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Nitrous oxide (N2O) is an important trace gas contributing to global warming and depletion of ozone in the stratosphere. Its increasing abundance is caused mainly by anthropogenic sources, such as application of fertilizers in agriculture or emissions from industry. To understand the N2O global budget, its sources and sinks need to be well-described and quantified. In this project, a new method for N2O source appointment was developed that can help with this task. The method is based on analysis of the eight most abundant isotopic molecules of N2O, using quantum cascade laser absorption spectroscopy (QCLAS). The applicability of the method towards the N2O biogeochemical cycle was demonstrated on a prominent N2O source (bacterial denitrification) and the most important N2O sink (UV photolysis) on samples prepared in laboratory experiments. An extension of the QCLAS method to natural samples can be achieved by hyphenation with a preconcentration technique that increases concentration of the analyte and standardizes the sample matrix. This article provides an overview of currently applied preconcentration techniques in the field of greenhouse-gas analysis and a description of the preconcentration device TREX that will be employed in future projects with the developed QCLAS method., (Copyright 2022 Kristýna Kantnerová, Matti Barthel, Johan Six, Lukas Emmenegger, Stefano M. Bernasconi, Joachim Mohn. License: This work is licensed under a Creative Commons Attribution 4.0 International License.)

CFCs (chlorofluorocarbons) and other strong ozone-depleting halogenated organic trace gases were used in numerous industrial, household and agriculture applications. First atmospheric measurements of CFCs were performed in the 1970s, well ahead of the detection of the ozone hole in the 1980s. The continuous observation of these ozone-depleting substances (ODSs) is crucial for monitoring their global ban within the Montreal Protocol. In addition, also HFCs (fluorinated hydrocarbons) are measured, which were introduced as substitutes of ODSs and are potent greenhouse gases. Since 2000, Empa continuously measures more than 50 halogenated trace gases at the high-Alpine station of Jungfraujoch (3850 m asl) as part of the global AGAGE network (Advanced Global Atmospheric Gases Experiment). Jungfraujoch is the highest location worldwide where such measurements are performed, and the site where several of these compounds were measured in the atmosphere for the first time. The measurements at Jungfraujoch and at other globally well-positioned sites serve as an early warning system, i. e. before potentially harmful halogenated organic substances can accumulate and detrimentally affect the natural environment.

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 15 N 14 N 18 O, 14 N 15 N 18 O, and 15 N 15 N 16 O, 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.