Oxidation of hydroxymethanesulfonic acid by Fenton's reagent

Martin, Leigh R.; Easton, Myriam P.; Foster, John W.; Hill, Michael W.

doi:10.1016/0004-6981(89)90005-x

Cited by 37 publications

(12 citation statements)

References 22 publications

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“…Similarly, AMS measurements may have identified HMS as sulfate as ex-plained above. This is also consistent with the explanation provided by Moch et al (2018) and Song et al (2019).…”

Section: Discussionsupporting

confidence: 93%

“…Wang et al (2014) suggested that a new heterogeneous pathway of SO 2− 4 formation could explain the missing SO 2− 4 . Moch et al (2018) suggested the contribution of HMS to explain the high observed SO 2− 4 concentrations during these low-light haze events with slow photochemistry. In order to distinguish the two hypotheses, i.e., condensed-phase reactions producing sulfate or contributions from HMS, measurement techniques that allow for quantitative speciated measurements of HMS and sulfate are needed.…”

Section: Sulfur Species In Cloud and Fog Watermentioning

confidence: 96%

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

et al. 2019

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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.

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“…Similarly, AMS measurements may have identified HMS as sulfate as ex-plained above. This is also consistent with the explanation provided by Moch et al (2018) and Song et al (2019).…”

Section: Discussionsupporting

confidence: 93%

Section: Sulfur Species In Cloud and Fog Watermentioning

confidence: 96%

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

et al. 2019

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“…The highest stability is thus observed at acidic pH (Sorensen and Andersen, 1970;Munger et al, 1986). HMSA is comparably stable and not readily oxidised (Hoigné et al, 1985;Martin et al, 1989;Ojo et al, 2004). It therefore accumulates in the atmosphere and can be found in high concentrations.…”

Section: Introductionmentioning

confidence: 91%

Hydroxymethanesulfonic acid in size-segregated aerosol particles at nine sites in Germany

et al. 2014

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Abstract. In the course of two field campaigns, sizesegregated particle samples were collected at nine sites in Germany, including traffic, urban, rural, marine and mountain sites. During the chemical characterisation of the samples some of them were found to contain an unknown substance that was later identified as hydroxymethanesulfonic acid (HMSA). HMSA is known to be formed during the reaction of S(IV) (HSO − 3 or SO 2− 3 ) with formaldehyde in the aqueous phase. Due to its stability, HMSA can act as a reservoir species for S(IV) in the atmosphere and is therefore of interest for the understanding of atmospheric sulfur chemistry. However, no HMSA data are available for atmospheric particles from central Europe, and even on a worldwide scale data are scarce. Thus, the present study now provides a representative data set with detailed information on HMSA concentrations in size-segregated central European aerosol particles. HMSA mass concentrations in this data set were highly variable: HMSA was found in 224 out of 738 samples (30 %), sometimes in high mass concentrations exceeding those of oxalic acid. On average over all 154 impactor runs, 31.5 ng m −3 HMSA was found in PM 10 , contributing 0.21 % to the total mass. The results show that the particle diameter, the sampling location, the sampling season and the air mass origin impact the HMSA mass concentration. Highest concentrations were found in the particle fraction 0.42-1.2 µm, at urban sites, in winter and with eastern (continental) air masses, respectively. The results suggest that HMSA is formed during aging of pollution plumes. A positive correlation of HMSA with sulfate, oxalate and PM is found (R 2 > 0.4). The results furthermore suggest that the fraction of HMSA in PM slightly decreases with increasing pH.

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“…HMS is resistant to oxidation by H2O2 and O3 but can be oxidized by OH in the aqueous phase (Martin et al, 1989;Olson and Fessenden, 1992). (R9) produces HCHO and peroxysulfate radical (SO 5 − ) with a rate constant of 2.7 × 10 8 M −1 s −1 (Olson and https://doi.org/10.5194/acp-2020-643 Preprint.…”

Section: Hms Oxidationmentioning

confidence: 99%

Global modeling of heterogeneous hydroxymethanesulfonate chemistry

Song¹,

Ma²,

Zhang³

et al. 2020

Preprint

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Abstract. Hydroxymethanesulfonate (HMS) has recently been identified as an abundant organosulfur compound in aerosols during winter haze episodes in northern China. It has also been detected in other regions, although the concentrations are low. Because of the sparse field measurements, the global significance of HMS and its spatial and seasonal patterns remain unclear. Here, we implement HMS chemistry into the GEOS-Chem chemical transport model and conduct multiple global simulations. The developed model accounts for cloud entrainment and gas–aqueous mass transfer within the rate expressions for heterogeneous sulfur chemistry. Our simulations can generally reproduce the available HMS observations, and show that East Asia has the highest HMS concentration, followed by Europe and North America. The simulated HMS shows a seasonal pattern with higher values in the colder period. Photochemical oxidizing capacity affects the competition of formaldehyde with oxidants (such as ozone and hydrogen peroxide) for sulfur dioxide and is a key factor influencing the seasonality of HMS. The highest average HMS concentration (1–3 μg m−3) and HMS/sulfate molar ratio (0.1–0.2) are found in northern China winter. The simulations suggest that aqueous clouds act as the major medium for HMS chemistry while aerosol liquid water may play a role if its rate constant for HMS formation is greatly enhanced compared to cloud water.

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Oxidation of hydroxymethanesulfonic acid by Fenton's reagent

Cited by 37 publications

References 22 publications

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

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

Hydroxymethanesulfonic acid in size-segregated aerosol particles at nine sites in Germany

Global modeling of heterogeneous hydroxymethanesulfonate chemistry

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