The gas-phase formation mechanism of iodic acid as an atmospheric aerosol source

Henning Finkenzeller; Siddharth Iyer; Xu-Cheng He; Mario Simon; Theodore K. Koenig; Christopher F. Lee; Rashid Valiev; Victoria Hofbauer; António Amorim; Rima Baalbaki; Andrea Baccarini; Lisa Beck; David M. Bell; Lucía Caudillo; Dexian Chen; Randall Chiu; Biwu Chu; Lubna Dada; Jonathan Duplissy; Martin Heinritzi; Deniz Kemppainen; Changhyuk Kim; Jordan Krechmer; Andreas Kürten; Alexandr Kvashnin; Houssni Lamkaddam; Chuan Ping Lee; Katrianne Lehtipalo; Zijun Li; Vladimir Makhmutov; Hanna E. Manninen; Guillaume Marie; Ruby Marten; Roy L. Mauldin; Bernhard Mentler; Tatjana Müller; Tuukka Petäjä; Maxim Philippov; Ananth Ranjithkumar; Birte Rörup; Jiali Shen; Dominik Stolzenburg; Christian Tauber; Yee Jun Tham; António Tomé; Miguel Vazquez-Pufleau; Andrea C. Wagner; Dongyu S. Wang; Mingyi Wang; Yonghong Wang; Stefan K. Weber; Wei Nie; Yusheng Wu; Mao Xiao; Qing Ye; Marcel Zauner-Wieczorek; Armin Hansel; Urs Baltensperger; Jérome Brioude; Joachim Curtius; Neil M. Donahue; Imad El Haddad; Richard C. Flagan; Markku Kulmala; Jasper Kirkby; Mikko Sipilä; Douglas R. Worsnop; Theo Kurten; Matti Rissanen; Rainer Volkamer

doi:10.1038/s41557-022-01067-z

The gas-phase formation mechanism of iodic acid as an atmospheric aerosol source

Henning Finkenzeller^*
, Siddharth Iyer
, Xu-Cheng He
, Mario Simon
, Theodore K. Koenig
, Christopher F. Lee
, Rashid Valiev
, Victoria Hofbauer
, António Amorim
, Rima Baalbaki
, Andrea Baccarini
, Lisa Beck
, David M. Bell
, Lucía Caudillo
, Dexian Chen
, Randall Chiu
, Biwu Chu
, Lubna Dada
, Jonathan Duplissy
, Martin Heinritzi

Deniz Kemppainen, Changhyuk Kim, Jordan Krechmer, Andreas Kürten, Alexandr Kvashnin, Houssni Lamkaddam, Chuan Ping Lee, Katrianne Lehtipalo, Zijun Li, Vladimir Makhmutov, Hanna E. Manninen, Guillaume Marie, Ruby Marten, Roy L. Mauldin, Bernhard Mentler, Tatjana Müller, Tuukka Petäjä, Maxim Philippov, Ananth Ranjithkumar, Birte Rörup, Jiali Shen, Dominik Stolzenburg, Christian Tauber, Yee Jun Tham, António Tomé, Miguel Vazquez-Pufleau, Andrea C. Wagner, Dongyu S. Wang, Mingyi Wang, Yonghong Wang, Stefan K. Weber, Wei Nie, Yusheng Wu, Mao Xiao, Qing Ye, Marcel Zauner-Wieczorek, Armin Hansel, Urs Baltensperger, Jérome Brioude, Joachim Curtius, Neil M. Donahue, Imad El Haddad, Richard C. Flagan, Markku Kulmala, Jasper Kirkby, Mikko Sipilä, Douglas R. Worsnop, Theo Kurten, Matti Rissanen, Rainer Volkamer

