Heterogeneous Reduction Pathways for Hg(II) Species on Dry Aerosols: A First-Principles Computational Study

Tacey, Sean A.; Xu, Lang; Mavrikakis, Manos; Schauer, James J.

doi:10.1021/acs.jpca.5b12769

Title: Heterogeneous Reduction Pathways for Hg(II) Species on Dry Aerosols: A First-Principles Computational Study

Journal Article · Fri Mar 25 00:00:00 EDT 2016 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.5b12769· OSTI ID:1395564

Tacey, Sean A. ^[1]; Xu, Lang ^[1]; Mavrikakis, Manos ^[1]; Schauer, James J. ^[1]

Univ. of Wisconsin-Madison, Madison, WI (United States)

Here, the atmospheric lifetime of mercury is greatly impacted by redox chemistry resulting from the high deposition rate of reactive mercury (Hg(II)) compared to elemental mercury (Hg⁰). Recent laboratory and field studies have observed the reduction of Hg(II) but the chemical mechanism for this reaction has not been identified. Recent laboratory studies have shown that the reduction reaction is heterogeneous and can occur on iron and sodium chloride aerosol surfaces. This study explores the use of density functional theory calculations to discern the reduction pathways of HgCl₂, HgBr₂, Hg(NO₃)₂, and HgSO₄ on clean Fe(110), NaCl(100), and NaCl(111)^Na surfaces. In doing so, potential energy surfaces have been prepared for the various reduction pathways, indicating that the reduction pathway leading to the production of gas-phase elemental mercury is highly favorable on Fe(110) and NaCl(111)^Na. Moreover, the Fe(110) surface requires an external energy source of approximately 0.5 eV to desorb the reduced mercury, whereas the NaCl(111)^Na surface requires no energy input. The results indicate that a number of mercury species can be reduced on metallic iron and sodium chloride surfaces, which are known aerosol components, and that a photochemical reaction involving the aerosol surface is likely needed for the reaction to be catalytic.

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Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15731

OSTI ID:: 1395564

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 120, Issue 13; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 9 works

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