Exploring atmospheric photooxidation with a new Gas Chromatograph Time-of-Flight Chemical Ionization Mass Spectrometer (GC-ToF-CIMS)

Abstract:

Atmospheric photooxidation is a fundamental process that effectively removes pollutants and greenhouse gases from the air we breathe. One way to explore these processes is to directly measure the stable intermediate oxidation products. Chemical Ionization Mass Spectrometry (CIMS) has proven to be a powerful tool to sensitively detect with high time resolution photooxidation products in the atmosphere such as hydroperoxides, acids, nitrates, and other oxygenated volatile organic compounds. Despite the potential to elucidate atmospheric photooxidation in detail, field observations of such compounds are sparse.

Here we present the development of a new Gas Chromatograph Time-of-Flight Chemical Ionization Mass Spectrometer (GC-ToF-CIMS) for field deployment. Using low pressure gas chromatography and CF₃O^- ionization chemistry, the selective operation of a GC is combined with the sensitive, specific, and fast detection of a high-resolution ToF-CIMS. The combination of chromatographic separation and exact mass identification allows detecting isomer resolved photooxidation products. Direct measurements in the atmosphere of such isomer distributions are particularly interesting due to the broad range of their individual atmospheric lifetimes and impacts.