Articles | Volume 25, issue 15
https://doi.org/10.5194/acp-25-8575-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-25-8575-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
07 Aug 2025
Research article |
| 07 Aug 2025
| 07 Aug 2025
Atmospheric fate of organosulfates through gas-phase and aqueous-phase reactions with hydroxyl radicals: implications for inorganic sulfate formation
Narcisse Tsona Tchinda
CORRESPONDING AUTHOR
Qingdao Key Laboratory for Prevention and Control of Atmospheric Pollution in Coastal Cities, Environment Research Institute, Shandong University, Qingdao, 266237, China
Xiaofan Lv
Qingdao Key Laboratory for Prevention and Control of Atmospheric Pollution in Coastal Cities, Environment Research Institute, Shandong University, Qingdao, 266237, China
Stanley Numbonui Tasheh
Department of Chemistry, Faculty of Science, The University of Bamenda, P.O. Box 39, Bambili–Bamenda, Cameroon
Julius Numbonui Ghogomu
Department of Chemistry, Faculty of Science, The University of Bamenda, P.O. Box 39, Bambili–Bamenda, Cameroon
Research Unit of Noxious Chemistry and Environmental Engineering, Department of Chemistry, Faculty of Science, University of Dschang, P.O. Box 67, Dschang, Cameroon
Qingdao Key Laboratory for Prevention and Control of Atmospheric Pollution in Coastal Cities, Environment Research Institute, Shandong University, Qingdao, 266237, China
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Atmos. Chem. Phys., 23, 10809–10822, https://doi.org/10.5194/acp-23-10809-2023, https://doi.org/10.5194/acp-23-10809-2023, 2023
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In this study, we have investigated the distinct impacts of humidity on the ozonolysis of two structurally different monoterpenes (limonene and Δ3-carene). We found that the molecular structure of precursors can largely influence the SOA formation under high RH by impacting the multi-generation reactions. Our results could advance knowledge on the roles of water content in aerosol formation and inform ongoing research on particle environmental effects and applications in models.
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Atmos. Chem. Phys., 23, 2235–2249, https://doi.org/10.5194/acp-23-2235-2023, https://doi.org/10.5194/acp-23-2235-2023, 2023
Short summary
Short summary
The promotion of soluble saccharides on sea spray aerosol (SSA) generation and the changes in particle morphology were observed. On the contrary, the coexistence of surface insoluble fatty acid film and soluble saccharides significantly inhibited the production of SSA. This is the first demonstration that hydrogen bonding mediated by surface-insoluble fatty acids contributes to saccharide transfer in seawater, providing a new mechanism for saccharide enrichment in SSA.
Zhaomin Yang, Kun Li, Narcisse T. Tsona, Xin Luo, and Lin Du
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Short summary
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SO2 significantly promotes particle formation during cyclooctene ozonolysis. Carboxylic acids and their dimers were major products in particles formed in the absence of SO2. SO2 can induce production of organosulfates with stronger particle formation ability than their precursors, leading to the enhancement in particle formation. Formation mechanisms and structures of organosulfates were proposed, which is helpful for better understanding how SO2 perturbs the formation and fate of particles.
Narcisse Tsona Tchinda, Lin Du, Ling Liu, and Xiuhui Zhang
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Short summary
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This study explores the effect of pyruvic acid (PA) both in the SO3 hydrolysis and in sulfuric-acid-based aerosol formation. Results show that in dry and polluted areas, PA-catalyzed SO3 hydrolysis is about 2 orders of magnitude more efficient at forming sulfuric acid than the water-catalyzed reaction. Moreover, PA can effectively enhance the ternary SA-PA-NH3 particle formation rate by up to 4.7×102 relative to the binary SA-NH3 particle formation rate at cold temperatures.
