Isotope ratio studies of atmospheric organic compounds: Principles, methods, applications and potential

In the atmosphere, both gas and particle phase organic trace compounds (OTC) have multiple effects on air quality and climate. Gaps exist in a fundamental understanding of the sources and sinks of organics and thus, knowledge needed to steer regulatory purposes is far from complete. Isotopes provide specific “fingerprints” in OTC. These fingerprints result from the isotopic composition at emission, as well as from chemical and physical processes in the atmosphere. Compound specific isotope ratio mass spectrometry (IRMS) in atmospheric OTC is therefore a promising tool to improve our understanding of sources and the atmospheric fate of OTC. Due to analytical challenges originating from the small sample amounts and a huge variety of physical and chemical properties of OTC present in the atmosphere, such measurements are not routinely performed. We present an overview of basic concepts as well as instrumental and measurement procedures used for compound specific IRMS in atmospheric OTC. Concepts for the interpretation of ambient observations are reviewed together with available literature data on source specific and ambient δ13C values of gas and particle phase OTC. Full deployment of the IRMS potential in future atmospheric studies will depend on the availability of laboratory kinetic data. Further method developments, such as increasing sensitivity and accuracy, as well as techniques for simultaneous isotope ratio measurement of multiple atoms are expected to further extend the potential use of isotope ratios for studies of atmospheric OTC