From August 22 to September 16, 2012, atmospheric mercury (Hg) was measured from a common manifold in the field during the Reno Atmospheric Mercury Intercomparison eXperiment. Data were collected using Tekran systems, laser induced fluorescence, and evolving new methods. The latter included the University of Washington-Detector for Oxidized Mercury, the University of Houston Mercury instrument, and a filter-based system under development by the University of Nevada-Reno. Good transmission of total Hg was found for the manifold. However, despite application of standard protocols and rigorous quality control, systematic differences in operationally defined forms of Hg were measured by the sampling systems. Concentrations of reactive Hg (RM) measured with new methods were at times 2-to-3-fold higher than that measured by Tekran system. The low RM recovery by the latter can be attributed to lack of collection as the system is currently configured. Concentrations measured by all instruments were influenced by their sampling location in-the-manifold and the instrument analytical configuration. On the basis of collective assessment of the data, we hypothesize that reactions forming RM were occurring in the manifold. Results provide a new framework for improved understanding of the atmospheric chemistry of Hg.
Abstract. KCl-coated denuders have become a standard method for measurement of gaseous oxidized mercury, but their performance has not been exhaustively evaluated, especially in field conditions. In this study, KCl-coated and uncoated quartz denuders loaded with HgCl 2 and HgBr 2 lost 29-55% of these compounds, apparently as elemental mercury, when exposed to ozone (range of 6-100 ppb tested). This effect was also observed for denuders loaded with gaseous oxidized mercury at a field site in Nevada (3-37% of oxidized mercury lost). In addition, collection efficiency decreased by 12-30% for denuders exposed to 50 ppb ozone during collection of HgCl 2 . While data presented were obtained from laboratory tests and as such do not exactly simulate field sampling conditions, these results indicate that the KCl denuder oxidized mercury collection method may not be as robust as previously thought. This work highlights needs for further testing of this method, clear identification of gaseous oxidized mercury compounds in the atmosphere, and development of field calibration methods for these compounds.
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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