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Short summary
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The promotion effects of SO2 and NH3 on particle and organosulfur compound formation from 1,2,4-trimethylbenzene (TMB) photooxidation were observed for the first time. The enhanced organosulfur compounds included hitherto unidentified aromatic sulfonates and organosulfates (OSs). OSs were produced via acid-driven heterogeneous chemistry of hydroperoxides. The production of organosulfur compounds might provide a new pathway for the fate of TMB in regions with considerable SO2 emissions.
Cited articles
An, G.-C.: Enhancement of atmospheric nucleation precursors on formic sulfuric anhydride induced nucleation: Theoretical mechanism, Chemosphere, 368, 143684, https://doi.org/10.1016/j.chemosphere.2024.143684, 2024.
Bennett, J. E. and Summers, R.: Product Studies of the Mutual Termination Reactions of sec-Alkylperoxy Radicals: Evidence for Non-Cyclic Termination, Can. J. Chem., 52, 1377–1379, https://doi.org/10.1139/v74-209, 1974.
Bork, N., Kurtén, T., and Vehkamäki, H.: Exploring the atmospheric chemistry of O2SO
Bork, N., Kurtén, T., Enghoff, M. B., Pedersen, J. O. P., Mikkelsen, K. V., and Svensmark, H.: Structures and reaction rates of the gaseous oxidation of SO2 by an O
Buehler, R. E., Staehelin, J., and Hoigne, J.: Ozone decomposition in water studied by pulse radiolysis. 1. Perhydroxyl (HO2)/hyperoxide (O2-) and HO3/O
Buhler, R., Staehelin, J., and Hoigne, J.: Ozone Decomposition in Water Studied by Pulse Radiolysis 1. HO2
Buxton, G. V., Greenstock, C. L., Helman, W. P., and Ross, A. B.: Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (OH
Cai, D., Wang, X., Chen, J., and Li, X.: Molecular Characterization of Organosulfates in Highly Polluted Atmosphere Using Ultra-High-Resolution Mass Spectrometry, J. Geophys. Res.-Atmos., 125, e2019JD032253, https://doi.org/10.1029/2019JD032253, 2020.
Chan, M. N., Surratt, J. D., Chan, A. W. H., Schilling, K., Offenberg, J. H., Lewandowski, M., Edney, E. O., Kleindienst, T. E., Jaoui, M., Edgerton, E. S., Tanner, R. L., Shaw, S. L., Zheng, M., Knipping, E. M., and Seinfeld, J. H.: Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene, Atmos. Chem. Phys., 11, 1735–1751, https://doi.org/10.5194/acp-11-1735-2011, 2011.
Cheng, J., Yue, L., Hua, J., Dong, H., Li, Y.-Y., Zhou, J., and Lin, R.: Hydrothermal heating with sulphuric acid contributes to improved fermentative hydrogen and methane co-generation from Dianchi Lake algal bloom, Energ. Convers. Manage., 192, 282–291, https://doi.org/10.1016/j.enconman.2019.04.003, 2019.
Cheng, Y., Wang, R., Chen, Y., Tian, S., Gao, N., Zhang, Z., and Zhang, T.: Hydrolysis of SO3 in Small Clusters of Sulfuric Acid: Mechanistic and Kinetic Study, ACS Earth and Space Chem., 6, 3078–3089, https://doi.org/10.1021/acsearthspacechem.2c00290, 2022.
Collins, F. C. and Kimball, G. E.: Diffusion-controlled reaction rates, J. Coll. Sci., 4, 425–437, https://doi.org/10.1016/0095-8522(49)90023-9, 1949.
Ding, C., Cheng, Y., Wang, H., Yang, J., Li, Z., Lily, M., Wang, R., and Zhang, T.: Determination of the influence of water on the SO3+ CH3OH reaction in the gas phase and at the air–water interface, Phys. Chem. Chem. Phys., 25, 15693–15701, https://doi.org/10.1039/D3CP01245J, 2023.