^*Corresponding author for this work

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

66 Citations (Scopus)

23 Downloads (Pure)

Abstract

Iodine is a reactive trace element in atmospheric chemistry that destroys ozone and nucleates particles. Iodine emissions have tripled since 1950 and are projected to keep increasing with rising O3 surface concentrations. Although iodic acid (HIO3) is widespread and forms particles more efficiently than sulfuric acid, its gas-phase formation mechanism remains unresolved. Here, in CLOUD atmospheric simulation chamber experiments that generate iodine radicals at atmospherically relevant rates, we show that iodooxy hypoiodite, IOIO, is efficiently converted into HIO3 via reactions (R1) IOIO + O3 → IOIO4 and (R2) IOIO4 + H2O → HIO3 + HOI + (1)O2. The laboratory-derived reaction rate coefficients are corroborated by theory and shown to explain field observations of daytime HIO3 in the remote lower free troposphere. The mechanism provides a missing link between iodine sources and particle formation. Because particulate iodate is readily reduced, recycling iodine back into the gas phase, our results suggest a catalytic role of iodine in aerosol formation.

Original language	English
Pages (from-to)	129-135
Number of pages	7
Journal	Nature Chemistry
Volume	15
Issue number	1
Early online date	14 Nov 2022
DOIs	https://doi.org/10.1038/s41557-022-01067-z
Publication status	Published - Jan 2023
Publication type	A1 Journal article-refereed

Funding

We thank the European Organization for Nuclear Research (CERN) for supporting CLOUD with important technical and financial resources. H.F. is recipient of a NASA Earth and Space Science Fellowship (NASA-80NSSC17K0369) (H.F. and R. Volkamer). This research has received support from the US National Science Foundation (AGS-1801280, AGS-1620530, AGS-2027252 (R. Volkamer); AGS-1447056, AGS-1439551, AGS-1531284, AGS-1801574, AGS-1801897 and AGS-2132089 (R.C.F. and N.M.D.)); the Academy of Finland (projects 346369 (T.K.); 331207 (M.R.); 1325656, 316114, 325647, 337549 and 302958 (M.K.); 296628 (M. Sipilä)); Russian Mega Grant project 075-15-2021-574 (M.K.); Jane and Aatos Erkko Foundation (2020-220-08-5835, X.-C. H.); Samsung PM2.5 SRP (M.K.); European Research Council under the European Union’s Horizon 2020 research and innovation programme (projects 714621 (M. Sipilä); 742206 and 895875 (M.K.); 616075 (M.V.-P.); 101002728 (M.R.)); Innovative Training Networks–ITN (CLOUD-Motion H2020-MSCA-ITN-2017 no. 764991, J.C.); German Ministry of Science and Education (CLOUD-16, 01LK1601A, J.C.); Wallace Research Foundation, Carnegie Mellon University Scott Institute for Energy Innovation (N.M.D.); Jenny and Antti Wihuri Foundation (X.-C.H.); Swiss National Science Foundation (200020_172602, BSSGI0_155846 and 20FI20_172622, C.P.L.); Ministry of Science and Higher Education of the Russian Federation (V.M.); National Natural Science Foundation of China (42175118, Y.J.T.); and the Portuguese National Funding Agency for Science, Research and Technology-CERN/FIS-COM/0028/2019 (A.T.). The Maïdo IOP was performed in the framework of the OCTAVE project of the ‘Belgian Research Action through Interdisciplinary Networks’ 5 (BRAIN-be) research programme (2017-2021) through the Belgian Science Policy Office (BELSPO; contract no. BR/175/A2/OCTAVE, J.B.) with ACTRIS-2 TNA support from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 654109 (M.R.), and support by UAR3365 of OSU-Réunion (J.B.).

