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Atmospheric mercury speciation is of paramount importance for understanding the behavior of mercury once it is emitted into the atmosphere as gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate-bound mercury (PBM). GOM and PBM can also be formed in the atmosphere; their sampling is the most problematic step in the atmospheric mercury speciation. GOM sampling with speciation traps composed of KCl sorbent materials and KCl trapping solutions are commonly used sampling methods, although the research conducted with them at ambient air concentrations is limited. The results of the specificity test demonstrated that the KCl sorbent traps are highly specific when using new traps, while their specificity drops dramatically when they are reused. The results of the stability test indicated that the highest Hg2+ losses (up to 5.5 % of Hg2+ loss) occur when low amounts of Hg2+ (< 1 ng) are loaded, due to a reduction of Hg2+ to Hg0. KCl trapping solutions have also been considered as a selective trapping media for GOM in atmospheric samples. A dimensionless Henry law constant was experimentally derived and was used to calculate the solubility of elemental Hg in KCl solution. The degree of GEM oxidation was established by purging elemental Hg calibration gas into a KCl solution and determining the GOM trapped using aqueous-phase propylation liquid–liquid extraction and gas chromatography–atomic fluorescence spectrometry (GC-AFS) measurement. A positive GOM bias was observed due to the solubility and oxidation of GEM in KCl trapping solutions, strongly suggesting that this approach is unsuitable for atmospheric mercury speciation measurements.

A primary mercury gas standard was developed at Van Swinden Laboratory (VSL) to establish an International System of Units (SI)-traceable reference point for mercury concentrations at emission and background levels in the atmosphere. The majority of mercury concentration measurements are currently made traceable to the empirically determined vapour pressure of mercury. The primary mercury gas standard can be used for the accurate and precise calibration of analytical systems used for measuring mercury concentrations in air. It has been especially developed to support measurements related to ambient air monitoring (1–2 ng m−3), indoor and workplace-related mercury concentration levels according to health standards (from 50 ng m−3 upwards) as well as stationary source emissions (from 1 µg m−3 upwards). The primary mercury gas standard is based on diffusion according to ISO 6154-8. Calibration gas mixtures are obtained by combining calibrated mass flows of nitrogen and air through a generator holding diffusion cells containing elemental mercury. In this paper, we present the results of comparisons between the primary gas standard and mercury calibration methods maintained by NPL (National Physical Laboratory in the United Kingdom), a National Metrology Institute (NMI), and the Jozef Stefan Institute (JSI), a Designated Institute (DI). The calibration methods currently used at NPL and JSI are based on the bell-jar calibration apparatus in combination with the Dumarey equation or a NIST (National Institute of Standards and Technology in the United States) reference material. For the comparisons, mercury was sampled on sorbent traps to obtain transfer standards with levels between 2 and 1000 ng with an expanded uncertainty not exceeding 3 % (k=2). The comparisons performed show that the results for the primary gas standard and the NIST reference material are comparable, whereas a difference of −8 % exists between results traceable to the primary gas standard and the Dumarey equation.