First investigation and absolute calibration of clumped isotopes in N₂ O by mid-infrared laser spectroscopy

Unravelling the biogeochemical cycle of the potent greenhouse gas nitrous oxide (N₂ O) is an underdetermined problem in environmental sciences due to the multiple source and sink processes involved, which complicate mitigation of its emissions. Measuring the doubly isotopically substituted molecules (isotopocules) of N₂ O can add new opportunities to fingerprint and constrain its cycle.

We present a laser spectroscopic technique to selectively and simultaneously measure the eight most abundant isotopocules of N₂ O, including three doubly substituted species - so called "clumped isotopes". For the absolute quantification of individual isotopocule abundances, we propose a new calibration scheme that combines thermal equilibration of a working standard gas with a direct mole fraction-based approach.

The method is validated for a large range of isotopic composition values by comparison with other established methods (laser spectroscopy using conventional isotopic scale and isotope ratio mass spectrometry). Direct intercomparison with recently developed ultrahigh-resolution mass spectrometry shows clearly the advantages of the new laser technique, especially with respect to site specificity of isotopic substitution in the N₂ O molecule.

Our study represents a new methodological basis for the measurements of both singly substituted and clumped N₂ O isotopes. It has a high potential to stimulate future research in the N₂ O community by establishing a new class of reservoir-insensitive tracers and molecular-scale insights.