ALBERT

Description: Nitrogen cycling in the subsurface biosphere: nitrate isotopes in porewaters underlying the oligotrophic North Atlantic Biogeosciences Discussions, 12, 13545-13591, 2015 Author(s): S. D. Wankel, C. Buchwald, W. Ziebis, C. B. Wenk, and M. F. Lehmann Nitrogen (N) is a key component of fundamental biomolecules. Hence, the cycling and availability of N is a central factor governing the extent of ecosystems across the Earth. In the organic-lean sediment porewaters underlying the oligotrophic ocean, where low levels of microbial activity persist despite limited organic matter delivery from overlying water, the extent and modes of nitrogen transformations have not been widely investigated. Here we use the N and oxygen (O) isotopic composition of porewater nitrate (NO 3 − ) from a site in the oligotrophic North Atlantic (IODP) to determine the extent and magnitude of microbial nitrate production (via nitrification) and consumption (via denitrification). We find that NO 3 − accumulates far above bottom seawater concentrations (∼ 21 μM) throughout the sediment column (up to ∼ 50 μM) down to the oceanic basement as deep as 90 mbsf, reflecting the predominance of aerobic nitrification/remineralization within the deep marine sediments. Large changes in the δ 15 N and δ 18 O of nitrate, however, reveal variable influence of nitrate respiration across the three sites. We use an inverse porewater diffusion–reaction model, constrained by the N and O isotope systematics of nitrification and denitrification and the porewater NO 3 − isotopic composition, to estimate rates of nitrification and denitrification throughout the sediment column. Results indicate variability of reaction rates across and within the three boreholes that are generally consistent with the differential distribution of dissolved oxygen at this site, though not necessarily with the canonical view of how redox thresholds separate nitrate regeneration from dissimilative consumption spatially. That is, we provide isotope evidence for expanded zones of co-ocurring nitrification and denitrification. The isotope biogeochemical modeling also yielded estimates for the δ 15 N and δ 18 O of newly produced nitrate (δ 15 N NTR and δ 18 O NTR ), as well as the isotope effect for denitrification ( 15 ϵ DNF ), parameters with high relevance to global ocean models of N cycling. Estimated values of δ 15 N NTR were generally lower than previously reported δ 15 N values for sinking PON in this region. We suggest that these values can be related to sedimentary N-fixation and remineralization of the newly fixed organic N. Values of δ 18 O NTR generally ranged between −2.8 and 0.0 ‰, consistent with recent estimates based on lab cultures of nitrifying bacteria. Notably, some δ 18 O NTR values were elevated, suggesting incorporation of 18 O-enriched dissolved oxygen during nitrification, and possibly indicating a tight coupling of NH 4 + and NO 2 − oxidation in this metabolically sluggish environment. Our findings indicate that the production of organic matter by in situ autotrophy (e.g., nitrification, nitrogen fixation) supply a large fraction of the biomass and organic substrate for heterotrophy in these sediments, supplementing the small organic matter pool derived from the overlying euphotic zone. This work sheds new light on an active nitrogen cycle operating, despite exceedingly low carbon inputs, in the deep sedimentary biosphere.