Deep-marine brine seeps in the modern ocean are considered analogues for settings that favoured the formation of sedimentary-exhalative zinc and lead deposits in deep time. Microbial activity plays an important role in the accumulation of ore minerals, meaning that the extent of mineralization is at least indirectly dependent on nutrient fluxes. Here, we investigated the biogeochemical nitrogen cycle in shallow (15-50 cm) sediment cores from the Orca Basin brine pool and surrounding sites, as well as from an active brine seep area near Dead Crab Lake in the Gulf of Mexico, with the aim of constraining the effect of brine seepage on this bio-essential element. We find high porewater ammonium concentrations in the millimolar range, paired with elevated ratios of organic carbon to nitrogen in sediments, which confirm previous hypotheses that the brine recycles ammonium from sedimentary strata back into the water column. Within Orca Basin, we note tentative evidence of microbial ammonium utilization. At the active seep, ammonium is mixed into the overlying water column and likely undergoes oxidation. Isotopic data from sediments and dissolved ammonium, paired with previously published genomic data, suggest the presence of dissimilatory nitrate reduction to ammonium (DNRA) at the brine-seawater interface. We conclude that brine seeps can stimulate biological nitrogen metabolisms in multiple ways. Our results may help calibrate studies of biogeochemical cycles around brine seeps that are archived in the rock record.

Rationale: Ion chromatography combined with inductively-coupled plasma mass spectrometry is an ideal tool for measuring low concentrations of anionic species such as phosphite; however, the high concentration of chloride and other anions in natural solutions may negatively impact chromatographic separation and data quality. Method: We developed an on-line mechanism of removing chloride from the sample within the ion chromatograph, using an additional valve and a separation column that transfers chloride to waste while phosphite and most other anions are retained. We installed this system in a coupled IC-ICPMS system (ICS6000 and Element 2 in medium resolution mode) and determined linearity and detection limits. In addition, we measured phosphorous species by NMR for comparison as an alternative method for phosphite determination. Results: Chloride was fully removed from the samples while phosphite was retained and could be analysed by IC-ICPMS. Concentrations could be measured down to 0.003 µmol/L and possibly less with good linearity over the explored range (up to 1.615 µmol/L; r 2 = 0.999). In contrast, the detection limit by NMR was 6.46 µmol/L. Conclusions: The on-line removal mechanism works well for simplifying sample matrices. It removes the need for costly pre-analytical sample treatment with OnGuard columns. We confirm that IC-ICPMS is the most powerful technique for quantifying phosphite in natural solutions. The new Cl-removal method may also be applicable to analyses of other anions.