Isotopologue ratios of N2O emitted from microcosms with NH4 fertilized arable soils under conditions favoring nitrification

Soils represent the major source of the atmospheric greenhouse gas nitrous oxide (N₂O) and there is a need to better constrain the total global flux and the relative contribution of the microbial source processes. The aim of our study was to determine variability and control of the isotopic fingerprint of N₂O fluxes following NH₄⁺-fertilization and dominated by nitrification. We conducted a microcosm study with three arable soils fertilized with 0–140 mg NH₄⁺–N kg⁻¹. Fractions of N₂O derived from nitrification and denitrification were determined in parallel experiments using the ¹⁵N tracer and acetylene inhibition techniques or by comparison with unfertilized treatments. Soils were incubated for 3–10 days at low moisture (30–55% water-filled pore space) in order to establish conditions favoring nitrification. Dual isotope and isotopomer ratios of emitted N₂O were determined by mass spectrometric analysis of δ¹⁸O, average δ¹⁵N (δ¹⁵N^bulk) and ¹⁵N site preference (SP = difference in δ¹⁵N between the central and peripheral N positions of the asymmetric N₂O molecule). N₂O originated mainly from nitrification (>80%) in all treatments and the proportion of NH₄⁺ nitrified that was lost as N₂O ranged between 0.07 and 0.45%. δ¹⁸O and SP of N₂O fluxes ranged from 15 to 28.4‰ and from 13.9 to 29.8‰, respectively. These ranges overlapped with isotopic signatures of N₂O from denitrification reported previously. There was a negative correlation between SP and δ¹⁸O which is opposite to reported trends in N₂O from denitrification. Variation of average ¹⁵N signatures of N₂O (δ¹⁵N^bulk) did not supply process information, apparently because a strong shift in precursor signatures masked process-specific effects on δ¹⁵N^bulk. Maximum SP of total N₂O fluxes and of nitrification fluxes was close to reported SP of N₂O from NH₄⁺ or NH₂OH conversion by autotrophic nitrifiers, suggesting that SP close to 30‰ is typical for autotrophic nitrification in soils following NH₄⁺-fertilization. The results suggest that the δ¹⁸O/SP fingerprint of N₂O might be used as a new indicator of the dominant source process of N₂O fluxes in soils.