The reaction between HgBr and O₃: kinetic study and atmospheric implications

The rate constants of many reactions currently considered to be important in the atmospheric chemistry of mercury remain to be measured in the laboratory. Here we report the first experimental determination of the rate constant of the gas-phase reaction between the HgBr radical and ozone, for which a value at room temperature of k(HgBr + O₃) = (7.5 ± 0.6) × 10^-11 cm³ molecule s^-1 (1σ) has been obtained. The rate constants of two reduction side reactions were concurrently determined: k(HgBr + O) = (5.3 ± 0.4) × 10^-11 cm³ molecule s^-1 and k(HgBrO + O) = (9.1 ± 0.6) × 10^-11 cm³ molecule s^-1. The value of k(HgBr + O₃) is slightly lower than the collision number, confirming the absence of a significant energy barrier. Considering the abundance of ozone in the troposphere, our experimental rate constant supports recent modelling results suggesting that the main atmospheric fate of HgBr is reaction with ozone to form BrHgO.