Eckart, C.: The Penetration of a Potential Barrier by Electrons, Phys. Rev. 35, 1303–1309, https://doi.org/10.1103/PhysRev.35.1303, 1930.
Ehn, M., Junninen, H., Petäjä, T., Kurtén, T., Kerminen, V.-M., Schobesberger, S., Manninen, H. E., Ortega, I. K., Vehkamäki, H., Kulmala, M., and Worsnop, D. R.: Composition and temporal behavior of ambient ions in the boreal forest, Atmos. Chem. Phys., 10, 8513–8530, https://doi.org/10.5194/acp-10-8513-2010, 2010.
Einstein, A.: Über die von der molekularkinetischen Theorie der Wärme geforderte Bewegung von in ruhenden Flüssigkeiten suspendierten Teilchen, Ann. Phys., 322, 549–560, https://doi.org/10.1002/andp.19053220806, 1905.
Enghoff, M. B. and Svensmark, H.: The role of atmospheric ions in aerosol nucleation – a review, Atmos. Chem. Phys., 8, 4911–4923, https://doi.org/10.5194/acp-8-4911-2008, 2008.
England, C. and Corcoran, W. H.: Kinetics and Mechanisms of the Gas-Phase Reaction of Water Vapor and Nitrogen Dioxide, Ind. Eng. Chem. Fund., 13, 373–384, https://doi.org/10.1021/i160052a014, 1974.
Estillore, A. D., Hettiyadura, A. P., Qin, Z., Leckrone, E., Wombacher, B., Humphry, T., Stone, E. A., and Grassian, V. H.: Water Uptake and Hygroscopic Growth of Organosulfate Aerosol, Environ. Sci. Technol, 50, 4259–4268, https://doi.org/10.1021/acs.est.5b05014, 2016.
Fehsenfeld, F. and Ferguson, E.: Laboratory studies of negative ion reactions with atmospheric trace constituents, J. Chem. Phys., 61, 3181–3193, https://doi.org/10.1063/1.1682474, 1974.
Ford, P. C. and Miranda, K. M.: The solution chemistry of nitric oxide and other reactive nitrogen species, Nitric Oxide, 103, 31-46, https://doi.org/10.1016/j.niox.2020.07.004, 2020.
George, I. J. and Abbatt, J. P. D.: Heterogeneous oxidation of atmospheric aerosol particles by gas-phase radicals, Nat. Chem., 2, 713–722, https://doi.org/10.1038/nchem.806, 2010.
Ghigo, G., Maranzana, A., and Tonachini, G.: Combustion and atmospheric oxidation of hydrocarbons: Theoretical study of the methyl peroxyl self-reaction, J. Chem. Phys., 118, 10575–10583, https://doi.org/10.1063/1.1574316, 2003.
Gweme, D. T. and Styler, S. A.: OH Radical Oxidation of Organosulfates in the Atmospheric Aqueous Phase, J. Phys. Chem. A, 128, 9462–9475, https://doi.org/10.1021/acs.jpca.4c02877, 2024.
Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, Th. F., Monod, A., Prévôt, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5236, https://doi.org/10.5194/acp-9-5155-2009, 2009.
Heindel, J. P., Yu, Q., Bowman, J. M., and Xantheas, S. S.: Benchmark Electronic Structure Calculations for H3O+(H2O)n, n = 0–5, Clusters and Tests of an Existing 1,2,3-Body Potential Energy Surface with a New 4-Body Correction, J. Chem. Theory Comput., 14, 4553–4566, https://doi.org/10.1021/acs.jctc.8b00598, 2018.
Hettiyadura, A. P. S., Stone, E. A., Kundu, S., Baker, Z., Geddes, E., Richards, K., and Humphry, T.: Determination of atmospheric organosulfates using HILIC chromatography with MS detection, Atmos. Meas. Tech., 8, 2347–2358, https://doi.org/10.5194/amt-8-2347-2015, 2015.
