nighttime atmospheric chemistry of iodine
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ID: 174228
2016
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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 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. The effect of this is exemplified by the indirect effect on
dimethyl sulfide (DMS) oxidation.
| Reference Key |
saiz-lopez2016atmosphericnighttime
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|---|---|
| Authors | ;A. Saiz-Lopez;J. M. C. Plane;C. A. Cuevas;A. S. Mahajan;J.-F. Lamarque;D. E. Kinnison |
| Journal | Journal of agricultural and food chemistry |
| Year | 2016 |
| DOI |
10.5194/acp-16-15593-2016
|
| URL | |
| Keywords |
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