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Nitrous oxide, N2O, is the environmentally most relevant constituent of the biogeochemical nitrogen cycle. Human activities, e.g. the agricultural use of mineral fertilizers, accelerate nitrogen transformations, leading to higher emissions of this strong greenhouse gas. Investigating the stable isotopic composition of N2O provides a better understanding of formation mechanisms to disentangle its variable source and sink processes. Mid-infrared (mid-IR) laser spectroscopy is a highly attractive technique to analyze N2O isotopocules based on their specific ro-vibrational absorption characteristics. Specifically, quantum cascade laser absorption spectroscopy (QCLAS) in combination with preconcentration has shown to be powerful for simultaneous and high-precision analysis of the main N2O isotopocules. Recently, in the scope of my PhD project, we have been advancing this analytical technique for the analysis of the very rare doubly substituted N2O isotopic species 15N14N18O, 14N15N18O, and 15N15N16O, also known as clumped isotopes. Currently, we are investigating the potential of these novel isotopic tracers to track the complex N2O production and consumption pathways. Improved understanding of the nitrogen cycle will be a major step towards N2O emission reduction.

Abstract. Nitrous oxide (N2O) is the primary atmospheric constituent involved in stratospheric ozone depletion and contributes strongly to changes in the climate system through a positive radiative forcing mechanism. The atmospheric abundance of N2O has increased from 270 ppb (parts per billion, 10−9 mole mole−1) during the pre-industrial era to approx. 330 ppb in 2018. Even though it is well known that microbial processes in agricultural and natural soils are the major N2O source, the contribution of specific soil processes is still uncertain. The relative abundance of N2O isotopocules (14N14N16N, 14N15N16O, 15N14N16O, and 14N14N18O) carries process-specific information and thus can be used to trace production and consumption pathways. While isotope ratio mass spectroscopy (IRMS) was traditionally used for high-precision measurement of the isotopic composition of N2O, quantum cascade laser absorption spectroscopy (QCLAS) has been put forward as a complementary technique with the potential for on-site analysis. In recent years, pre-concentration combined with QCLAS has been presented as a technique to resolve subtle changes in ambient N2O isotopic composition. From the end of May until the beginning of August 2016, we investigated N2O emissions from an intensively managed grassland at the study site Fendt in southern Germany. In total, 612 measurements of ambient N2O were taken by combining pre-concentration with QCLAS analyses, yielding δ15Nα, δ15Nβ, δ18O, and N2O concentration with a temporal resolution of approximately 1 h and precisions of 0.46 ‰, 0.36 ‰, 0.59 ‰, and 1.24 ppb, respectively. Soil δ15N-NO3- values and concentrations of NO3- and NH4+ were measured to further constrain possible N2O-emitting source processes. Furthermore, the concentration footprint area of measured N2O was determined with a Lagrangian particle dispersion model (FLEXPART-COSMO) using local wind and turbulence observations. These simulations indicated that night-time concentration observations were largely sensitive to local fluxes. While bacterial denitrification and nitrifier denitrification were identified as the primary N2O-emitting processes, N2O reduction to N2 largely dictated the isotopic composition of measured N2O. Fungal denitrification and nitrification-derived N2O accounted for 34 %–42 % of total N2O emissions and had a clear effect on the measured isotopic source signatures. This study presents the suitability of on-site N2O isotopocule analysis for disentangling source and sink processes in situ and found that at the Fendt site bacterial denitrification or nitrifier denitrification is the major source for N2O, while N2O reduction acted as a major sink for soil-produced N2O.

Methane (CH4) emissions from dairy husbandry are a hot topic in the context of active climate protection, where housing systems with slatted floors and slurry storage inside are in general expected to emit more than systems with solid floors. There are multiple factors, including climate conditions, that modulate the emission pattern. In this study, we investigated interrelations between CH4 emission patterns and climate conditions as well as differences between farm locations versus floor effects. We considered three data sets with 265, 264 and 275 hourly emission values from two housing systems (one slatted, one solid floor) in Switzerland and one system with solid floors in Germany. Each data set incorporated measurements in summer, winter and a transition season. The average CH4 emission was highest for the slatted floor system. For the solid floor systems, CH4 emissions at the Swiss location were around 30% higher compared to the German location. The shape of the distributions for the two solid floor systems was rather similar but very different from the distribution for the slatted floor system, which showed higher prevalence for extreme emissions. Rank correlations, which measure the degree of similarity between two rankings in terms of linear relation, were not able to detect dependencies at the selected significance level. In contrast, mutual information, which measures more general statistical dependencies in terms of shared information, revealed highly significant dependencies for almost all variable pairs. The weakest statistical relation was found between winds speed and CH4 emission, but the convection regime was found to play a key role. Clustering was consistent among the three data sets with five typical clusters related to high/low temperature and wind speed, respectively, as well as in some cases to morning and evening hours. Our analysis showed that despite the disparate and often insignificant correlation between environmental variables and CH4 emission, there is a strong relation between both, which shapes the emission pattern in many aspects much more in addition to differences in the floor type. Although a clear distinction of high and low emission condition clusters based on the selected environmental variables was not possible, trends were clearly visible. Further research with larger data sets is advisable to verify the detected trends and enable prognoses for husbandry systems under different climate conditions.