Hettiyadura, A. P. S., Jayarathne, T., Baumann, K., Goldstein, A. H., de Gouw, J. A., Koss, A., Keutsch, F. N., Skog, K., and Stone, E. A.: Qualitative and quantitative analysis of atmospheric organosulfates in Centreville, Alabama, Atmos. Chem. Phys., 17, 1343–1359, https://doi.org/10.5194/acp-17-1343-2017, 2017.
Hofmann, M. and Schleyer, P. v. R.: Acid Rain: Ab Initio Investigation of the H2OSO3 Complex and Its Conversion to H2SO4, J. Am. Chem. Soc., 116, 4947–4952, https://doi.org/10.1021/ja00090a045, 1994.
Hofmann-Sievert, R. and Castleman, A. W., Jr.: Reaction of sulfur trioxide with water clusters and the formation of sulfuric acid, J. Phys. Chem., 88, 3329–3333, https://doi.org/10.1021/j150659a038, 1984.
Huang, D. D., Li, Y. J., Lee, B. P., and Chan, C. K.: Analysis of Organic Sulfur Compounds in Atmospheric Aerosols at the HKUST Supersite in Hong Kong Using HR-ToF-AMS, Environ. Sci. Technol., 49, 3672–3679, https://doi.org/10.1021/es5056269, 2015.
Huang, R.-J., Cao, J., Chen, Y., Yang, L., Shen, J., You, Q., Wang, K., Lin, C., Xu, W., Gao, B., Li, Y., Chen, Q., Hoffmann, T., O'Dowd, C. D., Bilde, M., and Glasius, M.: Organosulfates in atmospheric aerosol: synthesis and quantitative analysis of PM2.5 from Xi'an, northwestern China, Atmos. Meas. Tech., 11, 3447–3456, https://doi.org/10.5194/amt-11-3447-2018, 2018.
Hughes, D. D. and Stone, E. A.: Organosulfates in the Midwestern United States: abundance, composition and stability, J. Environ. Chem., 16, 312–322, https://doi.org/10.1071/EN18260, 2019.
Iinuma, Y., Müller, C., Böge, O., Gnauk, T., and Herrmann, H.: The formation of organic sulfate esters in the limonene ozonolysis secondary organic aerosol (SOA) under acidic conditions, Atmos. Environ., 41, 5571–5583, https://doi.org/10.1016/j.atmosenv.2007.03.007, 2007.
Jensen, S. K., Keiding, S. R., and Thøgersen, J.: The hunt for HCO(aq), Phys. Chem. Chem. Phys., 12, 8926–8933, https://doi.org/10.1039/B924902H, 2010.
Kourtchev, I., Godoi, R. H. M., Connors, S., Levine, J. G., Archibald, A. T., Godoi, A. F. L., Paralovo, S. L., Barbosa, C. G. G., Souza, R. A. F., Manzi, A. O., Seco, R., Sjostedt, S., Park, J.-H., Guenther, A., Kim, S., Smith, J., Martin, S. T., and Kalberer, M.: Molecular composition of organic aerosols in central Amazonia: an ultra-high-resolution mass spectrometry study, Atmos. Chem. Phys., 16, 11899–11913, https://doi.org/10.5194/acp-16-11899-2016, 2016.
Kwong, K. C., Chim, M. M., Davies, J. F., Wilson, K. R., and Chan, M. N.: Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate, Atmos. Chem. Phys., 18, 2809–2820, https://doi.org/10.5194/acp-18-2809-2018, 2018.
Larson, L. J., Kuno, M., and Tao, F.-M.: Hydrolysis of sulfur trioxide to form sulfuric acid in small water clusters, J. Chem. Phys., 112, 8830–8838, 2000.
