Nighttime atmospheric chemistry of iodine
Abstract
Little attention has so far been paid to the nighttime atmospheric chemistry of iodine species. Current atmospheric models predict a buildup of HOI and I2 during the night that leads to a spike of IO at sunrise, which is not observed by measurements. In this work, electronic structure calculations are used to survey possible reactions that HOI and I2 could undergo at night in the lower troposphere, and hence reduce their nighttime accumulation. The new reaction NO3+ HOI → IO + HNO3 is proposed, with a rate coefficient calculated from statistical rate theory over the temperature range 260–300 K and at a pressure of 1000 hPa to be k(T) = 2.7 × 10-12 (300 K/T)2.66 cm3 molecule-1 s-1. This reaction is included in two atmospheric models, along with the known reaction between I2 and NO3, to explore a new nocturnal iodine radical activation mechanism. The results show that this iodine scheme leads to a considerable reduction of nighttime HOI and I2, which results in the enhancement of more than 25 % of nighttime ocean emissions of HOI + I2 and the removal of the anomalous spike of IO at sunrise. We suggest that active nighttime iodine can also have amore »
- Authors:
-
- Institute of Physical Chemistry Rocasolano, CSIC, Madrid (Spain)
- Univ. of Leeds, Leeds (United Kingdom)
- Indian Institute of Tropical Meteorology, Pune (India)
- National Center for Atmospheric Research, Boulder, CO (United States)
- Publication Date:
- Research Org.:
- Institute of Physical Chemistry Rocasolano, CSIC, Madrid (Spain). Dept. of Atmospheric Chemistry and Climate
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1375402
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Atmospheric Chemistry and Physics (Online)
- Additional Journal Information:
- Journal Volume: 16; Journal Issue: 24; Journal ID: ISSN 1680-7324
- Publisher:
- European Geosciences Union
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES
Citation Formats
Saiz-Lopez, Alfonso, Plane, John M. C., Cuevas, Carlos A., Mahajan, Anoop S., Lamarque, Jean -Francois, and Kinnison, Douglas E. Nighttime atmospheric chemistry of iodine. United States: N. p., 2016.
Web. doi:10.5194/acp-16-15593-2016.
Saiz-Lopez, Alfonso, Plane, John M. C., Cuevas, Carlos A., Mahajan, Anoop S., Lamarque, Jean -Francois, & Kinnison, Douglas E. Nighttime atmospheric chemistry of iodine. United States. https://doi.org/10.5194/acp-16-15593-2016
Saiz-Lopez, Alfonso, Plane, John M. C., Cuevas, Carlos A., Mahajan, Anoop S., Lamarque, Jean -Francois, and Kinnison, Douglas E. 2016.
"Nighttime atmospheric chemistry of iodine". United States. https://doi.org/10.5194/acp-16-15593-2016. https://www.osti.gov/servlets/purl/1375402.
@article{osti_1375402,
title = {Nighttime atmospheric chemistry of iodine},
author = {Saiz-Lopez, Alfonso and Plane, John M. C. and Cuevas, Carlos A. and Mahajan, Anoop S. and Lamarque, Jean -Francois and Kinnison, Douglas E.},
abstractNote = {Little attention has so far been paid to the nighttime atmospheric chemistry of iodine species. Current atmospheric models predict a buildup of HOI and I2 during the night that leads to a spike of IO at sunrise, which is not observed by measurements. In this work, electronic structure calculations are used to survey possible reactions that HOI and I2 could undergo at night in the lower troposphere, and hence reduce their nighttime accumulation. The new reaction NO3+ HOI → IO + HNO3 is proposed, with a rate coefficient calculated from statistical rate theory over the temperature range 260–300 K and at a pressure of 1000 hPa to be k(T) = 2.7 × 10-12 (300 K/T)2.66 cm3 molecule-1 s-1. This reaction is included in two atmospheric models, along with the known reaction between I2 and NO3, to explore a new nocturnal iodine radical activation mechanism. The results show that this iodine scheme leads to a considerable reduction of nighttime HOI and I2, which results in the enhancement of more than 25 % of nighttime ocean emissions of HOI + I2 and the removal of the anomalous spike of IO at sunrise. We suggest that active nighttime iodine can also have a considerable, so far unrecognized, impact on the reduction of the NO3 radical levels in the marine boundary layer (MBL) and hence upon the nocturnal oxidizing capacity of the marine atmosphere. In conclusion, the effect of this is exemplified by the indirect effect on dimethyl sulfide (DMS) oxidation.},
doi = {10.5194/acp-16-15593-2016},
url = {https://www.osti.gov/biblio/1375402},
journal = {Atmospheric Chemistry and Physics (Online)},
issn = {1680-7324},
number = 24,
volume = 16,
place = {United States},
year = {Mon Dec 19 00:00:00 EST 2016},
month = {Mon Dec 19 00:00:00 EST 2016}
}
Web of Science
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