In the atmosphere, reactive forms of mercury species can be produced by oxidation of the dominant gaseous elemental mercury (GEM). The oxidation of GEM is an important driver for deposition, but oxidation pathways currently are poorly constrained and likely differ among regions. In this study, continuous measurements of atmospheric nitrate radical (NO3) concentrations and mercury speciation (i.e., elemental and reactive, oxidized forms) were performed during a six week period in the urban air shed of Jerusalem, Israel during summer 2012, to investigate the potential nighttime contribution of nitrate radicals to oxidized mercury formation. Average nighttime concentrations of reactive gaseous mercury (RGM) were almost equivalent to daytime levels (25 pg m(-3) and 27 pg m(-3) respectively), in contrast to early morning and evening RGM levels which dropped to low levels (9 and 13 pg m(-3)). During daytime, the presence of RGM was increased when solar radiation exceeded 200 W m(-2), suggesting a photochemical process for daytime RGM formation. Ozone concentrations were largely unrelated to daytime RGM. Nighttime RGM concentrations were relatively high (with a maximum of 97 pg m(-3)) compared to nighttime levels in other urban regions. A strong correlation was observed between nighttime RGM concentrations and nitrate radical concentration (R(2) averaging 0.47), while correlations to other variables were weak (e.g., RH; R(2) = 0.35) or absent (e.g., ozone, wind speed and direction, pollution tracers such as CO or SO2). Detailed analyses suggest that advection processes or tropospheric influences were unlikely to explain the strong nighttime correlations between NO3 and RGM, although these processes may contribute to these relationships. Our observations suggest that NO3 radicals may play a role in RGM formation, possibly due to a direct chemical involvement in GEM oxidation. Since physical data, however, suggest that NO3 unlikely initiates GEM oxidation, NO3 may play a secondary role in GEM oxidation through the addition to an unstable Hg(I) radical species.
Deposition of atmospheric mercury is of global concern, primarily due to health effects associated with efficient bioaccumulation of mercury in marine food webs. Although oxidation of gaseous elementary mercury (GEM), the major fraction of atmospheric mercury, is a critical stage in regulating atmospheric mercury deposition efficiency, this oxidation is currently not well-characterized, limiting modeling-based assessments of mercury in the environment. Based on a previous study, we hypothesized that the oxidation of GEM is predominantly controlled by multistep bromine-and chlorine-induced oxidation (MBCO) in the remote marine boundary layer (RMBL), and by photochemical smog oxidants, primarily ozone (O 3 ) and hydroxyl radical (OH), in the polluted continental boundary layer (PCBL). To test this hypothesis, we used the following analyses: (i) application of a newly developed criterion to evaluate the gaseous oxidized mercury (GOM)-O 3 association based on previous studies in the RMBL and PCBL; (ii) measurement-based box simulations of GEM oxidation in the RMBL and at a PCBL site; and (iii) measurement-based analysis of photochemical oxidation vs. other processes which potentially influence GOM. Our model simulations indicated that the MBCO mechanism can reproduce GOM levels in the RMBL, but not in the PCBL. Our data analysis suggested the important role of photochemical smog oxidants in GEM oxidation in the PCBL, potentially masked by the effect of relative humidity and entrainment of free tropospheric air.
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