Significant Conversion of Organic Sulfur from Hydroxymethanesulfonate to Inorganic Sulfate and Peroxydisulfate Ions upon Heterogeneous OH Oxidation

Lai, Donger; Wong, Yau Shu; Xu, Rongshuang; Xing, Sinan; Ng, Sze In Madeleine; Kong, Lin; Wang, Yuchen; Huang, Dan Dan; Chan, Man Nin

doi:10.1021/acs.estlett.3c00472

Cited by 4 publications

(2 citation statements)

References 51 publications

(72 reference statements)

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“…Note in this paper that we mainly discussed the simulation results of the updated model since it investigated the role of aqueous aerosols and, more importantly, better reproduced the measurements of HMS. A very recent laboratory study showed that HMS in the aerosols could be oxidized heterogeneously by gas-phase OH, producing sulfate and HCHO . Our sensitivity analysis suggested that the heterogeneous oxidation of HMS was very slow and thus not important (Text S9, Figure S6).…”

Section: Methodsmentioning

confidence: 68%

Model Simulations and Predictions of Hydroxymethanesulfonate (HMS) in the Beijing-Tianjin-Hebei Region, China: Roles of Aqueous Aerosols and Atmospheric Acidity

Wang,

Li,

et al. 2023

Environ. Sci. Technol.

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Hydroxymethanesulfonate (HMS) has been found to be an abundant organosulfur aerosol compound in the Beijing-Tianjin-Hebei (BTH) region with a measured maximum daily mean concentration of up to 10 μg per cubic meter in winter. However, the production medium of HMS in aerosols is controversial, and it is unknown whether chemical transport models are able to capture the variations of HMS during individual haze events. In this work, we modify the parametrization of HMS chemistry in the nested-grid GEOS-Chem chemical transport model, whose simulations provide a good account of the field measurements during winter haze episodes. We find the contribution of the aqueous aerosol pathway to total HMS is about 36% in winter in Beijing, due primarily to the enhancement effect of the ionic strength on the rate constants of the reaction between dissolved formaldehyde and sulfite. Our simulations suggest that the HMS-to-inorganic sulfate ratio will increase from the baseline of 7% to 13% in the near future, given the ambitious clean air and climate mitigation policies for the BTH region. The more rapid reductions in emissions of SO 2 and NO x compared to NH 3 alter the atmospheric acidity, which is a critical factor leading to the rising importance of HMS in particulate sulfur species.

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Section: Methodsmentioning

confidence: 68%

Model Simulations and Predictions of Hydroxymethanesulfonate (HMS) in the Beijing-Tianjin-Hebei Region, China: Roles of Aqueous Aerosols and Atmospheric Acidity

Wang,

Li,

et al. 2023

Environ. Sci. Technol.

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“…These organosulfur compounds have been detected in atmospheric aerosols. For instance, MS and ES can be formed via the atmospheric processing (e.g., oxidation) of other organosulfates that are commonly found in the atmosphere. ,, MSA is abundant in marine aerosols, and the ratio of MSA to non-sea-salt sulfate (nss-sulfate) in aerosols is often used to indicate the contribution of biological activities to nss-sulfate in the marine boundary layer. − HMS has been recently recognized as an important organosulfur compound in urban environments, particularly in winter haze. − There are fewer reports on atmospheric occurrence of HES, but it is chosen to examine the effect of an additional −CH 2 group on the reactivity as compared to HMS.…”

Section: Introductionmentioning

confidence: 99%

Deactivating Effect of Hydroxyl Radicals Reactivity by Sulfate and Sulfite Functional Groups in Aqueous Phase─Atmospheric Implications for Small Organosulfur Compounds

Lai,

Schaefer,

Zhang

et al. 2024

ACS EST Air

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Aqueous-phase oxidation of organosulfur compounds initiated by •OH radicals could be an important transformation pathway and can play a significant role in the atmospheric abundance and fate of these compounds. Here, we measured the temperature-dependent kinetics of •OH reactions with five C1 and C2 organosulfur compounds (two alkyl sulfates, methyl sulfate (MS) and ethyl sulfate (ES), and three sulfonates, methanesulfonate (MSA), hydroxymethanesulfonate (HMS), and 2-hydroxyethylsulfonate (HES)) in aqueous phase using laser photolysis-long path absorption (LP-LPA) and competition kinetics methods. The rate constants ranged from 106 to 108 L mol–1 s–1 and exhibited a clear positive temperature (T) dependence over a temperature range of 278 to 318 K. Furthermore, the two sulfur-containing groups, sulfate (−OSO3 –) group for alkyl sulfates and sulfite (−SO3 −) group for sulfonates, exhibit strong deactivating effect on the kinetics. This could be explained by the strong electron-withdrawing nature of the −OSO3 – and −SO3 – groups, which lowers the hydrogen abstraction rates during •OH oxidation. Overall, this study demonstrates that the oxidation of small alkyl sulfates and sulfonates by •OH radical in aqueous phase is significantly modulated by the presence of the sulfur functional groups. The deactivating effect of sulfur functional groups sheds light on predicting the lifetimes of other organosulfur compounds in the atmosphere.

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Positive Feedback between Partitioning of Carbonyl Compounds and Particulate Sulfur Formation during Haze Episodes

Shen,

Huang,

Qian

et al. 2024

Environ. Sci. Technol.

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Carbonyl compounds are important precursors of aqueous aerosols in the atmosphere, while their gas-particle partitioning behaviors and roles in particulate sulfur formation are poorly understood. In this study, we investigate the partitioning of five carbonyl compounds (formaldehyde, acetaldehyde, acetone, glyoxal, and methylglyoxal) during haze episodes in Beijing, China. On haze days, the values of field-derived effective Henry's law coefficients (K H f ) on aerosols for these carbonyl compounds are 10 6 −10 8 M atm −1 , which are significantly higher (10 2 −10 4 times) than those in pure water. Sulfate is observed to have a pronounced "salting-in" effect on these carbonyl compounds, resulting in at least 1-order-of-magnitude increase in their particle-phase concentrations. Parameterization schemes for their partitioning in the ambient aerosols were provided and applied to the multiphase chemical box model (RACM2-CAPRAM). When incorporated into the field-derived parametrization, the model significantly increased hydroxymethanesulfonate (HMS) production by 50-fold compared to using the parameters obtained in pure water, increasing from 2.6 × 10 −2 to 1.23 μg m −3 h −1 . The formed HMS can facilitate sulfate formation in turn through further oxidation by OH radicals and enhance aerosol hygroscopicity. These findings indicate a positive feedback loop between the partitioning of carbonyl compounds and particulate sulfur formation during haze episodes, providing new insights for controlling particulate pollution and reducing SO 2 levels in urban areas.

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Significant Conversion of Organic Sulfur from Hydroxymethanesulfonate to Inorganic Sulfate and Peroxydisulfate Ions upon Heterogeneous OH Oxidation

Cited by 4 publications

References 51 publications

Model Simulations and Predictions of Hydroxymethanesulfonate (HMS) in the Beijing-Tianjin-Hebei Region, China: Roles of Aqueous Aerosols and Atmospheric Acidity

Model Simulations and Predictions of Hydroxymethanesulfonate (HMS) in the Beijing-Tianjin-Hebei Region, China: Roles of Aqueous Aerosols and Atmospheric Acidity

Deactivating Effect of Hydroxyl Radicals Reactivity by Sulfate and Sulfite Functional Groups in Aqueous Phase─Atmospheric Implications for Small Organosulfur Compounds

Positive Feedback between Partitioning of Carbonyl Compounds and Particulate Sulfur Formation during Haze Episodes

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