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

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

doi:10.1038/s41557-022-01067-z

Cited by 30 publications

(47 citation statements)

References 67 publications

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“…While the formation mechanism for HIO 3 has recently been established ( 22 ), the pathway for HIO 2 formation remains uncertain. A quantum chemical study provided a potential energy surface describing formation of HIO 2 from iodooxy hypoiodite, I 2 O 2 + H 2 O ( 30 ).…”

Section: Hio2 Accelerates Neutral Nucleationmentioning

confidence: 99%

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Iodine oxoacids enhance nucleation of sulfuric acid particles in the atmosphere

He,

Simon,

Iyer

et al. 2023

Science

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The main nucleating vapor in the atmosphere is thought to be sulfuric acid (H 2 SO 4 ), stabilized by ammonia (NH 3 ). However, in marine and polar regions, NH 3 is generally low, and H 2 SO 4 is frequently found together with iodine oxoacids [HIO x , i.e., iodic acid (HIO 3 ) and iodous acid (HIO 2 )]. In experiments performed with the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we investigated the interplay of H 2 SO 4 and HIO x during atmospheric particle nucleation. We found that HIO x greatly enhances H 2 SO 4 (-NH 3 ) nucleation through two different interactions. First, HIO 3 strongly binds with H 2 SO 4 in charged clusters so they drive particle nucleation synergistically. Second, HIO 2 substitutes for NH 3 , forming strongly bound H 2 SO 4 -HIO 2 acid-base pairs in molecular clusters. Global observations imply that HIO x is enhancing H 2 SO 4 (-NH 3 ) nucleation rates 10- to 10,000-fold in marine and polar regions.

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Section: Hio2 Accelerates Neutral Nucleationmentioning

confidence: 99%

“…In the marine atmosphere, iodine and sulfur precursors emitted from the ocean surface lead to the formation of both H 2 SO 4 and HIO x ( 22 ). HIO x has generally been observed at concentrations similar to or lower than H 2 SO 4 ( 6 , 18 , 21 , 23 ).…”

mentioning

confidence: 99%

Iodine oxoacids enhance nucleation of sulfuric acid particles in the atmosphere

He,

Simon,

Iyer

et al. 2023

Science

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“…The instrument was operational at Maïdo before, during, and after the April–June 2018 eruption of Piton de la Fournaise. 42,43 Spectra measured during the volcanic eruption were analyzed with respect to a reference spectrum measured in the absence of the volcanic plume using a DOAS spectral retrieval algorithm to retrieve SO 2 , BrO, and IO differential slant column densities (dSCDs).…”

Section: Methodsmentioning

confidence: 99%

Observed in-plume gaseous elemental mercury depletion suggests significant mercury scavenging by volcanic aerosols

Koenig,

Magand,

Rose

et al. 2023

Environ. Sci.: Atmos.

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“…In mass spectrometry laboratory studies, Martıń et al (2022) showed that new iodine containing (nano) particles and IO − 3 also form in the presence of NO − 3 and provide DH reaction data for the gas phase reactions involved. Experiments using the CERN CLOUD (Cosmics Leaving Outdoor Droplets) chamber documented the formation of HIO 3 via iodooxy hypoiodite, IOIO, as an intermediate (Finkenzeller et al, 2022) and the fast growth of HIO 3 as (nano)particles (He et al, 2021).…”

Section: Surface Seawater and Atmospheric Formation Of Io 3 - And Iod...mentioning

confidence: 99%

Review on the physical chemistry of iodine transformations in the oceans

Luther

2023

Front. Mar. Sci.

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The transformation between iodate (IO3−), the thermodynamically stable form of iodine, and iodide (I-), the kinetically stable form of iodine, has received much attention because these species are often dependent on the oxygen concentration, which ranges from saturation to non-detectable in the ocean. As suboxic conditions in the ocean’s major oxygen minimum zones indicate that IO3− is minimal or non-detectable, the incorporation of IO3− into carbonate minerals has been used as a redox proxy to determine the O2 state of the ocean. Here, I look at the one and two electron transfers between iodine species with a variety of oxidants and reductants to show thermodynamics of these transformations. The IO3− to IO2− conversion is shown to be the controlling step in the reduction reaction sequence due to thermodynamic considerations. As IO3− reduction to IO2− is more favorable than NO3− reduction to NO2− at oceanic pH values, there is no need for nitrate reductase for IO3− reduction as other reductants (e.g. Fe2+, Mn2+) and dissimilatory IO3− reduction by microbes during organic matter decomposition can affect the transformation. Unfortunately, there is a dearth of information on the kinetics of reductants with IO3−; thus, the thermodynamic calculations suggest avenues for research. Conversely, there is significant information on the kinetics of I- oxidation with various oxygen species. In the environment, I- oxidation is the controlling step for oxidation. The oxidants that can lead to IO3− are reactive oxygen species with O3 and •OH being the most potent as well as sedimentary oxidized Mn, which occurs at lower pH than ocean waters. Recent work has shown that iodide oxidizing bacteria can also form IO3−. I- oxidation is more facile at the sea surface microlayer and in the atmosphere due to O3.

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

Cited by 30 publications

References 67 publications

Iodine oxoacids enhance nucleation of sulfuric acid particles in the atmosphere

Iodine oxoacids enhance nucleation of sulfuric acid particles in the atmosphere

Observed in-plume gaseous elemental mercury depletion suggests significant mercury scavenging by volcanic aerosols

Review on the physical chemistry of iodine transformations in the oceans

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