Isotopologue fractionation during microbial reduction of N2O within soil mesocosms as a function of water-filled pore space

Isotopologue analyses of N₂O within soil mesocosm experiments were used to evaluate the influence of N₂O reduction on isotope fractionation. We investigated fractionation during N₂O reduction at 60%, 80% and 100% water-filled pore space (WFPS) and found net isotope effects (NIE) for δ¹⁵N of 4.2–7.8‰, δ¹⁸O of 12.5–19.1‰, δ¹⁵N^α of 6.4–9.7‰ and δ¹⁵N^β of 2.0–5.9‰. Consequently, N₂O reduction has a marked affect on isotopologue values and the importance of this process in flux chamber studies should not be ignored. With the exception of SP (the difference between the δ¹⁵N of the central, α, and terminal, β, atoms) inverse relationships between the NIE, reaction rate and reaction rate constant and WFPS were observed. Isotopic discrimination in SP during N₂O reduction was small and the average NIE for the treatments varied between 2.9‰ and 4.5‰. A strong correlation was evident between δ¹⁸O vs. δ¹⁵N and δ¹⁸O vs. δ¹⁵N^α during reduction with slopes of 2.6 and 1.9, respectively, which contrasts from a slope of <1 commonly observed for mixing between soil-derived and atmospheric N₂O in flux chambers.