Abstract
Abstract. Oxygenated volatile organic compounds (OVOCs) are formed during the oxidation of gas-phase hydrocarbons in the atmosphere. However, analytical challenges have hampered ambient measurements for many of these species, leaving unanswered questions regarding their atmospheric fate. We present the development of an in situ gas chromatography (GC) technique that, when combined with the sensitive and specific detection of chemical ionization mass spectrometry (CIMS), is capable of the isomer-resolved detection of a wide range of OVOCs. The instrument addresses many of the issues typically associated with chromatographic separation of such compounds (e.g., analyte degradation). The performance of the instrumentation is assessed through data obtained in the laboratory and during two field studies. We show that this instrument is able to successfully measure otherwise difficult-to-quantify compounds (e.g., organic hydroperoxides and organic nitrates) and observe the diurnal variations in a number of their isomers.
Highlights
The composition of the atmosphere is determined through a dynamic array of chemical emission, transport, deposition, and photochemical processing
Of particular interest is the photooxidation of non-methane hydrocarbons (NMHCs), which influence the distributions of key atmospheric constituents such as ozone (O3) and secondary organic aerosol (SOA)
The gas-phase oxidation of NMHCs is typically initiated by one of several atmospheric oxidants (i.e., OH, NO3, or O3) converting these hydrocarbons into oxygen-containing, often multifunctional, intermediates. These first-generation oxygenated volatile organic compounds, or Oxygenated volatile organic compounds (OVOCs), can undergo further transformations through a number of competing physical and photochemical sinks (Atkinson and Arey, 2003; Mellouki et al, 2015), each of which can have a unique effect on the atmosphere
Summary
The composition of the atmosphere is determined through a dynamic array of chemical emission, transport, deposition, and photochemical processing. The gas-phase oxidation of NMHCs is typically initiated by one of several atmospheric oxidants (i.e., OH, NO3, or O3) converting these hydrocarbons into oxygen-containing, often multifunctional, intermediates. These first-generation oxygenated volatile organic compounds, or OVOCs, can undergo further transformations through a number of competing physical and photochemical sinks (Atkinson and Arey, 2003; Mellouki et al, 2015), each of which can have a unique effect on the atmosphere. It has been shown that significant portions of OVOCs can be removed from the atmosphere through fast deposition processes
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