Le Breton, M., Wang, Y., Hallquist, Å. M., Pathak, R. K., Zheng, J., Yang, Y., Shang, D., Glasius, M., Bannan, T. J., Liu, Q., Chan, C. K., Percival, C. J., Zhu, W., Lou, S., Topping, D., Wang, Y., Yu, J., Lu, K., Guo, S., Hu, M., and Hallquist, M.: Online gas- and particle-phase measurements of organosulfates, organosulfonates and nitrooxy organosulfates in Beijing utilizing a FIGAERO ToF-CIMS, Atmos. Chem. Phys., 18, 10355–10371, https://doi.org/10.5194/acp-18-10355-2018, 2018.
Lee, Y. N. and Schwartz, S. E.: Reaction kinetics of nitrogen dioxide with liquid water at low partial pressure, J. Phys. Chem., 85, 840–848, https://doi.org/10.1021/j150607a022, 1981.
Liang, Y.-N., Li, J., Wang, Q.-D., Wang, F., and Li, X.-Y.: Computational Study of the Reaction Mechanism of the Methylperoxy Self-Reaction, J. Phys. Chem. A, 115, 13534–13541, https://doi.org/10.1021/jp2048508, 2011.
Liao, J., Froyd, K. D., Murphy, D. M., Keutsch, F. N., Yu, G., Wennberg, P. O., St. Clair, J. M., Crounse, J. D., Wisthaler, A., Mikoviny, T., Jimenez, J. L., Campuzano-Jost, P., Day, D. A., Hu, W., Ryerson, T. B., Pollack, I. B., Peischl, J., Anderson, B. E., Ziemba, L. D., Blake, D. R., Meinardi, S., and Diskin, G.: Airborne measurements of organosulfates over the continental U.S, J. Geophys. Res.-Atmos., 120, 2990–3005, https://doi.org/10.1002/2014JD022378, 2015.
Lin, Y.-H., Budisulistiorini, S. H., Chu, K., Siejack, R. A., Zhang, H., Riva, M., Zhang, Z., Gold, A., Kautzman, K. E., and Surratt, J. D.: Light-Absorbing Oligomer Formation in Secondary Organic Aerosol from Reactive Uptake of Isoprene Epoxydiols, Environ. Sci. Technol., 48, 12012–12021, https://doi.org/10.1021/es503142b, 2014.
Loerting, T. and Liedl, K. R.: Toward elimination of discrepancies between theory and experiment: The rate constant of the atmospheric conversion of SO3 to H2SO4, P. Natl Acad. Sci. USA, 97, 8874–8878, https://doi.org/10.1073/pnas.97.16.8874, 2000.
Lovato, M. E., Martín, C. A., and Cassano, A. E.: A reaction kinetic model for ozone decomposition in aqueous media valid for neutral and acidic pH, Chem. Eng. J., 146, 486–497, https://doi.org/10.1016/j.cej.2008.11.001, 2009.
Lu, T. and Chen, F.: Multiwfn: A multifunctional wavefunction analyzer, J. Comput. Chem., 33, 580–592, https://doi.org/10.1002/jcc.22885, 2012.
Markovitch, O. and Agmon, N.: Structure and Energetics of the Hydronium Hydration Shells, J. Phys. Chem. A, 111, 2253–2256, https://doi.org/10.1021/jp068960g, 2007.
Morokuma, K. and Muguruma, C.: Ab initio Molecular Orbital Study of the Mechanism of the Gas Phase Reaction SO3+ H2O: Importance of the Second Water Molecule, J. Am. Chem. Soc., 116, 10316–10317, https://doi.org/10.1021/ja00101a068, 1994.
Nangia, P. S. and Benson, S. W.: The kinetics of the interaction of peroxy radicals. II. Primary and secondary alkyl peroxy, Int. J. Chem. Kinet., 12, 43–53, https://doi.org/10.1002/kin.550120105, 1980.
