Abstract. The isotopic composition of soil-derived N2O can help differentiate between N2O production pathways and estimate the fraction of N2O reduced to N2. Until now, δ18O of N2O has been rarely used in the interpretation of N2O isotopic signatures because of the rather complex oxygen isotope fractionations during N2O production by denitrification. The latter process involves nitrate reduction mediated through the following three enzymes: nitrate reductase (NAR), nitrite reductase (NIR) and nitric oxide reductase (NOR). Each step removes one oxygen atom as water (H2O), which gives rise to a branching isotope effect. Moreover, denitrification intermediates may partially or fully exchange oxygen isotopes with ambient water, which is associated with an exchange isotope effect. The main objective of this study was to decipher the mechanism of oxygen isotope fractionation during N2O production by soil denitrification and, in particular, to investigate the relationship between the extent of oxygen isotope exchange with soil water and the δ18O values of the produced N2O. In our soil incubation experiments Δ17O isotope tracing was applied for the first time to simultaneously determine the extent of oxygen isotope exchange and any associated oxygen isotope effect. We found that N2O formation in static anoxic incubation experiments was typically associated with oxygen isotope exchange close to 100 % and a stable difference between the 18O ∕ 16O ratio of soil water and the N2O product of δ18O(N2O ∕ H2O)  =  (17.5 ± 1.2) ‰. However, flow-through experiments gave lower oxygen isotope exchange down to 56 % and a higher δ18O(N2O ∕ H2O) of up to 37 ‰. The extent of isotope exchange and δ18O(N2O ∕ H2O) showed a significant correlation (R2 = 0.70, p <  0.00001). We hypothesize that this observation was due to the contribution of N2O from another production process, most probably fungal denitrification. An oxygen isotope fractionation model was used to test various scenarios with different magnitudes of branching isotope effects at different steps in the reduction process. The results suggest that during denitrification, isotope exchange occurs prior to isotope branching and that this exchange is mostly associated with the enzymatic nitrite reduction mediated by NIR. For bacterial denitrification, the branching isotope effect can be surprisingly low, about (0.0 ± 0.9) ‰, in contrast to fungal denitrification where higher values of up to 30 ‰ have been reported previously. This suggests that δ18O might be used as a tracer for differentiation between bacterial and fungal denitrification, due to their different magnitudes of branching isotope effects.

Monitoring the sources and fate of freshwater in the East Greenland Current (EGC) is important, as this water has the potential to suppress deep convection in the Nordic and Labrador Seas if the outflow of freshwater from the Arctic Ocean increases in response to climate change. Here, hydrographic, oxygen isotope ratio and dissolved barium concentration sections across Denmark Strait collected in 1998 and 1999 are used to determine the freshwater composition of the EGC at these times. Comparison of meltwater fluxes at Denmark Strait and Fram Strait indicates a net melting of sea ice into the EGC between these two locations, with a significant proportion of sea ice drifting into the Nordic Seas or on to the East Greenland Shelf. We conclude that the phase of freshwater exiting the Arctic Ocean through Fram Strait is important in determining its possible impact on deep water formation in the Nordic and Labrador Seas

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The snowpack acts as a sink for atmospheric reactive nitrogen, but several postdeposition pathways have been reported to alter the concentration and isotopic composition of snow nitrate with implications for atmospheric boundary layer chemistry, ice core records, and terrestrial ecology following snow melt. Careful daily sampling of surface snow during winter (11-15 February 2010) and springtime (9 April to 5 May 2010) near Ny-Ålesund, Svalbard reveals a complex pattern of processes within the snowpack. Dry deposition was found to dominate over postdeposition losses, with a net nitrate deposition rate of (0.6 ± 0.2) μmol m À2 d À1 to homogeneous surface snow. At Ny-Ålesund, such surface dry deposition can either solely result from long-range atmospheric transport of oxidized nitrogen or include the redeposition of photolytic/bacterial emission originating from deeper snow layers. Our data further confirm that polar basin air masses bring 15 N-depleted nitrate to Svalbard, while high nitrate δ( 18 O) values only occur in connection with ozone-depleted air, and show that these signatures are reflected in the deposited nitrate. Such ozone-depleted air is attributed to active halogen chemistry in the air masses advected to the site. However, here the Ny-Ålesund surface snow was shown to have an active role in the halogen dynamics for this region, as indicated by declining bromide concentrations and increasing nitrate δ( 18 O), during high BrO (low-ozone) events. The data also indicate that the snowpack BrO-NO x cycling continued in postevent periods, when ambient ozone and BrO levels recovered.

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