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Environ Sci Technol. 2016 Feb 2;50(3):1280-7. doi: 10.1021/acs.est.5b05148. Epub 2016 Jan 22.

Production of Molecular Iodine and Tri-iodide in the Frozen Solution of Iodide: Implication for Polar Atmosphere.

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School of Environmental Science and Engineering, Pohang University of Science and Technology (POSTECH) , Pohang 790-784, Korea.
Korea Polar Research Institute (KOPRI) , Incheon 406-840, Korea.
Department of Molecular Engineering, Kyoto University , Kyoto 615-8510, Japan.
Department of Molecular and Material Sciences, Kyushu University , Kasuga, Fukuoka 816-8580, Japan.
Department of Atmospheric Chemistry and Climate, Institute of Physical Chemistry Rocasolano, CSIC , Madrid, Spain.
Department of Physical, Environmental and Computer Sciences Medgar Evers College-City, University of New York , Brooklyn, New York 11235, United States.


The chemistry of reactive halogens in the polar atmosphere plays important roles in ozone and mercury depletion events, oxidizing capacity, and dimethylsulfide oxidation to form cloud-condensation nuclei. Among halogen species, the sources and emission mechanisms of inorganic iodine compounds in the polar boundary layer remain unknown. Here, we demonstrate that the production of tri-iodide (I3(-)) via iodide oxidation, which is negligible in aqueous solution, is significantly accelerated in frozen solution, both in the presence and the absence of solar irradiation. Field experiments carried out in the Antarctic region (King George Island, 62°13'S, 58°47'W) also showed that the generation of tri-iodide via solar photo-oxidation was enhanced when iodide was added to various ice media. The emission of gaseous I2 from the irradiated frozen solution of iodide to the gas phase was detected by using cavity ring-down spectroscopy, which was observed both in the frozen state at 253 K and after thawing the ice at 298 K. The accelerated (photo-)oxidation of iodide and the subsequent formation of tri-iodide and I2 in ice appear to be related with the freeze concentration of iodide and dissolved O2 trapped in the ice crystal grain boundaries. We propose that an accelerated abiotic transformation of iodide to gaseous I2 in ice media provides a previously unrecognized formation pathway of active iodine species in the polar atmosphere.

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