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

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

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

39 Citations (Scopus)

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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 H₂SO₄from 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 H₂SO₄production 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_xeffect 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.

Original language	English
Pages (from-to)	13931-13944
Number of pages	14
Journal	Environmental Science and Technology
Volume	56
Issue number	19
DOIs	https://doi.org/10.1021/acs.est.2c05154
Publication status	Published - 2022
Publication type	A1 Journal article-refereed

Funding

This research has received funding from the Academy of Finland ACCC Flagship (no. 337549), the Academy of Finland Academy professorship (no. 302958), the Academy of Finland (nos. 307331, 337550, 296628, 328290), the European Research Council (ERC) (Projects 742206, 714621, 101002728, and 850614); the EU H2020 programme Marie Skłodowska Curie ITN “CLOUD-TRAIN” (764991), the Swiss National Science Foundation (no. 200021_169090, 200020_172602, 20FI20_172622), the US National Science Foundation (no. AGS1531284, AGS1801574, AGS1801897, AGS1801280, AGS2215522); the European Union’s Horizon 2020 Research and Innovation Programme (Marie Skłodowska Curie no. 895875 “NPF-PANDA”), the Portuguese Foundation for Science and Technology (no. CERN/FIS-COM/0028/2019), the Swedish Research Council Formas Project (no. 2018-01745-COBACCA), the Swedish Research Council VR Project (no. 2019-05006), the Crafoord Foundation Project (no. 20210969), EU H2020 project FORCeS (no. 821205), German Federal Ministry of Education and Research, CLOUD-16 (01LK1601A), and the doctoral scholarship (2021/1) of the University of Innsbruck.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 13 Climate Action

Keywords

dimethyl sulfide (DMS)
low temperatures
methanesulfinic acid (CHS(O)OH, MSIA)
methanesulfonic acid (MSA)
OH-initiated oxidation

Publication forum classification

Publication forum level 2

ASJC Scopus subject areas

General Chemistry
Environmental Chemistry

Access to Document

10.1021/acs.est.2c05154Licence: CC BY

acs.est.2c05154-1Final published version, 3.87 MBLicence: CC BY

https://urn.fi/URN:NBN:fi:tuni-202211028096Licence: CC BY

Cite this

Shen, J., Scholz, W., He, X. C., Zhou, P., Marie, G., Wang, M., Marten, R., Surdu, M., Rörup, B., Baalbaki, R., Amorim, A., Ataei, F., Bell, D. M., Bertozzi, B., Brasseur, Z., Caudillo, L., Chen, D., Chu, B., Dada, L., ... Worsnop, D. R. (2022). High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures. Environmental Science and Technology, 56(19), 13931-13944. https://doi.org/10.1021/acs.est.2c05154

@article{e06f65e2c93e452f9252aa5f256adc63,

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

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 H2SO4from 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 H2SO4production 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 NOxeffect 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 = "dimethyl sulfide (DMS), low temperatures, methanesulfinic acid (CHS(O)OH, MSIA), methanesulfonic acid (MSA), OH-initiated oxidation",

author = "Jiali Shen and Wiebke Scholz and He, \{Xu Cheng\} and Putian Zhou and Guillaume Marie and Mingyi Wang and Ruby Marten and Mihnea Surdu and Birte R{\"o}rup and Rima Baalbaki and Antonio Amorim and Farnoush Ataei and Bell, \{David M.\} and Barbara Bertozzi and Zo{\'e} Brasseur and Luc{\'i}a Caudillo and Dexian Chen and Biwu Chu and Lubna Dada and Jonathan Duplissy and Henning Finkenzeller and Manuel Granzin and Roberto Guida and Martin Heinritzi and Victoria Hofbauer and Siddharth Iyer and Deniz Kemppainen and Weimeng Kong and Krechmer, \{Jordan E.\} and Andreas K{\"u}rten and Houssni Lamkaddam and Lee, \{Chuan Ping\} and Brandon Lopez and Mahfouz, \{Naser G.A.\} and Manninen, \{Hanna E.\} and Dario Massab{\`o} and Mauldin, \{Roy L.\} and Bernhard Mentler and Tatjana M{\"u}ller and Joschka Pfeifer and Maxim Philippov and Piedehierro, \{Ana A.\} and Pontus Roldin and Siegfried Schobesberger and Mario Simon and Dominik Stolzenburg and Tham, \{Yee Jun\} and Ant{\'o}nio Tom{\'e} and Umo, \{Nsikanabasi Silas\} and Dongyu Wang and Yonghong Wang and Weber, \{Stefan K.\} and Andr{\'e} Welti and \{Wollesen De Jonge\}, Robin and Yusheng Wu and Marcel Zauner-Wieczorek and Felix Zust and Urs Baltensperger and Joachim Curtius and Flagan, \{Richard C.\} and Armin Hansel and Ottmar M{\"o}hler and Tuukka Pet{\"a}j{\"a} and Rainer Volkamer and Markku Kulmala and Katrianne Lehtipalo and Matti Rissanen and Jasper Kirkby and Imad El-Haddad and Federico Bianchi and Mikko Sipil{\"a} and Donahue, \{Neil M.\} and Worsnop, \{Douglas R.\}",