Nguyen, Q. T., Christensen, M. K., Cozzi, F., Zare, A., Hansen, A. M. K., Kristensen, K., Tulinius, T. E., Madsen, H. H., Christensen, J. H., Brandt, J., Massling, A., Nøjgaard, J. K., and Glasius, M.: Understanding the anthropogenic influence on formation of biogenic secondary organic aerosols in Denmark via analysis of organosulfates and related oxidation products, Atmos. Chem. Phys., 14, 8961–8981, https://doi.org/10.5194/acp-14-8961-2014, 2014.
Nozière, B., Ekstrom, S., Alsberg, T., and Holmstrom, S.: Radical-initiated formation of organosulfates and surfactants in atmospheric aerosols, Geophys. Res. Lett., 37, L05806, https://doi.org/10.1029/2009gl041683, 2010.
Nozière, B., Kalberer, M., Claeys, M., Allan, J., D'Anna, B., Decesari, S., Finessi, E., Glasius, M., Grgić, I., Hamilton, J. F., Hoffmann, T., Iinuma, Y., Jaoui, M., Kahnt, A., Kampf, C. J., Kourtchev, I., Maenhaut, W., Marsden, N., Saarikoski, S., Schnelle-Kreis, J., Surratt, J. D., Szidat, S., Szmigielski, R., and Wisthaler, A.: The Molecular Identification of Organic Compounds in the Atmosphere: State of the Art and Challenges, Chem. Rev., 115, 3919–3983, https://doi.org/10.1021/cr5003485, 2015.
Ostovari, H., Zahedi, E., Sarvi, I., and Shiroudi, A.: Kinetic and mechanistic insight into the formation of amphetamine using the Leuckart–Wallach reaction and interaction of the drug with GpC⚫ CpG base-pair step of DNA: a DFT study, Monatsh. Chem., 149, 1045–1057, https://doi.org/10.1007/s00706-018-2145-7, 2018.
Passananti, M., Kong, L., Shang, J., Dupart, Y., Perrier, S., Chen, J., Donaldson, D. J., and George, C.: Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Fatty Acids and Long-Chain Alkenes, Angew. Chem. Int. Edit., 55, 10336–10339, https://doi.org/10.1002/anie.201605266, 2016.
Peng, C., Razafindrambinina, P. N., Malek, K. A., Chen, L., Wang, W., Huang, R.-J., Zhang, Y., Ding, X., Ge, M., Wang, X., Asa-Awuku, A. A., and Tang, M.: Interactions of organosulfates with water vapor under sub- and supersaturated conditions, Atmos. Chem. Phys., 21, 7135–7148, https://doi.org/10.5194/acp-21-7135-2021, 2021.
Riplinger, C. and Neese, F.: An efficient and near linear scaling pair natural orbital based local coupled cluster method, J. Chem. Phys., 138, 034106, https://doi.org/10.1063/1.4773581, 2013.
Rudziński, K. J., Gmachowski, L., and Kuznietsova, I.: Reactions of isoprene and sulphoxy radical-anions – a possible source of atmospheric organosulphites and organosulphates, Atmos. Chem. Phys., 9, 2129–2140, https://doi.org/10.5194/acp-9-2129-2009, 2009.
Russell, G. A.: Deuterium-isotope Effects in the Autoxidation of Aralkyl Hydrocarbons. Mechanism of the Interaction of PEroxy Radicals1, J. Am. Chem. Soc., 79, 3871–3877, https://doi.org/10.1021/ja01571a068, 1957.
Salo, V.-T., Valiev, R., Lehtola, S., and Kurtén, T.: Gas-Phase Peroxyl Radical Recombination Reactions: A Computational Study of Formation and Decomposition of Tetroxides, J. Phys. Chem. A, 126, 4046–4056, https://doi.org/10.1021/acs.jpca.2c01321, 2022.
Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, John Wiley & Sons, New York, 88 pp., https://doi.org/10.1063/1.882420, 1998.