Publication forum classification

Publication forum level 3

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering

Access to Document

10.1038/s41557-022-01067-zLicence: CC BY

The gas-phase formation mechanismFinal published version, 3.24 MBLicence: CC BY

https://urn.fi/URN:NBN:fi:tuni-202211188452Licence: CC BY

Cite this

Finkenzeller, H., Iyer, S., He, X.-C., Simon, M., Koenig, T. K., Lee, C. F., Valiev, R., Hofbauer, V., Amorim, A., Baalbaki, R., Baccarini, A., Beck, L., Bell, D. M., Caudillo, L., Chen, D., Chiu, R., Chu, B., Dada, L., Duplissy, J., ... Volkamer, R. (2023). The gas-phase formation mechanism of iodic acid as an atmospheric aerosol source. Nature Chemistry, 15(1), 129-135. https://doi.org/10.1038/s41557-022-01067-z

@article{41ea4ea00b244bb4bd30430c535ce15b,

title = "The gas-phase formation mechanism of iodic acid as an atmospheric aerosol source",

abstract = "Iodine is a reactive trace element in atmospheric chemistry that destroys ozone and nucleates particles. Iodine emissions have tripled since 1950 and are projected to keep increasing with rising O3 surface concentrations. Although iodic acid (HIO3) is widespread and forms particles more efficiently than sulfuric acid, its gas-phase formation mechanism remains unresolved. Here, in CLOUD atmospheric simulation chamber experiments that generate iodine radicals at atmospherically relevant rates, we show that iodooxy hypoiodite, IOIO, is efficiently converted into HIO3 via reactions (R1) IOIO + O3 → IOIO4 and (R2) IOIO4 + H2O → HIO3 + HOI + (1)O2. The laboratory-derived reaction rate coefficients are corroborated by theory and shown to explain field observations of daytime HIO3 in the remote lower free troposphere. The mechanism provides a missing link between iodine sources and particle formation. Because particulate iodate is readily reduced, recycling iodine back into the gas phase, our results suggest a catalytic role of iodine in aerosol formation.",

author = "Henning Finkenzeller and Siddharth Iyer and Xu-Cheng He and Mario Simon and Koenig, \{Theodore K.\} and Lee, \{Christopher F.\} and Rashid Valiev and Victoria Hofbauer and Ant{\'o}nio Amorim and Rima Baalbaki and Andrea Baccarini and Lisa Beck and Bell, \{David M.\} and Luc{\'i}a Caudillo and Dexian Chen and Randall Chiu and Biwu Chu and Lubna Dada and Jonathan Duplissy and Martin Heinritzi and Deniz Kemppainen and Changhyuk Kim and Jordan Krechmer and Andreas K{\"u}rten and Alexandr Kvashnin and Houssni Lamkaddam and Lee, \{Chuan Ping\} and Katrianne Lehtipalo and Zijun Li and Vladimir Makhmutov and Manninen, \{Hanna E.\} and Guillaume Marie and Ruby Marten and Mauldin, \{Roy L.\} and Bernhard Mentler and Tatjana M{\"u}ller and Tuukka Pet{\"a}j{\"a} and Maxim Philippov and Ananth Ranjithkumar and Birte R{\"o}rup and Jiali Shen and Dominik Stolzenburg and Christian Tauber and Tham, \{Yee Jun\} and Ant{\'o}nio Tom{\'e} and Miguel Vazquez-Pufleau and Wagner, \{Andrea C.\} and Wang, \{Dongyu S.\} and Mingyi Wang and Yonghong Wang and Weber, \{Stefan K.\} and Wei Nie and Yusheng Wu and Mao Xiao and Qing Ye and Marcel Zauner-Wieczorek and Armin Hansel and Urs Baltensperger and J{\'e}rome Brioude and Joachim Curtius and Donahue, \{Neil M.\} and Haddad, \{Imad El\} and Flagan, \{Richard C.\} and Markku Kulmala and Jasper Kirkby and Mikko Sipil{\"a} and Worsnop, \{Douglas R.\} and Theo Kurten and Matti Rissanen and Rainer Volkamer",

