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 low-light conditions, current models underestimate the levels of sulfate formation that occur exclusively via the oxidation of sulfur dioxide. We show here that measurement techniques commonly used in the field to analyze PM composition can fail to efficiently separate sulfur-containing species, resulting in the 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 low-light conditions. In this work, we evaluate two techniques for the specific quantification of HMS and sulfate in PM, ion chromatography (IC) and aerosol mass spectrometry (AMS). In cases in which 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 the variability of fractional contributions of HxSOy+ ions as a function of the matrix. We describe an improved IC method that provides efficient separation of sulfate and HMS and thus allows for the 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 of S(IV) versus S(VI) species to PM under low-light atmospheric conditions.
Highlights
1.1 Sulfur species in cloud and fog waterHydroxymethanesulfonate (HMS; HOCH2SO−3 ) is the product of the aqueous-phase reaction between dissolved sulfur dioxide (SO2) and formaldehyde (HCHO) and is considered an important compound in cloud and fog water (Munger et al, 1986; Dixon and Aasen, 1999; Whiteaker and Prather, 2003)
Even though mass spectrometry has been widely used for the analysis of sulfur species (Neubauer et al, 1996, 1997; Whiteaker and Prather, 2003), there is indication that chromatography methods could provide an efficient separation of these species (Zuo and Chen, 2003)
The area signal of the sulfate increased but the intensity of the peak decreased, and the reverse phenomenon was observed for HMS. Considering both the signal contribution and the intensity of the compounds, the results indicate that amounts of both compounds are probably incorporated in both peaks, and since we have an increase in the area of sulfate it is more likely that some of HMS is attributed to sulfate in this analysis
Summary
Hydroxymethanesulfonate (HMS; HOCH2SO−3 ) is the product of the aqueous-phase reaction between dissolved sulfur dioxide (SO2) and formaldehyde (HCHO) and is considered an important compound in cloud and fog water (Munger et al, 1986; Dixon and Aasen, 1999; Whiteaker and Prather, 2003). Studies reporting the presence of HMS in ambient PM using single-particle mass spectrometry have been conducted (Neubauer et al, 1996, 1997; Whiteaker and Prather, 2003; Lee et al, 2003; Dall’Osto et al, 2009). All mass spectrometry techniques share the challenge that the majority of the fragments, such as SO−3 and HSO−3 , are common to different sulfur-containing species, including organic compounds potentially in the measured PM Even though mass spectrometry has been widely used for the analysis of sulfur species (Neubauer et al, 1996, 1997; Whiteaker and Prather, 2003), there is indication that chromatography methods could provide an efficient separation of these species (Zuo and Chen, 2003)
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