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Organosulfur compounds (OSCs) are naturally emitted via various processes involving phytoplankton and algae in marine regions, from animal metabolism, and from biomass decomposition inland. These compounds are malodorant and reactive. Their oxidation to methanesulfonic and sulfuric acids leads to the formation and growth of atmospheric particles, which are known to influence clouds and climate, atmospheric chemical processes. In addition, particles in air have been linked to negative impacts on visibility and human health. Accurate measurements of the OSC precursors are thus essential to reduce uncertainties in their sources and contributions to particle formation in air. Two different approaches, proton-transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) and canister sampling coupled to gas chromatography with flame ionization detector (GC-FID), are compared for both laboratory standards (dimethyl sulfide, DMS; dimethyl disulfide, DMDS; dimethyl trisulfide, DMTS; and methanethiol, MTO) and for a complex sample. Results show that both techniques produce accurate quantification of DMS. While PTR-ToF-MS provides real-time measurements of all four OSCs individually, significant fragmentation of DMDS and DMTS occurs, which can complicate their identification in complex mixtures. Canister sampling coupled with GC-FID provides excellent sensitivity for DMS, DMDS, and DMTS. However, MTO was observed to react on metal surfaces to produce DMDS and, in the presence of hydrogen sulfide, even DMTS. Avoiding metal in sampling systems seems to be necessary for measuring all but dimethyl sulfide in air.

Proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) is a technique commonly used to measure ambient volatile organic compounds (VOCs) in urban, rural, and remote environments. PTR-ToF-MS is known to produce artifacts from ion fragmentation, which complicates the interpretation and quantification of key atmospheric VOCs. This study evaluates the extent to which fragmentation and other ionization processes impact urban measurements of the PTR-ToF-MS ions typically assigned to isoprene (m/z 69, C 5 H 8 H +), acetaldehyde (m/z 45, CH 3 CHO +), and benzene (m/z 79, C 6 H 6 H +). Interferences from fragmentation are identified using gas chromatography (GC) pre-separation, and the impact of these interferences is quantified using ground-based and airborne measurements in a number of US cities, including Las Vegas, Los Angeles, New York City, and Detroit. In urban regions with low biogenic isoprene emissions (e.g., Las Vegas), fragmentation from higher-carbon aldehydes and cycloalkanes emitted from anthropogenic sources may contribute to m/z 69 by as much as 50 % during the day, while the majority of the signal at m/z 69 is attributed to fragmentation during the night. Interferences are a higher fraction of m/z 69 during airborne studies, which likely results from differences in the reactivity between isoprene and the interfering species along with the subsequent changes to the VOC mixture at higher altitudes. For other PTR masses, including m/z 45 and m/z 79, interferences are observed due to fragmentation and O 2+ ionization of VOCs typically used in solvents, which are becoming a more important source of anthropogenic VOCs in urban areas. We present methods to correct these interferences, which provide better agreement with GC measurements of isomer-specific molecules. These observations show the utility of deploying GC pre-separation for the interpretation PTR-ToF-MS spectra. [ABSTRACT FROM AUTHOR]