note = "Funding Information: This research has received funding from the Academy of Finland ACCC Flagship (no. 337549), the Academy of Finland Academy professorship (no. 302958), the Academy of Finland (nos. 307331, 337550, 296628, 328290), the European Research Council (ERC) (Projects 742206, 714621, 101002728, and 850614); the EU H2020 programme Marie Sk{\l}odowska Curie ITN “CLOUD-TRAIN” (764991), the Swiss National Science Foundation (no. 200021\_169090, 200020\_172602, 20FI20\_172622), the US National Science Foundation (no. AGS1531284, AGS1801574, AGS1801897, AGS1801280, AGS2215522); the European Union{\textquoteright}s Horizon 2020 Research and Innovation Programme (Marie Sk{\l}odowska Curie no. 895875 “NPF-PANDA”), the Portuguese Foundation for Science and Technology (no. CERN/FIS-COM/0028/2019), the Swedish Research Council Formas Project (no. 2018-01745-COBACCA), the Swedish Research Council VR Project (no. 2019-05006), the Crafoord Foundation Project (no. 20210969), EU H2020 project FORCeS (no. 821205), German Federal Ministry of Education and Research, CLOUD-16 (01LK1601A), and the doctoral scholarship (2021/1) of the University of Innsbruck. Publisher Copyright: {\textcopyright} 2022 American Chemical Society. All rights reserved.",

year = "2022",

doi = "10.1021/acs.est.2c05154",

language = "English",

volume = "56",

pages = "13931--13944",

journal = "Environmental Science and Technology",

issn = "1520-5851",

publisher = "American Chemical Society",

number = "19",

}

Shen, J, Scholz, W, He, XC, Zhou, P, Marie, G, Wang, M, Marten, R, Surdu, M, Rörup, B, Baalbaki, R, Amorim, A, Ataei, F, Bell, DM, Bertozzi, B, Brasseur, Z, Caudillo, L, Chen, D, Chu, B, Dada, L, Duplissy, J, Finkenzeller, H, Granzin, M, Guida, R, Heinritzi, M, Hofbauer, V, Iyer, S, Kemppainen, D, Kong, W, Krechmer, JE, Kürten, A, Lamkaddam, H, Lee, CP, Lopez, B, Mahfouz, NGA, Manninen, HE, Massabò, D, Mauldin, RL, Mentler, B, Müller, T, Pfeifer, J, Philippov, M, Piedehierro, AA, Roldin, P, Schobesberger, S, Simon, M, Stolzenburg, D, Tham, YJ, Tomé, A, Umo, NS, Wang, D, Wang, Y, Weber, SK, Welti, A, Wollesen De Jonge, R, Wu, Y, Zauner-Wieczorek, M, Zust, F, Baltensperger, U, Curtius, J, Flagan, RC, Hansel, A, Möhler, O, Petäjä, T, Volkamer, R, Kulmala, M, Lehtipalo, K, Rissanen, M, Kirkby, J, El-Haddad, I, Bianchi, F, Sipilä, M, Donahue, NM & Worsnop, DR 2022, 'High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures', Environmental Science and Technology, vol. 56, no. 19, pp. 13931-13944. https://doi.org/10.1021/acs.est.2c05154

TY - JOUR

T1 - High Gas-Phase Methanesulfonic Acid Production in the OH-Initiated Oxidation of Dimethyl Sulfide at Low Temperatures

AU - Shen, Jiali

AU - Scholz, Wiebke

AU - He, Xu Cheng

AU - Zhou, Putian

AU - Marie, Guillaume

AU - Wang, Mingyi

AU - Marten, Ruby

AU - Surdu, Mihnea

AU - Rörup, Birte

AU - Baalbaki, Rima

AU - Amorim, Antonio

AU - Ataei, Farnoush

AU - Bell, David M.

