Abstract

This review focuses on providing the history of measurement efforts to quantify and characterize the compounds of reactive mercury (RM), and the current status of measurement methods and knowledge. RM collectively represents gaseous oxidized mercury (GOM) and that bound to particles. The presence of RM was first recognized through measurement of coal-fired power plant emissions. Once discovered, researchers focused on developing methods for measuring RM in ambient air. First, tubular KCl-coated denuders were used for stack gas measurements, followed by mist chambers and annular denuders for ambient air measurements. For ~15 years, thermal desorption of an annular KCl denuder in the Tekran® speciation system was thought to be the gold standard for ambient GOM measurements. Research over the past ~10 years has shown that the KCl denuder does not collect GOM compounds with equal efficiency, and there are interferences with collection. Using a membrane-based system and an automated system—the Detector for Oxidized mercury System (DOHGS)—concentrations measured with the KCl denuder in the Tekran speciation system underestimate GOM concentrations by 1.3 to 13 times. Using nylon membranes it has been demonstrated that GOM/RM chemistry varies across space and time, and that this depends on the oxidant chemistry of the air. Future work should focus on development of better surfaces for collecting GOM/RM compounds, analytical methods to characterize GOM/RM chemistry, and high-resolution, calibrated measurement systems.

Highlights

  • These results showed that the denuder collected more gaseous oxidized mercury (GOM) [19]; the quartz fiber filter could have influenced the amount of GOM collected on the ion exchange membrane [8,29,30]

  • Another Tekran system simultaneously measured Hg in ambient air that passed through KCl denuders, and it was assumed GOM was scrubbed by the denuder

  • Novel technologies and alternate methods tested during the comparison were the: University of Washington Detector for Oxidized Hg Species (DOHGS; [45]); University of Houston Mercury instrument (UHMERC); University of Miami Laser Induced Fluorescence (LIF; [46]); cavity ring-down spectroscopy system (Desert Research Institute); and nylon membranes

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Summary

Discovery of GOM

Mercury (Hg) exists in the atmosphere as three forms: gaseous elemental (GEM), gaseous oxidized (GOM), and particulate-bound (PBM). The atmospheric Hg research community focused on development of methods for GEM and did not know GOM existed. In 1996, in a critical review paper on Hg speciation in flue gases associated with coal combustion, Galbreath and Zygarlicke [12] pointed out that a variety of RM compounds should exist, including Cl-, O-, and S-based compounds.

Early Development of Methods
Early Method Intercomparisons
Work Pointing to Issues with the Tekran Speciation System
Surrogate Surface Data
Additional
Development of New Methods
Additional Tests Following or Associated with RAMIX
Dual Channel Systems
Other Work Using CEM
Mass Spectrometric Methods
Oxidized Mercury Calibration Systems
What We Have Learned
Findings
Work Needed
Full Text
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