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Title: 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 » 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.« less

Authors:
 [1]; ORCiD logo [2];  [1]; ORCiD logo [3];  [4];  [4]
  1. Institute of Physical Chemistry Rocasolano, CSIC, Madrid (Spain)
  2. Univ. of Leeds, Leeds (United Kingdom)
  3. Indian Institute of Tropical Meteorology, Pune (India)
  4. 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}
}

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Cited by: 25 works
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Works referenced in this record:

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journal, January 2010


Latitudinal distribution of reactive iodine in the Eastern Pacific and its link to open ocean sources
journal, January 2012


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journal, January 2004


A theoretical study of the kinetics of the forward and reverse reactions HI+CH3=I+CH4
journal, December 2011


Rate constant of the reaction of NO3 with CH2I2 measured with use of cavity ring-down spectroscopy
journal, October 2006


Marine aerosol formation from biogenic iodine emissions
journal, June 2002


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journal, January 2012


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journal, January 2015


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journal, January 2015


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journal, June 2008


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Accommodation coefficient of HOBr on deliquescent sodium bromide aerosol particles
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Enhanced production of oxidised mercury over the tropical Pacific Ocean: a key missing oxidation pathway
journal, January 2014


Iodine monoxide in the Western Pacific marine boundary layer
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Bromine partitioning in the tropical tropopause layer: implications for stratospheric injection
journal, January 2014


Iodine chemistry in the troposphere and its effect on ozone
journal, January 2014


A negative feedback between anthropogenic ozone pollution and enhanced ocean emissions of iodine
journal, January 2014


Observations of I2 at a remote marine site
posted_content, October 2013


Accommodation coefficient of HOBr on deliquescent sodium bromide aerosol particles
posted_content, January 2002


Reactive Halogens in the Marine Boundary Layer (RHaMBLe): the tropical North Atlantic experiments
posted_content, October 2009


Latitudinal distribution of reactive iodine in the Eastern Pacific and its link to open ocean sources
posted_content, June 2012


A theoretical study of the kinetics of the forward and reverse reactions HI+CH3=I+CH4
journal, December 2011


A Density Functional Theory and ab Initio Investigation of the Oxidation Reaction of CO by IO Radicals
journal, March 2016


Stochastic models of the interconversion of three or more chemical species
journal, May 1974


Enhanced production of oxidised mercury over the tropical Pacific Ocean: a key missing oxidation pathway
journal, January 2014


A laboratory characterisation of inorganic iodine emissions from the sea surface: dependence on oceanic variables and parameterisation for global modelling
journal, January 2014


Direct evidence for coastal iodine particles from Laminaria macroalgae – linkage to emissions of molecular iodine
journal, January 2004


Iodine chemistry in the troposphere and its effect on ozone
journal, January 2014


Accommodation coefficient of HOBr on deliquescent sodium bromide aerosol particles
posted_content, January 2002


Reactive Halogens in the Marine Boundary Layer (RHaMBLe): the tropical North Atlantic experiments
posted_content, October 2009


Works referencing / citing this record:

A theoretical study of the microhydration processes of iodine nitrogen oxides
journal, October 2018


Rapid increase in atmospheric iodine levels in the North Atlantic since the mid-20th century
journal, April 2018


Organic bromine compounds produced in sea ice in Antarctic winter
journal, December 2018


Natural halogens buffer tropospheric ozone in a changing climate
journal, January 2020


Evidence for renoxification in the tropical marine boundary layer
journal, January 2017


Diurnal cycle of iodine, bromine, and mercury concentrations in Svalbard surface snow
journal, January 2019


Evidence for renoxification in the tropical marine boundary layer
posted_content, January 2017


Rapid increase in atmospheric iodine levels in the North Atlantic since the mid-20th century
journal, April 2018


Organic bromine compounds produced in sea ice in Antarctic winter
journal, December 2018


Diurnal cycle of iodine, bromine, and mercury concentrations in Svalbard surface snow
journal, January 2019


Evidence for renoxification in the tropical marine boundary layer
posted_content, January 2017


Characterization of aerosol number size distributions and their effect on cloud properties at Syowa Station, Antarctica
journal, August 2021


Characterization of aerosol number size distributions and their effect on cloud properties at Syowa Station, Antarctica
journal, August 2021