High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures

Jiali Shen; Wiebke Scholz; Xu-Cheng He; Putian Zhou; Guillaume Marie; Mingyi Wang; Ruby Marten; Mihnea Surdu; Birte Rörup; Rima Baalbaki; Antonio Amorim; Farnoush Ataei; David M Bell; Barbara Bertozzi; Zoé Brasseur; Lucía Caudillo; Dexian Chen; Biwu Chu; Lubna Dada; Jonathan Duplissy; Henning Finkenzeller; Manuel Granzin; Roberto Guida; Martin Heinritzi; Victoria Hofbauer; Siddharth Iyer; Deniz Kemppainen; Weimeng Kong; Jordan E Krechmer; Andreas Kürten; Houssni Lamkaddam; Chuan Ping Lee; Brandon Lopez; Naser G A Mahfouz; Hanna E Manninen; Dario Massabò; Roy L Mauldin; Bernhard Mentler; Tatjana Müller; Joschka Pfeifer; Maxim Philippov; Ana A Piedehierro; Pontus Roldin; Siegfried Schobesberger; Mario Simon; Dominik Stolzenburg; Yee Jun Tham; António Tomé; Nsikanabasi Silas Umo; Dongyu Wang; Yonghong Wang; Stefan K Weber; André Welti; Robin Wollesen de Jonge; Yusheng Wu; Marcel Zauner-Wieczorek; Felix Zust; Urs Baltensperger; Joachim Curtius; Richard C Flagan; Armin Hansel; Ottmar Möhler; Tuukka Petäjä; Rainer Volkamer; Markku Kulmala; Katrianne Lehtipalo; Matti Rissanen; Jasper Kirkby; Imad El-Haddad; Federico Bianchi; Mikko Sipilä; Neil M Donahue; Douglas R Worsnop

doi:10.1021/acs.est.2c05154

High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures

Environ Sci Technol. 2022 Oct 4;56(19):13931-13944. doi: 10.1021/acs.est.2c05154. Epub 2022 Sep 22.

Authors

Jiali Shen¹, Wiebke Scholz², Xu-Cheng He¹, Putian Zhou¹, Guillaume Marie³, Mingyi Wang⁴, Ruby Marten⁵, Mihnea Surdu⁵, Birte Rörup¹, Rima Baalbaki¹, Antonio Amorim⁶, Farnoush Ataei⁷, David M Bell⁵, Barbara Bertozzi⁸, Zoé Brasseur¹, Lucía Caudillo³, Dexian Chen⁴, Biwu Chu¹, Lubna Dada⁵, Jonathan Duplissy^{1

9}, Henning Finkenzeller¹⁰, Manuel Granzin³, Roberto Guida¹¹, Martin Heinritzi³, Victoria Hofbauer⁴, Siddharth Iyer¹², Deniz Kemppainen¹, Weimeng Kong¹³, Jordan E Krechmer¹⁴, Andreas Kürten³, Houssni Lamkaddam⁵, Chuan Ping Lee⁵, Brandon Lopez⁴, Naser G A Mahfouz¹⁵, Hanna E Manninen¹¹, Dario Massabò¹⁶, Roy L Mauldin^{17

18}, Bernhard Mentler², Tatjana Müller³, Joschka Pfeifer¹¹, Maxim Philippov¹⁹, Ana A Piedehierro²⁰, Pontus Roldin²¹, Siegfried Schobesberger²², Mario Simon³, Dominik Stolzenburg¹, Yee Jun Tham^{1

23}, António Tomé²⁴, Nsikanabasi Silas Umo⁸, Dongyu Wang⁵, Yonghong Wang¹, Stefan K Weber^{3

11}, André Welti²⁰, Robin Wollesen de Jonge²¹, Yusheng Wu¹, Marcel Zauner-Wieczorek³, Felix Zust², Urs Baltensperger⁵, Joachim Curtius³, Richard C Flagan¹³, Armin Hansel², Ottmar Möhler⁸, Tuukka Petäjä¹, Rainer Volkamer¹⁰, Markku Kulmala^{1

