Knowledge of atmospheric mercury speciation is critical to understanding its fate once released from point sources. The water-soluble compounds of Hg that exist in flue gases (termed reactive gaseous mercury, RGM) are subject to far greater local removal rates than is elemental Hg vapor, but few ambient air data exist. We developed a method using refluxing mist chambers to quantify the airborne concentrations of RGM in more than 250 ∼1-h samples under ambient conditions and summarize here the results of several RGM sampling campaigns in Tennessee and Indiana from 1992 to 1995. Measured levels of RGM were generally on the order of 50−200 pg/m3, representing about 3% of total gaseous mercury (TGM) and generally exceeding regional particulate Hg concentra tions. RGM exhibits significant correlations (p < 0.05) with temperature, solar radiation, O3, SO2, and TGM, suggesting seasonal trends similar to those of other regional air pollutants. The concentrations of RGM show reproducible diel trends, peaking during midday and decreasing sharply at night. A sharp spike in RGM was measured during a local plume impaction event in Tennessee. Concentration gradients over vegetation suggested a strong ground-level sink for RGM, and RGM concentrations decreased sharply during rain events, as expected for a water-soluble gas. The levels of RGM measured here support the hypothesis that Hg dry and wet deposition may be strongly influenced by the behavior of RGM and that elevated ecosystem exposure may be possible near major point sources of RGM compounds.

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.

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Wet deposition of nitrogen compounds was measured and dry and cloud water deposition were estimated at 11 forested sites in North America and one site in Europe. Dry deposition was a significant pathway of N input to all the forests, averaging 46% of the total deposition. At most of these sites, NH4+ was the dominant form of fixed N in the air, but HNO3 vapor dominated the dry deposition of N. Coarse-particle deposition was often important, but fine-particle deposition usually contributed only a small amount of the dry-deposited N. The deposition rates of inorganic N, which ranged between 4.8 and 27 kg N•ha−1•year−1, were generally much higher than has been reported by other studies measuring only wet or bulk deposition. The highest deposition rates were at the high-elevation sites in the southeastern and northeastern United States and much of the deposition at these sites was attributed to cloud water. Throughfall and stemflow (TF + SF) flux was also measured at all sites, and the net canopy exchange (NCE = (TF + SF)–total deposition) was found to be negative (indicating consumption of N in the canopy) for NH4+ and NO3−, and positive (indicating canopy release) for organic N. Past reports of canopy release of NO3− can probably be attributed to washoff of dry-deposited NO3− species. Consumption of inorganic N in the canopy ranged from 1 to 12 kg N•ha−1•year−1, and was highest in the spruce and spruce–fir stands. When organic N was included in the canopy N balance, the net canopy uptake of N was generally < 15% of the total system N requirement. Total N deposition was a linear function of wet deposition for low-elevation sites, and dry deposition was a linear function of the net throughfall flux for NO3−.

Airborne particles and vapors contributed significantly to the nutrient requirements and the pollutant load of a mixed hardwood forest in the eastern United States. Dry deposition was an important mechanism of atmospheric input to the foliar canopy, occurring primarily by vapor uptake for sulfur, nitrogen, and free acidity and by particle deposition for calcium and potassium. The canopy retained 50 to 70 percent of the deposited free acidity and nitrogen, but released calcium and potassium. Atmospheric deposition supplied 40 and 100 percent of the nitrogen and sulfur requirements, respectively, for the annual woody increment. This contribution was underestimated significantly by standard bulk deposition collectors.