note = "Funding Information: We thank the European Organization for Nuclear Research (CERN) for supporting CLOUD with important technical and financial resources. H.F. is recipient of a NASA Earth and Space Science Fellowship (NASA-80NSSC17K0369) (H.F. and R. Volkamer). This research has received support from the US National Science Foundation (AGS-1801280, AGS-1620530, AGS-2027252 (R. Volkamer); AGS-1447056, AGS-1439551, AGS-1531284, AGS-1801574, AGS-1801897 and AGS-2132089 (R.C.F. and N.M.D.)); the Academy of Finland (projects 346369 (T.K.); 331207 (M.R.); 1325656, 316114, 325647, 337549 and 302958 (M.K.); 296628 (M. Sipil{\"a})); Russian Mega Grant project 075-15-2021-574 (M.K.); Jane and Aatos Erkko Foundation (2020-220-08-5835, X.-C. H.); Samsung PM2.5 SRP (M.K.); European Research Council under the European Union{\textquoteright}s Horizon 2020 research and innovation programme (projects 714621 (M. Sipil{\"a}); 742206 and 895875 (M.K.); 616075 (M.V.-P.); 101002728 (M.R.)); Innovative Training Networks{\textendash}ITN (CLOUD-Motion H2020-MSCA-ITN-2017 no. 764991, J.C.); German Ministry of Science and Education (CLOUD-16, 01LK1601A, J.C.); Wallace Research Foundation, Carnegie Mellon University Scott Institute for Energy Innovation (N.M.D.); Jenny and Antti Wihuri Foundation (X.-C.H.); Swiss National Science Foundation (200020\_172602, BSSGI0\_155846 and 20FI20\_172622, C.P.L.); Ministry of Science and Higher Education of the Russian Federation (V.M.); National Natural Science Foundation of China (42175118, Y.J.T.); and the Portuguese National Funding Agency for Science, Research and Technology-CERN/FIS-COM/0028/2019 (A.T.). The Ma{\"i}do IOP was performed in the framework of the OCTAVE project of the {\textquoteleft}Belgian Research Action through Interdisciplinary Networks{\textquoteright} 5 (BRAIN-be) research programme (2017-2021) through the Belgian Science Policy Office (BELSPO; contract no. BR/175/A2/OCTAVE, J.B.) with ACTRIS-2 TNA support from the European Union{\textquoteright}s Horizon 2020 research and innovation programme under grant agreement no. 654109 (M.R.), and support by UAR3365 of OSU-R{\'e}union (J.B.). Publisher Copyright: {\textcopyright} 2022, The Author(s).",

year = "2023",

month = jan,

doi = "10.1038/s41557-022-01067-z",

language = "English",

volume = "15",

pages = "129--135",

journal = "Nature Chemistry",

issn = "1755-4330",

publisher = "Nature Publishing Group",

number = "1",

}

Finkenzeller, H, Iyer, S, He, X-C, Simon, M, Koenig, TK, Lee, CF, Valiev, R, Hofbauer, V, Amorim, A, Baalbaki, R, Baccarini, A, Beck, L, Bell, DM, Caudillo, L, Chen, D, Chiu, R, Chu, B, Dada, L, Duplissy, J, Heinritzi, M, Kemppainen, D, Kim, C, Krechmer, J, Kürten, A, Kvashnin, A, Lamkaddam, H, Lee, CP, Lehtipalo, K, Li, Z, Makhmutov, V, Manninen, HE, Marie, G, Marten, R, Mauldin, RL, Mentler, B, Müller, T, Petäjä, T, Philippov, M, Ranjithkumar, A, Rörup, B, Shen, J, Stolzenburg, D, Tauber, C, Tham, YJ, Tomé, A, Vazquez-Pufleau, M, Wagner, AC, Wang, DS, Wang, M, Wang, Y, Weber, SK, Nie, W, Wu, Y, Xiao, M, Ye, Q, Zauner-Wieczorek, M, Hansel, A, Baltensperger, U, Brioude, J, Curtius, J, Donahue, NM, Haddad, IE, Flagan, RC, Kulmala, M, Kirkby, J, Sipilä, M, Worsnop, DR, Kurten, T, Rissanen, M & Volkamer, R 2023, 'The gas-phase formation mechanism of iodic acid as an atmospheric aerosol source', Nature Chemistry, vol. 15, no. 1, pp. 129-135. https://doi.org/10.1038/s41557-022-01067-z

