Novel laser spectroscopic technique for continuous analysis of N2O isotopomers - application and intercomparison with isotope ratio mass spectrometry

RATIONALE Nitrous oxide (N2O), a highly climate-relevant trace gas, is mainly derived from microbial denitrification and nitrification processes in soils. Apportioning N2O to these source processes is a challenging task, but better understanding of the processes is required to improve mitigation strategies. The N2O site-specific 15?N signatures from denitrification and nitrification have been shown to be clearly different, making this signature a potential tool for N2O source identification. We have applied for the first time quantum cascade laser absorption spectroscopy (QCLAS) for the continuous analysis of the intramolecular 15?N distribution of soil-derived N2O and compared this with state-of-the-art isotope ratio mass spectrometry (IRMS). METHODS Soil was amended with nitrate and sucrose and incubated in a laboratory setup. The N2O release was quantified by FTIR spectroscopy, while the N2O intramolecular 15?N distribution was continuously analyzed by online QCLAS at 1?Hz resolution. The QCLAS results on time-integrating flask samples were compared with those from the IRMS analysis. RESULTS The analytical precision (2 sigma) of QCLAS was around 0.3 parts per thousand for the delta 15Nbulk and the 15?N site preference (SP) for 1-min average values. Comparing the two techniques on flask samples, excellent agreement (R2?=?0.99; offset of 1.2 parts per thousand) was observed for the delta 15Nbulk values while for the SP values the correlation was less good (R2?=?0.76; offset of 0.9 parts per thousand), presumably due to the lower precision of the IRMS SP measurements. CONCLUSIONS These findings validate QCLAS as a viable alternative technique with even higher precision than state-of-the-art IRMS. Thus, laser spectroscopy has the potential to contribute significantly to a better understanding of N turnover in soils, which is crucial for advancing strategies to mitigate emissions of this efficient greenhouse gas. Copyright (c) 2012 John Wiley & Sons, Ltd.