Journal cover Journal topic
Biogeosciences An interactive open-access journal of the European Geosciences Union
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Volume 13, issue 4
Biogeosciences, 13, 1129-1144, 2016
https://doi.org/10.5194/bg-13-1129-2016
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.
Biogeosciences, 13, 1129-1144, 2016
https://doi.org/10.5194/bg-13-1129-2016
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 24 Feb 2016

Research article | 24 Feb 2016

Oxygen isotope fractionation during N2O production by soil denitrification

Dominika Lewicka-Szczebak1, Jens Dyckmans3, Jan Kaiser2, Alina Marca2, Jürgen Augustin4, and Reinhard Well1 Dominika Lewicka-Szczebak et al.
  • 1Thünen Institute of Climate-Smart Agriculture, Federal Research Institute for Rural Areas, Forestry and Fisheries, Bundesallee 50, 38116 Braunschweig, Germany
  • 2Centre for Ocean and Atmospheric Sciences, School of Environmental Sciences, University of East Anglia, Norwich, NR4 7TJ, UK
  • 3Centre for Stable Isotope Research and Analysis, University of Göttingen, Büsgenweg 2, 37077 Göttingen, Germany
  • 4Leibniz Centre for Agricultural Landscape Research, Eberswalder Straße 84, 15374 Müncheberg, Germany

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 18O16O ratio of soil water and the N2O product of δ18O(N2OH2O) = (17.5±1.2)‰. However, flow-through experiments gave lower oxygen isotope exchange down to 56% and a higher δ18O(N2OH2O) of up to 37‰. The extent of isotope exchange and δ18O(N2OH2O) 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.

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Oxygen isotopic signatures of N2O are formed in complex multistep enzymatic reactions and depend on isotopic fractionation during enzymatic reduction of nitrate to N2O and on the oxygen isotope exchange with soil water. We propose a new method for quantification of oxygen isotope exchange, with simultaneous determination of oxygen isotopic signatures, to decipher the mechanism of oxygen isotopic fractionation. We indicate the differences between fractionation mechanisms by various pathways.
Oxygen isotopic signatures of N2O are formed in complex multistep enzymatic reactions and depend...
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