Abiotic formation of methyl iodide on synthetic birnessite: A mechanistic study

Methyl iodide is a well-known volatile halogenated organic compound that contributes to the iodine content in the troposphere, potentially resulting in damage to the ozone layer. Most methyl iodide sources derive from biological activity in oceans and soils with very few abiotic mechanisms proposed...

Full description

Bibliographic Details
Main Authors: Allard, Sebastien, Gallard, H.
Format: Journal Article
Published: Elsevier 2013
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/34566
_version_ 1848754257799413760
author Allard, Sebastien
Gallard, H.
author_facet Allard, Sebastien
Gallard, H.
author_sort Allard, Sebastien
building Curtin Institutional Repository
collection Online Access
description Methyl iodide is a well-known volatile halogenated organic compound that contributes to the iodine content in the troposphere, potentially resulting in damage to the ozone layer. Most methyl iodide sources derive from biological activity in oceans and soils with very few abiotic mechanisms proposed in the literature. In this study we report that synthetic manganese oxide (birnessite δ-MnO2) can catalyze the formation of methyl iodide in the presence of natural organic matter (NOM) and iodide. Methyl iodide formation was only observed at acidic pH (4–5) where iodide is oxidized to iodine and NOM is adsorbed on δ-MnO2. The effect of δ-MnO2, iodide and NOM concentrations, nature of NOM and ionic strength was investigated. High concentrations of methyl iodide were formed in experiments conducted with the model compound pyruvate. The Lewis acid property of δ-MnO2 leads to a polarization of the iodine molecule, and catalyzes the reaction with natural organic matter. As manganese oxides are strong oxidants and are ubiquitous in the environment, this mechanism could significantly contribute to the global atmospheric input of iodine.
first_indexed 2025-11-14T08:37:32Z
format Journal Article
id curtin-20.500.11937-34566
institution Curtin University Malaysia
institution_category Local University
last_indexed 2025-11-14T08:37:32Z
publishDate 2013
publisher Elsevier
recordtype eprints
repository_type Digital Repository
spelling curtin-20.500.11937-345662019-02-19T04:28:02Z Abiotic formation of methyl iodide on synthetic birnessite: A mechanistic study Allard, Sebastien Gallard, H. Iodide Volatile halogenated organic compound Natural organic matter Atmospheric iodine Iodine Manganese oxide Methyl iodide is a well-known volatile halogenated organic compound that contributes to the iodine content in the troposphere, potentially resulting in damage to the ozone layer. Most methyl iodide sources derive from biological activity in oceans and soils with very few abiotic mechanisms proposed in the literature. In this study we report that synthetic manganese oxide (birnessite δ-MnO2) can catalyze the formation of methyl iodide in the presence of natural organic matter (NOM) and iodide. Methyl iodide formation was only observed at acidic pH (4–5) where iodide is oxidized to iodine and NOM is adsorbed on δ-MnO2. The effect of δ-MnO2, iodide and NOM concentrations, nature of NOM and ionic strength was investigated. High concentrations of methyl iodide were formed in experiments conducted with the model compound pyruvate. The Lewis acid property of δ-MnO2 leads to a polarization of the iodine molecule, and catalyzes the reaction with natural organic matter. As manganese oxides are strong oxidants and are ubiquitous in the environment, this mechanism could significantly contribute to the global atmospheric input of iodine. 2013 Journal Article http://hdl.handle.net/20.500.11937/34566 10.1016/j.scitotenv.2013.05.079 Elsevier fulltext
spellingShingle Iodide
Volatile halogenated organic compound
Natural organic matter
Atmospheric iodine
Iodine
Manganese oxide
Allard, Sebastien
Gallard, H.
Abiotic formation of methyl iodide on synthetic birnessite: A mechanistic study
title Abiotic formation of methyl iodide on synthetic birnessite: A mechanistic study
title_full Abiotic formation of methyl iodide on synthetic birnessite: A mechanistic study
title_fullStr Abiotic formation of methyl iodide on synthetic birnessite: A mechanistic study
title_full_unstemmed Abiotic formation of methyl iodide on synthetic birnessite: A mechanistic study
title_short Abiotic formation of methyl iodide on synthetic birnessite: A mechanistic study
title_sort abiotic formation of methyl iodide on synthetic birnessite: a mechanistic study
topic Iodide
Volatile halogenated organic compound
Natural organic matter
Atmospheric iodine
Iodine
Manganese oxide
url http://hdl.handle.net/20.500.11937/34566