Shang, J., Passananti, M., Dupart, Y., Ciuraru, R., Tinel, L., Rossignol, S., Perrier, S., Zhu, T., and George, C.: SO2 Uptake on Oleic Acid: A New Formation Pathway of Organosulfur Compounds in the Atmosphere, Environ. Sci. Tech. Let., 3, 67–72, https://doi.org/10.1021/acs.estlett.6b00006, 2016.
Smoluchowski, M. V.: Mathematical Theory of the Kinetics of the Coagulation of Colloidal Solutions, Z. Phys. Chem., 92, 129–168, 1917.
Staehelin, J. and Hoigne, J.: Decomposition of ozone in water: rate of initiation by hydroxide ions and hydrogen peroxide, Environ. Sci. Technol., 16, 676–681, https://doi.org/10.1021/es00104a009, 1982.
Staehelin, J., Buehler, R. E., and Hoigne, J.: Ozone decomposition in water studied by pulse radiolysis. 2. Hydroxyl and hydrogen tetroxide (HO4) as chain intermediates, J. Phys. Chem., 88, 5999–6004, https://doi.org/10.1021/j150668a051, 1984.
Stone, E. A., Yang, L., Yu, L. E., and Rupakheti, M.: Characterization of organosulfates in atmospheric aerosols at Four Asian locations, Atmos. Environ., 47, 323–329, https://doi.org/10.1016/j.atmosenv.2011.10.058, 2012.
Surratt, J. D., Gomez-Gonzalez, Y., Chan, A. W. H., Vermeylen, R., Shahgholi, M., Kleindienst, T. E., Edney, E. O., Offenberg, J. H., Lewandowski, M., Jaoui, M., Maenhaut, W., Claeys, M., Flagan, R. C., and Seinfeld, J. H.: Organosulfate formation in biogenic secondary organic aerosol, J. Phys. Chem. A, 112, 8345–8378, https://doi.org/10.1021/jp802310p, 2008.
Svensmark, H., Pedersen, J. O. P., Marsh, N. D., Enghoff, M. B., and Uggerhoj, U. I.: Experimental evidence for the role of ions in particle nucleation under atmospheric conditions, P. R. Soc. A, 463, 385–396, https://doi.org/10.1098/rspa.2006.1773, 2007.
Tan, S. P. and Piri, M.: Modeling the Solubility of Nitrogen Dioxide in Water Using Perturbed-Chain Statistical Associating Fluid Theory, Ind. Eng. Chem. Res., 52, 16032–16043, https://doi.org/10.1021/ie402417p, 2013.
Truhlar, D. G.: Nearly encounter-controlled reactions: The equivalence of the steady-state and diffusional viewpoints, J. Chem. Educ., 62, 104, https://doi.org/10.1021/ed062p104, 1985.
Truhlar, D. G., Garrett, B. C., and Klippenstein, S. J.: Current Status of Transition-State Theory, J. Phys. Chem., 100, 12771–12800, https://doi.org/10.1021/jp953748q, 1996.
Tsona, N. T. and Du, L.: Hydration of glycolic acid sulfate and lactic acid sulfate: Atmospheric implications, Atmos. Environ., 216, 116921, https://doi.org/10.1016/j.atmosenv.2019.116921, 2019a.
Tsona, N. T. and Du, L.: A potential source of atmospheric sulfate from O2−-induced SO2 oxidation by ozone, Atmos. Chem. Phys., 19, 649–661, https://doi.org/10.5194/acp-19-649-2019, 2019b.
Wang, R., Kang, J., Zhang, S., Shao, X., Jin, L., Zhang, T., and Wang, Z.: Catalytic effect of (H2O)n (n=1–2) on the hydrogen abstraction reaction of H2O2+HS → H2S+HO2 under tropospheric conditions, Comput. Theor. Chem., 1110, 25-34, https://doi.org/10.1016/j.comptc.2017.03.045, 2017.
