Atmospheric Measurement Techniques Discussions | 2019
Measurement techniques of identifying and quantifying sulfur compounds in fog and cloud water
Abstract
Abstract. Oxidation of sulfur dioxide (SO2) in the gas phase and in cloud and fog water leads to the formation of sulfate that contributes to ambient particulate matter (PM). For severe haze events with dim conditions, current models underestimate the levels of sulfate formation which occurs exclusively via the oxidation of sulfur dioxide. We show here that measurement techniques commonly used in the field to analyse PM composition can fail to efficiently separate sulfur-containing species resulting in possible misidentification of compounds. Hydroxymethanesulfonate (HMS), a sulfur(IV) species that can be present in fog and cloud water, has been largely neglected in both chemical models and field measurements of PM composition. As HMS is formed without oxidation it represents a pathway for SO2 to contribute to PM under dim conditions. In this work, we evaluate two techniques for specific quantification of HMS and sulfate in PM, Ion Chromatography (IC) and Aerosol Mass Spectrometry (AMS). In cases where the dominant sulfur-containing species are ammonium sulfate or HMS, differences in AMS fragmentation patterns can be used to identify HMS. However, the AMS quantification of HMS in complex ambient mixtures containing multiple inorganic and organic sulfur species is challenging due to the lack of unique organic fragments and variability of fractional contributions of HxSOy+ ions as a function of matrix. We describe an improved IC method that provides efficient separation of sulfate and HMS and thus allows identification and quantification of both. The results of this work provide a technical description of the efficiency and limitations of these techniques as well as a method that enables further studies of the contribution and role of S(IV) versus S(VI) species to PM under dim atmospheric conditions.