trapped waves and associated bottom-water oxygenation events can be expected to induce a transient biogeochemical environment with highly variable release of Fe2+ and TPO4.