Effects of relative humidity and CO(g) on the O3-initiated oxidation reaction of Hg0(g): kinetic & product studies

Ozone is assumed to be the predominant tropospheric oxidant of gaseous elemental mercury (Hg0(g)), defining mercury global atmospheric lifetime. In this study we have examined the effects of two atmospherically relevant polar compounds, H2O(g) and CO(g), on the absolute rate coefficient of the O3-initiated oxidation of Hg0(g), at 296 +/- 2 K using gas chromatography coupled to mass spectrometry (GC-MS). In CO-added experiments, we observed a significant increase in the reaction rate that could be explained by pure gas-phase chemistry. In contrast, we found the apparent rate constant, k(net), varied with the surface-to-volume ratio (0.6 to 5.5 L flasks) in water-added experiments. We have observed small increases in k(net) for nonzero relative humidity, RH < 100%, but substantial increase at RH > or = 100%. Product studies were performed using mass spectrometry and high resolution transmission electron microscopy coupled to an electron dispersive spectrometer (HRTEM-EDS). Our results give evidence for enhanced chain growth of HgO(s) on a carbon grid at RH = 50%. A water/surface/ozone independent ozone oxidation rate is estimated to be (6.2 +/- (1.1; tsigma/ radicaln) x 10(-19) cm3 molecule(-1) s(-1). The total uncertainty associated with the ensemble of experiments amount to approximately < or = 20%. The atmospheric implications of our results and the effect of an added reaction partner in homogeneous and heterogeneous atmospheric chemistry will be discussed.