Nitrous oxide cycling in the Black Sea inferred from stable isotope and isotopomer distributions

The low-oxygen regions of the worldʹs oceans have been shown to be major sources of nitrous oxide, a trace gas in the atmosphere that contributes to both greenhouse warming and the destruction of stratospheric ozone. Nitrous oxide can be produced as a by-product of nitrification or an intermediate of denitrification; low oxygen conditions enhance the yield of nitrous oxide from both pathways. We measured the concentration and isotopic composition of dissolved nitrous oxide at several stations in the Black Sea, an anoxic basin with a well-defined suboxic layer that separates the ventilated surface waters from the sulfidic deep waters. Our data show that in contrast to other low-oxygen marine regions, nitrous oxide does not accumulate in the Black Sea at significant levels. Moreover, whereas the reduction of nitrous oxide by denitrification usually yields residual gas that is enriched in both stable isotopes, in the Black Sea declining nitrous oxide concentrations are accompanied by enrichment in 18O-N2O but depletion in 15N-N2O. We measured a minimum δ15N-N2O value of −10.8±0.8‰ vs. air N2, by far the lowest measured to date for seawater. Measurements of the distribution of 15N within the linear nitrous oxide molecule reveal that this unusual isotopic signal is most pronounced in the end-position nitrogen, and that site preference, or the tendency for 15N to be found in the center-position nitrogen, co-varies positively with 18O-N2O. We surmise that the highly unusual isotopic composition of Black Sea nitrous oxide is the result of two processes: production of 15N-depleted nitrous oxide by ammonium oxidation followed by its reduction by denitrification, which causes enrichment in 18O and enhancement of 15N-site preference. Bottle incubation experiments with 15N-ammonium and 15N-nitrite reveal that both oxidation and reduction pathways to nitrous oxide are active in the Black Sea suboxic zone.