Challenges associated with the sampling and analysis of organosulfur compounds in air using real-time PTR-ToF-MS and offline GC-FID

Abstract. 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.