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. Oxidation of sulfur dioxide( SO2 ) in the gas phase and in cloud and fogwater leads to the formation of sulfate that contributes to ambientparticulate matter (PM). For severe haze events with low-light conditions,current models underestimate the levels of sulfate formation that occurexclusively via the oxidation of sulfur dioxide. We show here thatmeasurement techniques commonly used in the field to analyze PM compositioncan fail to efficiently separate sulfur-containing species, resulting inthe possible misidentification of compounds. Hydroxymethanesulfonate (HMS), asulfur(IV) species that can be present in fog and cloud water, has beenlargely neglected in both chemical models and field measurements of PMcomposition. As HMS is formed without oxidation, it represents a pathway for SO2 to contribute to PM under low-lightconditions. In this work, we evaluate two techniques for the specificquantification of HMS and sulfate in PM, ion chromatography (IC) and aerosolmass spectrometry (AMS). In cases in which the dominant sulfur-containingspecies are ammonium sulfate or HMS, differences in AMS fragmentationpatterns can be used to identify HMS. However, the AMS quantification of HMSin complex ambient mixtures containing multiple inorganic and organic sulfurspecies is challenging due to the lack of unique organic fragments andthe variability of fractional contributions of H x SO y + ionsas a function of the matrix. We describe an improved IC method that providesefficient separation of sulfate and HMS and thus allows for the identification andquantification of both. The results of this work provide a technicaldescription of the efficiency and limitations of these techniques as well asa method that enables further studies of the contribution of S(IV)versus S(VI) species to PM under low-light atmospheric conditions.

atmospheric measurement techniques

Measurement techniques for identifying and quantifying hydroxymethanesulfonate (HMS) in an aqueous matrix and particulate matter using aerosol mass spectrometry and ion chromatography