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. Mercury (Hg) is a global health concern due to its toxicity and ubiquitous presence in the environment. Here we review current methods for measuring the forms of Hg in the atmosphere and models used to interpret these data. There are three operationally defined forms of atmospheric Hg: gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and particulate bound mercury (PBM). There is relative confidence in GEM measurements (collection on a gold surface), but GOM (collection on potassium chloride (KCl)-coated denuder) and PBM (collected using various methods) are less well understood. Field and laboratory investigations suggest the methods to measure GOM and PBM are impacted by analytical interferences that vary with environmental setting (e.g., ozone, relative humidity), and GOM concentrations measured by the KCl-coated denuder can be too low by a factor of 1.6 to 12 depending on the chemical composition of GOM. The composition of GOM (e.g., HgBr2, HgCl2, HgBrOH) varies across space and time. This has important implications for refining existing measurement methods and developing new ones, model/measurement comparisons, model development, and assessing trends. Unclear features of previously published data may now be re-examined and possibly explained, which is demonstrated through a case study. Priorities for future research include identification of GOM compounds in ambient air and development of information on their chemical and physical properties and GOM and PBM calibration systems. With this information, identification of redox mechanisms and associated rate coefficients may be developed.

The chemical compounds that make up gaseous oxidized mercury (GOM) in the atmosphere, and the reactions responsible for their formation, are not well understood. The limitations and uncertainties associated with the current method applied to measure these compounds, the KCl-coated denuder, are not known due to lack of calibration and testing. This study systematically compared the uptake of specific GOM compounds by KCl-coated denuders with that collected using nylon and cation exchange membranes in the laboratory and field. In addition, a new method for identifying different GOM compounds using thermal desorption is presented. Different GOM compounds (HgCl2, HgBr2, and HgO) were found to have different affinities for the denuder surface and the denuder underestimated each of these compounds. Membranes measured 1.3 to 3.7 times higher GOM than denuders in laboratory and field experiments. Cation exchange membranes had the highest collection efficiency. Thermodesorption profiles for the release of GOM compounds from the nylon membrane were different for HgO versus HgBr2 and HgCl2. Application of the new field method for collection and identification of GOM compounds demonstrated these vary as a function of location and time of year. Understanding the chemistry of GOM across space and time has important implications for those developing policy regarding this environmental contaminant.