A theoretical study on the formation and oxidation mechanism of hydroxyalkylsulfonate in the atmospheric aqueous phase

Zhang, Danna; Lv, Guochun; Sun, Xiaomin; Zhang, Chenxi; Li, Zhiqiang

doi:10.1039/c9ra05193g

Cited by 7 publications

(4 citation statements)

References 47 publications

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“…2). The low kinetic data are also closer to the rate constants from the recent quantum chemical calculations by Zhang et al (2019) (k 1 = 0.9 M −1 s −1 , k 2 = 2 × 10 6 M −1 s −1 , at 298 K). Consequently, the low formation rate constants from Boyce and Hoffmann (1984) are adopted for the default model simulation, while the high ones are used in a sensitivity simulation.…”

Section: Kinetics and Thermodynamics Of Hms Chemistrysupporting

confidence: 83%

Global modeling of heterogeneous hydroxymethanesulfonate chemistry

Song

Zhang

et al. 2021

Atmos. Chem. Phys.

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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 modify and add to the implementation of HMS chemistry in the GEOS-Chem chemical transport model and conduct multiple global simulations. The model accounts for cloud entrainment and gas–aqueous mass transfer within the rate expressions for heterogeneous sulfur chemistry. Our simulations can generally reproduce quantitative HMS observations from Beijing 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 in 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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Section: Kinetics and Thermodynamics Of Hms Chemistrysupporting

confidence: 83%

Global modeling of heterogeneous hydroxymethanesulfonate chemistry

Song

Zhang

et al. 2021

Atmos. Chem. Phys.

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“…2). The low kinetic data are also closer to the rate constants from the recent quantum chemical calculations by Zhang et al (2019)…”

Section: Hms Formationsupporting

confidence: 76%

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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“…In general, high concentrations of HMS can be preserved under acidic conditions and are resistant to the oxidation by O 3 and H 2 O 2 . The oxidation of HMS by aqueous hydroxyl radical and O 2 produces peroxymonosulfate radicals (SO 5 – ) and initiates the radical oxidation chain of S(IV). , These conversions are expected to contribute indirectly to sulfate production. The oxidation of HMS by hydroxyl radicals is expected to be a main sink pathway of HMS during the daytime .…”

Section: Resultsmentioning

confidence: 99%

Quantitative Determination of Hydroxymethanesulfonate (HMS) Using Ion Chromatography and UHPLC-LTQ-Orbitrap Mass Spectrometry: A Missing Source of Sulfur during Haze Episodes in Beijing

Wei

Chen

et al. 2020

Environ. Sci. Technol. Lett.

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Hydroxymethanesulfonate (HMS), the product of HSO 3 − and SO 3 2− reacting with dissolved formaldehyde in fog, cloud, and aerosol liquid water, has been suggested to be an important source of particulate sulfur during haze events. However, there have been limited studies of high concentrations of HMS in atmospheric aerosol. We report here two feasible analytical methods for the identification of HMS using ion chromatography and UHPLC-LTQ-Orbitrap mass spectrometry. The concentrations of HMS in fine particles in wintertime Beijing ranged from below the detection limit to 7.3 μg m −3 (with an average at 2.0 ± 2.1 μg m −3 ). Increased concentrations of HMS and sulfate were associated with the occurrence of fog. The results reveal that HMS may be a potential S(IV) reservoir and an effective tracer of aqueous-phase chemistry. The atmospheric aqueous-phase chemistry promoted the rapid conversion of S(IV) under haze−fog conditions. The kinetic modeling results suggest that the aqueous pH should be taken into account when exploring the mechanism of HMS formation in atmospheric sulfur chemistry.

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A theoretical study on the formation and oxidation mechanism of hydroxyalkylsulfonate in the atmospheric aqueous phase

Abstract: We report the formation of an important organosulfur compound HMS and its oxidation using theoretical calculation.

Cited by 7 publications

References 47 publications

Global modeling of heterogeneous hydroxymethanesulfonate chemistry

Global modeling of heterogeneous hydroxymethanesulfonate chemistry

Global modeling of heterogeneous hydroxymethanesulfonate chemistry

Quantitative Determination of Hydroxymethanesulfonate (HMS) Using Ion Chromatography and UHPLC-LTQ-Orbitrap Mass Spectrometry: A Missing Source of Sulfur during Haze Episodes in Beijing

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