TY - JOUR

T1 - The gas-phase formation mechanism of iodic acid as an atmospheric aerosol source

AU - Finkenzeller, Henning

AU - Iyer, Siddharth

AU - He, Xu-Cheng

AU - Simon, Mario

AU - Koenig, Theodore K.

AU - Lee, Christopher F.

AU - Valiev, Rashid

AU - Hofbauer, Victoria

AU - Amorim, António

AU - Baalbaki, Rima

AU - Baccarini, Andrea

AU - Beck, Lisa

AU - Bell, David M.

AU - Caudillo, Lucía

AU - Chen, Dexian

AU - Chiu, Randall

AU - Chu, Biwu

AU - Dada, Lubna

AU - Duplissy, Jonathan

AU - Heinritzi, Martin

AU - Kemppainen, Deniz

AU - Kim, Changhyuk

AU - Krechmer, Jordan

AU - Kürten, Andreas

AU - Kvashnin, Alexandr

AU - Lamkaddam, Houssni

AU - Lee, Chuan Ping

AU - Lehtipalo, Katrianne

AU - Li, Zijun

AU - Makhmutov, Vladimir

AU - Manninen, Hanna E.

AU - Marie, Guillaume

AU - Marten, Ruby

AU - Mauldin, Roy L.

AU - Mentler, Bernhard

AU - Müller, Tatjana

AU - Petäjä, Tuukka

AU - Philippov, Maxim

AU - Ranjithkumar, Ananth

AU - Rörup, Birte

AU - Shen, Jiali

AU - Stolzenburg, Dominik

AU - Tauber, Christian

AU - Tham, Yee Jun

AU - Tomé, António

AU - Vazquez-Pufleau, Miguel

AU - Wagner, Andrea C.

AU - Wang, Dongyu S.

AU - Wang, Mingyi

AU - Wang, Yonghong

AU - Weber, Stefan K.

AU - Nie, Wei

AU - Wu, Yusheng

AU - Xiao, Mao

AU - Ye, Qing

AU - Zauner-Wieczorek, Marcel

AU - Hansel, Armin

AU - Baltensperger, Urs

AU - Brioude, Jérome

AU - Curtius, Joachim

AU - Donahue, Neil M.

AU - Haddad, Imad El

AU - Flagan, Richard C.

AU - Kulmala, Markku

AU - Kirkby, Jasper

AU - Sipilä, Mikko

AU - Worsnop, Douglas R.