9

25

26}, Katrianne Lehtipalo^{1

20}, Matti Rissanen¹², Jasper Kirkby^{3

11}, Imad El-Haddad⁵, Federico Bianchi¹, Mikko Sipilä¹, Neil M Donahue^{4

17

27

28}, Douglas R Worsnop^{1

14}

Affiliations

¹ Institute for Atmospheric and Earth System Research/Physics, Faculty of Science, University of Helsinki, 00014 Helsinki, Finland.
² Institute of Ion Physics and Applied Physics, University of Innsbruck, 6020 Innsbruck, Austria.
³ Institute for Atmospheric and Environmental Sciences, Goethe University Frankfurt, 60438 Frankfurt am Main, Germany.
⁴ Center for Atmospheric Particle Studies, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.
⁵ Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, CH-5232 Villigen, Switzerland.
⁶ CENTRA and Faculdade de Ciências da Universidade de Lisboa, 1749-016 Campo Grande, Lisboa, Portugal.
⁷ Leibniz Institute for Tropospheric Research, Permoserstrasse 15, 04318 Leipzig, Germany.
⁸ Institute of Meteorology and Climate Research, Karlsruhe Institute of Technology, 76344 Karlsruhe, Germany.
⁹ Helsinki Institute of Physics, University of Helsinki, 00014 Helsinki, Finland.
¹⁰ Department of Chemistry and Cooperative Institute for Research in the Environmental Sciences, University of Colorado Boulder, Boulder, Colorado 80309, United States.
¹¹ CERN, the European Organization for Nuclear Research, CH-1211 Geneva 23, Switzerland.
¹² Aerosol Physics Laboratory, Physics Unit, Faculty of Engineering and Natural Sciences, Tampere University, 33014 Tampere, Finland.
¹³ Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
¹⁴ Aerodyne Research, Inc., Billerica, Massachusetts 01821, United States.
¹⁵ Atmospheric and Oceanic Sciences, Princeton University, Princeton, New Jersey 08540, United States.
¹⁶ Department of Physics, University of Genoa & INFN, 16146 Genoa, Italy.
¹⁷ Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.
¹⁸ Department of Atmospheric and Oceanic Sciences, University of Colorado Boulder, Boulder, Colorado 80309, United States.
¹⁹ P.N. Lebedev Physical Institute of the Russian Academy of Sciences, 119991 Moscow, Russia.
²⁰ Finnish Meteorological Institute, Erik Palmenin aukio 1, 00560 Helsinki, Finland.
²¹ Division of Nuclear Physics, Lund University, 22100 Lund, Sweden.
²² Department of Applied Physics, University of Eastern Finland, 70211 Kuopio, Finland.
²³ School of Marine Sciences, Sun Yat-sen University, 519082 Zhuhai, China.
²⁴ Institute Infante Dom Luíz, University of Beira Interior, 6200-001 Covilhã, Portugal.
²⁵ Joint International Research Laboratory of Atmospheric and Earth System Sciences, School of Atmospheric Sciences, Nanjing University, 210023 Nanjing, China.
²⁶ Aerosol and Haze Laboratory, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, 100029 Beijing, China.
²⁷ Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.
²⁸ Department of Engineering and Public Policy, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States.

Abstract

Dimethyl sulfide (DMS) influences climate via cloud condensation nuclei (CCN) formation resulting from its oxidation products (mainly methanesulfonic acid, MSA, and sulfuric acid, H₂SO₄). Despite their importance, accurate prediction of MSA and H₂SO₄ from DMS oxidation remains challenging. With comprehensive experiments carried out in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at CERN, we show that decreasing the temperature from +25 to -10 °C enhances the gas-phase MSA production by an order of magnitude from OH-initiated DMS oxidation, while H₂SO₄ production is modestly affected. This leads to a gas-phase H₂SO₄-to-MSA ratio (H₂SO₄/MSA) smaller than one at low temperatures, consistent with field observations in polar regions. With an updated DMS oxidation mechanism, we find that methanesulfinic acid, CH₃S(O)OH, MSIA, forms large amounts of MSA. Overall, our results reveal that MSA yields are a factor of 2-10 higher than those predicted by the widely used Master Chemical Mechanism (MCMv3.3.1), and the NO_x effect is less significant than that of temperature. Our updated mechanism explains the high MSA production rates observed in field observations, especially at low temperatures, thus, substantiating the greater importance of MSA in the natural sulfur cycle and natural CCN formation. Our mechanism will improve the interpretation of present-day and historical gas-phase H₂SO₄/MSA measurements.

Keywords: OH-initiated oxidation; dimethyl sulfide (DMS); low temperatures; methanesulfinic acid (CH3S(O)OH, MSIA); methanesulfonic acid (MSA).