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Currently there is no standard method for measurement of atmospheric mercury dry deposition. While all operationally defined forms of atmospheric mercury (elemental, oxidized, and particulate) can be dry deposited, oxidized forms are of concern due to high deposition velocities, water solubility, and reactivity. This paper describes the development of a surrogate surface for characterizing potential dry deposition of gaseous oxidized mercury (GOM). Laboratory tests showed that the surface collected HgCl2, HgBr2, and HgO with equal efficiency, and deposition was not significantly influenced by temperature, humidity, or ozone concentrations. Deposition of mercury to surfaces in field deployments was correlated with GOM concentrations (r2 = 0.84, p < 0.01, n = 326. Weekly mean GOM deposition velocities from surface deployments (1.1 +/- 0.6 cm s(-1)) were higher than modeled values (0.4 +/- 0.2 cm s(-1)) at four field sites, but were within the range reported for direct measurements. Although the surfaces do not simulate the heterogeneity of natural surfaces and need to be validated by direct measurements, they do provide a physical means for estimating temporal trends and spatial variability of dry deposition of GOM.

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Atmospheric models and limited measurements indicate that dry deposition of atmospheric mercury is an important process by which mercury is input to ecosystems. To begin to fill the measurement data gap, multiple methods were used simultaneously during seasonal campaigns conducted in 2005 and 2006 to estimate dry deposition of atmospheric mercury at two Mercury Deposition Network (MDN) sites in rural Nevada and in Reno, Nevada. Gaseous elemental mercury (Hg0), reactive gaseous mercury (RGM), and particulate-bound mercury (Hgp) concentrations were measured using Tekran 2537A/1130/ 1135 systems. These speciated measurements were combined with on-site meteorological measurements to estimate depositional fluxes of RGM and Hgp using dry deposition models. Modeled fluxes were compared with more direct measurements obtained using polysulfone cation-exchange membranes and foliar surfaces. Dynamic flux chambers were used to measure soil mercury exchange. RGM concentrations were higher during warmer months at all sites, leading to seasonal variation in the modeled importance of RGM as a component of total depositional load. The ratio of dry to wet deposition was between 10 and 90%, and varied with season and with the methods used for dry deposition approximations. This work illustrates the variability of mercury dry deposition with location and time and highlights the need for direct dry deposition measurements.

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The rigorous validation of a previously developed research method for the determination of dimethyl mercury ((CH3)2Hg) in environmental samples is presented. During atmospheric analysis, (CH3)2Hg was trapped on Carbotrap™ and analyzed by thermal desorption, isothermal GC separation, and cold vapor atomic fluorescence spectrometry (CVAFS). Water samples were analyzed after direct purging of 100mL aliquots onto Carbotrap™, while sediment and tissue samples were digested with 10mL of 25% KOH in methanol at 60°C and diluted to 40mL with methanol. An ambient air-spiking manifold, which allowed simultaneous replicate sampling, was constructed in a room controlled for temperature and humidity. (CH3)2Hg was introduced into the feed airflow (0.4m3min-1) from a well-calibrated diffusion cell, to obtain a concentration of approximately 5.5ngm-3 as Hg. Samples were collected onto Carbotrap™ columns, and the total volumes quantified by integrating mass flow meters. Trapping efficiency was investigated over a range of sampler flow rates (0.05-0.25Lmin-1), volumes (2-200L), collection temperatures (15-42°C) and relative humidity levels (10-70%). Method detection limits (MDLs), analytical precision and accuracy were quantified for all media. Carbotrap™ was found to be the best choice as a sampling media, whereas Tenax™ was found to be inadequate due to high breakthrough (>70%). This study verified that the method is sufficiently precise, accurate and robust for field sampling at mercury contaminated sites. No interferences were observed from elevated levels of potential co-contaminants, Hg0 (125ngm-3) and H2S (1.27ppmv).

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In this study, gas-phase elemental mercury (Hg0) and related species (including inorganic reactive gaseous mercury (RGM) and particulate mercury (PHg)) were measured at Cheeka Peak Observatory (CPO), Washington State, in the marine boundary layer during 2001-2002. Air of continental origin containing anthropogenic pollutants from the urban areas to the east contained on average 5.3% lower Hg0 levels as compared to the marine background. This result is difficult to reconcile since it is known that industrial emissions in our region are sources of Hg0. The rate of removal of Hg0 from a pollution plume necessary to account for our observations is inconsistent with the accepted view of Hg0 as a stable atmospheric pollutant. The largest and most frequent Hg0 loss events occurred in the presence of increased ozone (O3) during the summer. Hg0 and O3 also display diurnal cycles that are out-of-phase with one another. In other seasons Hg0 behavior is less consistent, as we observe weak positive correlations with O3 and occasional Hg0 enhancements in local pollution. RGM and PHg concentrations are enhanced only slightly during Hg0 loss events, comprising a small fraction of the mercury pool (approximately 3%). Long-range transported pollution of Asian origin was also detected at CPO, and this contains both higher and lower levels of Hg0 as compared to the background with maximum changes being <20%. Here, the more photochemically processed the air mass, as determined by propane/ethane ratios, the more likely we are to observe Hg0 loss. Air from the marine background in summer displays a significant diurnal cycle with a phase that matches the diurnal cycles seen in polluted air masses. A Junge lifetime for Hg0 in the clean marine boundary layer is calculated to be 7.1 months, which is on the low end of previous estimates (0.5-2 yr).

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Atmospheric mercury is predominantly present in the gaseous elemental form (Hg0). However, anthropogenic emissions (e.g., incineration, fossil fuel combustion) emit and natural processes create particulate-phase mercury(Hg(p)) and divalent reactive gas-phase mercury (RGM). RGM species (e.g., HgCl2, HgBr2) are water-soluble and have much shorter residence times in the atmosphere than Hg0 due to their higher removal rates through wet and dry deposition mechanisms. Manual and automated annular denuder methodologies, to provide high-resolution (1-2 h) ambient RGM measurements, were developed and evaluated. Following collection of RGM onto KCl-coated quartz annular denuders, RGM was thermally decomposed and quantified as Hg0. Laboratory and field evaluations of the denuders found the RGM collection efficiency to be >94% and mean collocated precision to be <15%. Method detection limits for sampling durations ranging from 1 to 12 h were 6.2-0.5 pg m(-3), respectively. As part of this research, the authors observed that methods to measure Hg(p) had a significant positive artifact when RGM coexists with Hg(p). This artifact was eliminated if a KCl-coated annular denuder preceded the filter. This new atmospheric mercury speciation methodology has dramatically enhanced our ability to investigate the mechanisms of transformation and deposition of mercury in the atmosphere.

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