Porewater and particulate geochemistry during Maria S. Merian cruise MSM17/4

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 /m2 d) and decreased quasi-exponentially with water depth to -3.2 mmol O2 /m2 d. Average denitrification rates estimated from a flux balance decreased with water depth from 2.2 to 0.2 mmol N /m2 d. Overall, the sediments acted as net sink for DIN. Observed increases in delta 15NNO3 and delta 18ONO3 in the benthic chamber deployed on the shelf, characterized by muddy sand, were used to calculate apparent benthic nitrate fractionation factors of 8.0 pro mille (15epsilon app) and 14.1 pro mille (18epsilon app). Measurements of delta 15NNO2 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 (epsilon DEN) was 12.9 ± 1.7pro mille, (ii) inverse fractionation during nitrite oxidation leads to an efflux of isotopically light NO2- (-22 ± 1.9 pro mille), and (iii) direct coupling between nitrification and denitrification in the sediment is negligible. Previously reported epsilon DEN for fine-grained sediments are much lower (4-8 pro mille). 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.

Distribution of neodymium isotopes and concentrations during M77/3 and M77/4

The radiogenic isotope composition of the Rare Earth Element (REE) neodymium (Nd) is a powerful water mass proxy for present and past ocean circulation. The processes controlling the Nd budget of the global ocean are not quantitatively understood and in particular source and sink mechanisms are still under debate. In this study we present the first full water column data set of dissolved Nd isotope compositions and Nd concentrations for the Eastern Equatorial Pacific (EEP), where one of the globally largest Oxygen Minimum Zones (OMZ) is located. This region is of particular interest for understanding the biogeochemical cycling of REEs because anoxic conditions may lead to release of REEs from the shelf, whereas high particle densities and fluxes potentially remove the REEs from the water column. Data were obtained between 11400N and 161S along a nearshore and an offshore transect. Near surface zonal current bands, such as the Equatorial Undercurrent (EUC) and the Subsurface Countercurrent (SSCC), which are supplying oxygen-rich water to the OMZ are characterized by radiogenic Nd isotope signatures (eNd=-2). Surface waters in the northernmost part of the study area are even more radiogenic (eNd = +3), most likely due to release of Nd from volcanogenic material. Deep and bottom waters at the southernmost offshore station (141S) are clearly controlled by advection of water masses with less radiogenic signatures (eNd=- 7) originating from the Southern Ocean. Towards the equator, however, the deep waters show a clear trend towards more radiogenic values of up to eNd=-2. The northernmost station located in the Panama basin shows highly radiogenic Nd isotope signatures in the entire water column, which indicates that particle scavenging, downward transport and release processes play an important role. This is supported by relatively low Nd concentrations in deep waters (3000-6000 m) in the EEP (20 pmol/kg) compared to locations in the Northern and Central Pacific (40-60 pmol/kg), which suggests enhanced removal of Nd in the EEP.