AU - Kurten, Theo

AU - Rissanen, Matti

AU - Volkamer, Rainer

N1 - Funding Information: We thank the European Organization for Nuclear Research (CERN) for supporting CLOUD with important technical and financial resources. H.F. is recipient of a NASA Earth and Space Science Fellowship (NASA-80NSSC17K0369) (H.F. and R. Volkamer). This research has received support from the US National Science Foundation (AGS-1801280, AGS-1620530, AGS-2027252 (R. Volkamer); AGS-1447056, AGS-1439551, AGS-1531284, AGS-1801574, AGS-1801897 and AGS-2132089 (R.C.F. and N.M.D.)); the Academy of Finland (projects 346369 (T.K.); 331207 (M.R.); 1325656, 316114, 325647, 337549 and 302958 (M.K.); 296628 (M. Sipilä)); Russian Mega Grant project 075-15-2021-574 (M.K.); Jane and Aatos Erkko Foundation (2020-220-08-5835, X.-C. H.); Samsung PM2.5 SRP (M.K.); European Research Council under the European Union’s Horizon 2020 research and innovation programme (projects 714621 (M. Sipilä); 742206 and 895875 (M.K.); 616075 (M.V.-P.); 101002728 (M.R.)); Innovative Training Networks–ITN (CLOUD-Motion H2020-MSCA-ITN-2017 no. 764991, J.C.); German Ministry of Science and Education (CLOUD-16, 01LK1601A, J.C.); Wallace Research Foundation, Carnegie Mellon University Scott Institute for Energy Innovation (N.M.D.); Jenny and Antti Wihuri Foundation (X.-C.H.); Swiss National Science Foundation (200020_172602, BSSGI0_155846 and 20FI20_172622, C.P.L.); Ministry of Science and Higher Education of the Russian Federation (V.M.); National Natural Science Foundation of China (42175118, Y.J.T.); and the Portuguese National Funding Agency for Science, Research and Technology-CERN/FIS-COM/0028/2019 (A.T.). The Maïdo IOP was performed in the framework of the OCTAVE project of the ‘Belgian Research Action through Interdisciplinary Networks’ 5 (BRAIN-be) research programme (2017-2021) through the Belgian Science Policy Office (BELSPO; contract no. BR/175/A2/OCTAVE, J.B.) with ACTRIS-2 TNA support from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 654109 (M.R.), and support by UAR3365 of OSU-Réunion (J.B.). Publisher Copyright: © 2022, The Author(s).

PY - 2023/1

Y1 - 2023/1

N2 - Iodine is a reactive trace element in atmospheric chemistry that destroys ozone and nucleates particles. Iodine emissions have tripled since 1950 and are projected to keep increasing with rising O3 surface concentrations. Although iodic acid (HIO3) is widespread and forms particles more efficiently than sulfuric acid, its gas-phase formation mechanism remains unresolved. Here, in CLOUD atmospheric simulation chamber experiments that generate iodine radicals at atmospherically relevant rates, we show that iodooxy hypoiodite, IOIO, is efficiently converted into HIO3 via reactions (R1) IOIO + O3 → IOIO4 and (R2) IOIO4 + H2O → HIO3 + HOI + (1)O2. The laboratory-derived reaction rate coefficients are corroborated by theory and shown to explain field observations of daytime HIO3 in the remote lower free troposphere. The mechanism provides a missing link between iodine sources and particle formation. Because particulate iodate is readily reduced, recycling iodine back into the gas phase, our results suggest a catalytic role of iodine in aerosol formation.

AB - Iodine is a reactive trace element in atmospheric chemistry that destroys ozone and nucleates particles. Iodine emissions have tripled since 1950 and are projected to keep increasing with rising O3 surface concentrations. Although iodic acid (HIO3) is widespread and forms particles more efficiently than sulfuric acid, its gas-phase formation mechanism remains unresolved. Here, in CLOUD atmospheric simulation chamber experiments that generate iodine radicals at atmospherically relevant rates, we show that iodooxy hypoiodite, IOIO, is efficiently converted into HIO3 via reactions (R1) IOIO + O3 → IOIO4 and (R2) IOIO4 + H2O → HIO3 + HOI + (1)O2. The laboratory-derived reaction rate coefficients are corroborated by theory and shown to explain field observations of daytime HIO3 in the remote lower free troposphere. The mechanism provides a missing link between iodine sources and particle formation. Because particulate iodate is readily reduced, recycling iodine back into the gas phase, our results suggest a catalytic role of iodine in aerosol formation.

U2 - 10.1038/s41557-022-01067-z

DO - 10.1038/s41557-022-01067-z

M3 - Article

SN - 1755-4330

VL - 15

SP - 129

EP - 135

JO - Nature Chemistry

JF - Nature Chemistry

IS - 1

ER -

The gas-phase formation mechanism of iodic acid as an atmospheric aerosol source

Abstract

Funding

Publication forum classification

ASJC Scopus subject areas

Access to Document

Fingerprint

Cite this