Wang, R., Cheng, Y., Chen, S., Li, R., Hu, Y., Guo, X., Zhang, T., Song, F., and Li, H.: Reaction of SO3 with H2SO4 and its implications for aerosol particle formation in the gas phase and at the air–water interface, Atmos. Chem. Phys., 24, 4029–4046, https://doi.org/10.5194/acp-24-4029-2024, 2024.
Wang, R., Yao, Q., Wen, M., Tian, S., Wang, Y., Wang, Z., Yu, X., Shao, X., and Chen, L.: Catalytic effect of (H2O)n (n= 1–3) clusters on the HO2+ SO2 → HOSO +3O2 reaction under tropospheric conditions, RSC Adv., 9, 16195–16207, https://doi.org/10.1039/C9RA00169G, 2019.
Wang, Y., Zhao, Y., Wang, Y., Yu, J.-Z., Shao, J., Liu, P., Zhu, W., Cheng, Z., Li, Z., Yan, N., and Xiao, H.: Organosulfates in atmospheric aerosols in Shanghai, China: seasonal and interannual variability, origin, and formation mechanisms, Atmos. Chem. Phys., 21, 2959–2980, https://doi.org/10.5194/acp-21-2959-2021, 2021.
Worton, D. R., Goldstein, A. H., Farmer, D. K., Docherty, K. S., Jimenez, J. L., Gilman, J. B., Kuster, W. C., de Gouw, J., Williams, B. J., Kreisberg, N. M., Hering, S. V., Bench, G., McKay, M., Kristensen, K., Glasius, M., Surratt, J. D., and Seinfeld, J. H.: Origins and composition of fine atmospheric carbonaceous aerosol in the Sierra Nevada Mountains, California, Atmos. Chem. Phys., 11, 10219–10241, https://doi.org/10.5194/acp-11-10219-2011, 2011.
Xu, L. and Coote, M. L.: Methods To Improve the Calculations of Solvation Model Density Solvation Free Energies and Associated Aqueous pKa Values: Comparison between Choosing an Optimal Theoretical Level, Solute Cavity Scaling, and Using Explicit Solvent Molecules, J. Phys. Chem. A, 123, 7430–7438, https://doi.org/10.1021/acs.jpca.9b04920, 2019.
Xu, R., Ng, S. I. M., Chow, W. S., Wong, Y. K., Wang, Y., Lai, D., Yao, Z., So, P.-K., Yu, J. Z., and Chan, M. N.: Chemical transformation of α-pinene-derived organosulfate via heterogeneous OH oxidation: implications for sources and environmental fates of atmospheric organosulfates, Atmos. Chem. Phys., 22, 5685–5700, https://doi.org/10.5194/acp-22-5685-2022, 2022.
Zhang, P., Wang, W., Zhang, T., Chen, L., Du, Y., Li, C., and Lü, J.: Theoretical Study on the Mechanism and Kinetics for the Self-Reaction of C2H5O2 Radicals, J. Phys. Chem. A, 116, 4610–4620, https://doi.org/10.1021/jp301308u, 2012.
Zhang, X., Lian, Y., Tan, S., and Yin, S.: Organosulfate produced from consumption of SO3 speeds up sulfuric acid–dimethylamine atmospheric nucleation, Atmos. Chem. Phys., 24, 3593–3612, https://doi.org/10.5194/acp-24-3593-2024, 2024.
Zhao, Y. and Truhlar, D. G.: The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals, Theor. Chem. Acc., 120, 215–241, https://doi.org/10.1007/s00214-007-0310-x, 2008.
Short summary
This study examines the transformation of organosulfates through reaction with HO• radicals. The results show that the nature of substituents on the carbon chain can effectively affect the decomposition rate of organosulfates, and ozone is unveiled as a complementary oxidant in the intermediate steps of this decomposition. The primary products from these reactions include carbonyl compounds and inorganic sulfate, which highlights the role of organosulfates in altering aerosol chemical composition.
This study examines the transformation of organosulfates through reaction with HO• radicals. The...
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