First on-line isotopic characterization of N2O above intensively managed grassland

The analysis of the four main isotopic N2O species ((NNO)-N-14-N-14-O-16, (NNO)-N-14-N-15-O-16, (NNO)-N-15-N-14-O-16, (NNO)-N-14-N-14-O-18) and especially the intramolecular distribution of N-15 (site preference, SP) has been suggested as a tool to distinguish source processes and to help constrain the global N2O budget. However, current studies suffer from limited spatial and temporal resolution capabilities due to the combination of discrete flask sampling with subsequent laboratory-based mass-spectrometric analysis. Quantum cascade laser absorption spectroscopy (QCLAS) allows the selective high-precision analysis of N2O isotopic species at trace levels and is suitable for in situ measurements. Here, we present results from the first field campaign, conducted on an intensively managed grassland site in central Switzerland. N2O mole fractions and isotopic composition were determined in the atmospheric surface layer (at 2.2 m height) at a high temporal resolution with a modified state-of-the-art laser spectrometer connected to an automated N2O preconcentration unit. The analytical performance was determined from repeated measurements of a compressed air tank and resulted in measurement repeatability of 0.20, 0.12 and 0.11% for delta N-15(alpha), delta N-15(beta) and delta O-18, respectively. Simultaneous eddy-covariance N2O flux measurements were used to determine the flux-averaged isotopic signature of soil-emitted N2O. Our measurements indicate that, in general, nitrifier-denitrification and denitrification were the prevalent sources of N2O during the campaign and that variations in isotopic composition were due to alterations in the extent to which N2O was reduced to N-2 rather than to other path-ways, such as hydroxylamine oxidation. Management and rewetting events were characterized by low values of the intramolecular N-15 site preference (SP), delta N-15(bulk) and delta O-18, suggesting that nitrifier-denitrification and incomplete heterotrophic bacterial denitrification responded most strongly to the induced disturbances. The flux-averaged isotopic composition of N2O from intensively managed grassland was 6.9 +/- 4.3, -17.4 +/- 6.2 and 27.4 +/- 3.6% for SP, delta N-15(bulk) and delta O-18, respectively. The approach presented here is capable of providing long-term data sets also for other N2O-emitting ecosystems, which can be used to further constrain global N2O inventories.