Abstract. The analysis of the four main isotopic N2O species (14N14N16O, 14N15N16O, 15N14N16O, 14N14N18O) and especially the intramolecular distribution of 15N ("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 δ15Nα, δ15Nβ and δ18O, 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 N2 rather than to other pathways, such as hydroxylamine oxidation. Management and rewetting events were characterized by low values of the intramolecular 15N site preference (SP), δ15Nbulk and δ18O, 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, δ15Nbulk and δ18O, 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.

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Abstract. Important information about the biogeochemical cycle of nitrous oxide (N 2 O) can be obtained by measuring its three main isotopic species, 14 N 15 N 16 O, 15 N 14 N 16 O, and 14 N 14 N 16 O, and the respective site-specific relative isotope ratio differences δ 15 N α and δ 15 N β . Absorption laser spectroscopy in the mid-infrared is a direct method for the analysis of the 15 N isotopic composition of N 2 O, yet not sensitive enough for atmospheric N 2 O mixing ratios (320 ppb). To enable a fully-automated high precision analysis of N 2 O isotopic species at ambient mixing ratios, we built and optimized a liquid nitrogen-free preconcentration unit to be coupled to a quantum cascade laser (QCL) based spectrometer. During standard operation 10 l of ambient air are preconcentrated on a HayeSep D trap and desorbed in 50 ml of synthetic air. Rigorous tests were conducted, using FTIR, quantum cascade laser absorption spectroscopy (QCLAS), GC-FID and component-specific ozone and oxygen analysers to investigate recovery rates, conservation of isotopic signatures and spectral interferences after preconcentration. We achieve quantitative N 2 O recovery of >99% with only minor, statistically not significant isotopic fractionation and no relevant spectral interferences from other atmospheric constituents. The developed preconcentration unit also has the potential to be applied to other trace gases and their isotopic composition.

Intermittent scanning for continuous-wave quantum cascade lasers is proposed along with a custom-built laser driver optimized for such operation. This approach lowers the overall heat dissipation of the laser by dropping its drive current to zero between individual scans and holding a longer pause between scans. This allows packaging cw-QCLs in TO–3 housings with built-in collimating optics, thus reducing cost and footprint of the device. The fully integrated, largely analog, yet flexible laser driver eliminates the need for any external electronics for current modulation, lowers the demands on power supply performance, and allows shaping of the tuning current in a wide range. Optimized ramp shape selection leads to large and nearly linear frequency tuning (>1.5 cm−1). Experimental characterization of the proposed scheme with a QCL emitting at 7.7 μm gave a frequency stability of 3.2×10−5 cm−1 for the laser emission, while a temperature dependence of 2.3×10−4 cm−1/K was observed when the driver electronics was exposed to sudden temperature changes. We show that these characteristics make the driver suitable for high precision trace gas measurements by analyzing methane absorption lines in the respective spectral region.

Abstract. Important information about the biogeochemical cycle of nitrous oxide (N2O) can be obtained by measuring its three main isotopomers, 14N15N16O, 15N14N16O, and 14N14N16O, and the respective site-specific isotope ratios δ15Nα and δ15Nβ. Absorption laser spectroscopy in the mid-infrared is a direct method for N2O isotopomer analysis, yet not sensitive enough for atmospheric N2O concentrations (320 ppb). To enable a fully-automated high precision N2O isotopomer analysis at ambient concentrations, we built and optimized a liquid nitrogen-free preconcentration unit to be coupled to a quantum cascade laser (QCL) based spectrometer. Rigorous tests were conducted, using FTIR and quantum cascade laser absorption spectroscopy (QCLAS), to investigate recovery rates, conservation of isotopic signatures and spectral interferences after preconcentration. We achieve quantitative N2O recovery of >99% with only minor, statistically not significant isotopic fractionation and no relevant spectral interferences from other atmospheric constituents. The developed preconcentration unit also has the potential to be applied to other trace gases and their isotopic composition.