AU - Bertozzi, Barbara

AU - Brasseur, Zoé

AU - Caudillo, Lucía

AU - Chen, Dexian

AU - Chu, Biwu

AU - Dada, Lubna

AU - Duplissy, Jonathan

AU - Finkenzeller, Henning

AU - Granzin, Manuel

AU - Guida, Roberto

AU - Heinritzi, Martin

AU - Hofbauer, Victoria

AU - Iyer, Siddharth

AU - Kemppainen, Deniz

AU - Kong, Weimeng

AU - Krechmer, Jordan E.

AU - Kürten, Andreas

AU - Lamkaddam, Houssni

AU - Lee, Chuan Ping

AU - Lopez, Brandon

AU - Mahfouz, Naser G.A.

AU - Manninen, Hanna E.

AU - Massabò, Dario

AU - Mauldin, Roy L.

AU - Mentler, Bernhard

AU - Müller, Tatjana

AU - Pfeifer, Joschka

AU - Philippov, Maxim

AU - Piedehierro, Ana A.

AU - Roldin, Pontus

AU - Schobesberger, Siegfried

AU - Simon, Mario

AU - Stolzenburg, Dominik

AU - Tham, Yee Jun

AU - Tomé, António

AU - Umo, Nsikanabasi Silas

AU - Wang, Dongyu

AU - Wang, Yonghong

AU - Weber, Stefan K.

AU - Welti, André

AU - Wollesen De Jonge, Robin

AU - Wu, Yusheng

AU - Zauner-Wieczorek, Marcel

AU - Zust, Felix

AU - Baltensperger, Urs

AU - Curtius, Joachim

AU - Flagan, Richard C.

AU - Hansel, Armin

AU - Möhler, Ottmar

AU - Petäjä, Tuukka

AU - Volkamer, Rainer

AU - Kulmala, Markku

AU - Lehtipalo, Katrianne

AU - Rissanen, Matti

AU - Kirkby, Jasper

AU - El-Haddad, Imad

AU - Bianchi, Federico

AU - Sipilä, Mikko

AU - Donahue, Neil M.

AU - Worsnop, Douglas R.

N1 - Funding Information: This research has received funding from the Academy of Finland ACCC Flagship (no. 337549), the Academy of Finland Academy professorship (no. 302958), the Academy of Finland (nos. 307331, 337550, 296628, 328290), the European Research Council (ERC) (Projects 742206, 714621, 101002728, and 850614); the EU H2020 programme Marie Skłodowska Curie ITN “CLOUD-TRAIN” (764991), the Swiss National Science Foundation (no. 200021_169090, 200020_172602, 20FI20_172622), the US National Science Foundation (no. AGS1531284, AGS1801574, AGS1801897, AGS1801280, AGS2215522); the European Union’s Horizon 2020 Research and Innovation Programme (Marie Skłodowska Curie no. 895875 “NPF-PANDA”), the Portuguese Foundation for Science and Technology (no. CERN/FIS-COM/0028/2019), the Swedish Research Council Formas Project (no. 2018-01745-COBACCA), the Swedish Research Council VR Project (no. 2019-05006), the Crafoord Foundation Project (no. 20210969), EU H2020 project FORCeS (no. 821205), German Federal Ministry of Education and Research, CLOUD-16 (01LK1601A), and the doctoral scholarship (2021/1) of the University of Innsbruck. Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022

Y1 - 2022

N2 - 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 H2SO4from 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 H2SO4production 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 NOxeffect 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.

AB - 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 H2SO4from 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 H2SO4production 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 NOxeffect 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.

KW - dimethyl sulfide (DMS)

KW - low temperatures

KW - methanesulfinic acid (CHS(O)OH, MSIA)

KW - methanesulfonic acid (MSA)

KW - OH-initiated oxidation

U2 - 10.1021/acs.est.2c05154

DO - 10.1021/acs.est.2c05154

M3 - Article

C2 - 36137236

AN - SCOPUS:85138953803

SN - 1520-5851

VL - 56

SP - 13931

EP - 13944

JO - Environmental Science and Technology

JF - Environmental Science and Technology

IS - 19

ER -

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

Abstract

Funding

UN SDGs

Keywords

Publication forum classification

ASJC Scopus subject areas

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