BrHgO• + C2H4 and BrHgO• + HCHO in Atmospheric Oxidation of Mercury: Determining Rate Constants of Reactions with Prereactive Complexes and Bifurcation.

Models suggest BrHgONO to be the major Hg(II) species formed in the global oxidation of Hg(0), and BrHgONO undergoes rapid photolysis to produce the thermally stable radical BrHgO•. We previously used quantum chemistry to demonstrate that BrHgO• can, like •OH radicals, readily abstract hydrogen atoms from sp3-hybridized carbon atoms as well as add to NO and NO2. In the present work, we reveal that BrHgO• can also add to C2H4 to form BrHgOCH2CH2•, although this addition appears to proceed with a lower rate constant than the analogous addition of •OH to C2H4. Additionally, BrHgO• can readily react with HCHO in two different ways: either by addition to carbon or by abstraction of a hydrogen atom. The minimum energy path for the BrHgO• + HCHO reaction bifurcates, forming two prereactive complexes, each of which passes over a separate transition state to form different products. Rate constants computed using Master Equation simulations indicate that hydrogen abstraction dominates over addition at atmospheric temperatures (200 K ≤ T ≤ 333 K) and pressures (0.01 atm ≤ P ≤ 1 atm). Subsequently, we compute the atmospheric fate of BrHgO• in a variety of air masses and find that BrHgOH formation via hydrogen abstraction will be the predominant fate (∼70-99%), with major competition (∼20%) coming from addition to NO and NO2 in polluted urban regions and stratospheric air. Given the absence of either field data on the identity of Hg(II) compounds or experimental data on the kinetics of BrHgO• reactions, the present manuscript should provide guidance to a range of scientists studying atmospheric mercury.

Computational Study on the Photolysis of BrHgONO and the Reactions of BrHgO• with CH4, C2H6, NO, and NO2: Implications for Formation of Hg(II) Compounds in the Atmosphere.

Global models suggest BrHgONO to be the major Hg(II) species initially formed in atmospheric oxidation of Hg(0) in most of the atmosphere, but its atmospheric fate has not been previously investigated. In the present work, we use quantum chemistry to predict that BrHgONO photolysis produces the thermally stable radical BrHgO•. Subsequently, BrHgO• may react with NO2 to form thermally stable BrHgONO2, or with NO to re-form BrHgONO. Additionally, BrHgO• abstracts hydrogen atoms from CH4 and C2H6 with higher rate constants than does •OH, producing a stable BrHgOH molecule. Because BrHgO• can abstract hydrogen atoms from sp3-hybridized carbons on many organic compounds, we expect production of BrHgOH to dominate globally, although formation of BrHgONO and BrHgONO2 may compete in urban regions. In the absence of experimental data on the kinetics and fate of BrHgONO and BrHgO•, we aim to guide modelers and other scientists in their search for Hg(II) compounds in the atmosphere.