Atmospheric Chemistry of HOHg(II)O• Mimics That of a Hydroxyl Radical.

Abstract

HOHg(II)O•, formed from HOHg(I)• + O3, is a key intermediate in the OH-initiated oxidation of Hg(0) in the atmosphere. As no experimental data are available for HOHg(II)O•, we use computational chemistry (CCSD(T)//M06-2X/AVTZ) to characterize its reactions with atmospheric trace gases (NO, NO2, CH4, C2H4, CH2O and CO). In summary, HOHg(II)O•, like the analogous BrHg(II)O• radical, largely mimics the reactivity of •OH in reactions with NOx, alkanes, alkenes, and aldehydes. The rate constant for its reaction with methane (HOHg(II)O• + CH4 → Hg(II)(OH)2 + •CH3) is about four times higher than that of •OH at 298 K. All of these reactions maintain mercury as Hg(II), except for HOHg(II)O• + CO → HOHg(I)• + CO2. Considering only the six reactions studied here, we find that reduction by CO dominates the fate of HOHg(II)O• (79-93%) in many air masses (in the stratosphere and at ground level in rural, marine, and polluted urban regions) with only modest competition from HOHg(II)O• + CH4 (<15%). We expect that this work will help global modeling of atmospheric mercury chemistry.