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Abstract: To better understand the methylation and demethylation of mercury (Hg) in the atmosphere, monomethyl mercury (MMHg) concentrations in wet deposition samples collected in the Minamata Bay area from September, 2009 to August, 2010 were determined. The concentrations of total Hg (dissolved Hg + particulate Hg) and dissolved reactive Hg were also measured. The volume-weighted mean concentrations of dissolved MMHg and total Hg were 0.061 and 5.9 ng L−1, respectively. Almost 90% of total Hg was in the dissolved phase and dissolved reactive Hg was the dominant Hg species in the wet deposition. The wet deposition fluxes of total Hg and reactive Hg increased in the rainy season (summer and fall), while the concentrations and wet deposition fluxes of MMHg were higher in winter and spring than in summer. Factors affecting this seasonal variation of MMHg were also considered. The MMHg in wet depositions may be decomposed by the increased levels of UV radiation in summer months, although MMHg can also be emitted from anthropogenic and biogenic sources and/or produced by photochemical reactions. Long-range transport from the Asian continent may also contribute to the seasonal variation of the wet MMHg deposition flux. [Copyright &y& Elsevier]

The variability of atmospheric mercury in elemental, reactive, and particulate forms has been studied at a remote site (Cape Hedo Observatory, CHO) at Okinawa Island (Japan) March 23 to May 2, 2004, downwind of the major Asian source regions. Under prevailing meteorological conditions, episodes of higher levels of atmospheric mercury and other atmospheric species are observed at CHO. The mean (±1σ) concentrations of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate-bound mercury (PHg) are 2.04±0.38ngm−3, 4.5±5.4pgm−3 and 3.0±2.5pgm−3, respectively. In Asian outflow the combined contribution of RGM and PHg constitutes less than 1% of the GEM in the boundary layer, which indicates that most mercury export in the marine boundary layer is due to the GEM form, and direct outflow of RGM and PHg is very low. While the data from Okinawa suggest minimal export of RGM and PHg, this does not preclude greater export of these species at higher elevations. Based on the correlations of PHg and submicron aerosol mass (SAM), we found a ΔPHg/ΔSAM ratio of 0.20μgg−1 (R =0.58, p <0.01), which we believe to be characteristic of East Asian industrial aerosols during outflow. A diurnal variation is observed in RGM with a peak near noon. Using a rate constant of 9×10−14 cm3 molecule−1 s−1 for the OH oxidation rate (Sommar, J., Gardfeldt, K., Stromberg, D., Feng, X., 2001. A kinetic study of the gas phase reaction between the hydroxyl radical and atomic mercury. Atmospheric Environment 35, 3049–3054; Pal, B., Ariya, P.A., 2004a. Gas-phase HO center dot-initiated reactions of elemental mercury: kinetics, product studies, and atmospheric implications. Environmental Science and Technology 38 (21), 5555–5566.) and a typical OH concentration of 1–5×106 cm−3 would result in RGM production rates of 0.6–3.0pgm−3 h−1. Although OH may not be the sole oxidant, this is consistent with the observed change in concentration during daytime of 1.4±1.5pgm−3 h−1. A significant correlation is found between GEM and CO; GEM and SAM; and PHg and SAM. Lower ΔSAM/ΔCO and ΔGEM/ΔCO are observed for transport events with rainfall and for air parcels remaining in the mixed layer. Back trajectory analysis along with the correlation study suggests that the air from China has a higher GEM concentration compared to the air coming from southern Japan. [Copyright &y& Elsevier]

Mercury wet deposition is dependent on both the scavenging of divalent reactive gaseous mercury (RGM) and atmospheric particulate mercury (Hg(p)) by precipitation. Estimating the contribution of precipitation scavenging of RGM and Hg(p) is important for better understanding the causes of the regional and seasonal variations in mercury wet deposition. In this study, the contribution of Hg(p) scavenging was estimated on the basis of the scavenging ratios of other trace elements (i. E. , Cd, Cu, Mn, Ni, Pb and V) existing entirely in particulate form. Their wet deposition fluxes and concentrations in air, which were measured concurrently from April 2004 to March 2005 at 10 sites in Japan, were used in this estimation. The monthly wet deposition flux of mercury at each site correlated with the amount of monthly precipitation, whereas the Hg(p) concentrations in air tended to decrease during summer. There was a significant correlation (P<0. 001) among the calculated monthly average scavenging ratios of trace elements, and the values in each month at each site were similar. Therefore, it is assumed the monthly scavenging ratio of Hg(p) is equivalent to the mean value of other trace elements. Using this scavenging ratio (W), the wet deposition flux (F) due to Hg(p) scavenging in each month was calculated by F=WKP, where K and P are the Hg(p) concentration and amount of precipitation, respectively. Relatively large fluxes due to Hg(p) scavenging were observed at a highly industrial site and at sites on the Japan Sea coast, which are strongly affected by the local sources and the long-range transport from the Asian continent, respectively. However, on average, at the 10 sites, the contribution of Hg(p) scavenging to the annual mercury deposition flux was 26%, suggesting that mercury wet deposition in Japan is dominated by RGM scavenging. This RGM should originate mainly from the in situ oxidation of Hg0 in the atmosphere. [Copyright &y& Elsevier]