Behavior of KCl sorbent traps and KCl trapping solutions used for atmospheric mercury speciation: stability and specificity

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.

Behaviour of KCl sorbent traps and KCl trapping solutions used for atmospheric mercury speciation: stability and specificity

Atmospheric mercury speciation is of paramount importance for understanding the behavior of mercury once it is emitted into the atmosphere as gaseous elemental (GEM), gaseous oxidized (GOM) and particulate-bound (PBM) mercury. GOM and PBM sampling are the most problematic steps in the analytical procedure. GOM sampling with speciation traps composed of KCl sorbent materials and KCl trapping solutions are commonly used sampling methods, although the work done at ambient air concentrations is limited. The results of the specificity test showed that the KCl sorbent traps are very specific when using new traps, while their specificity drops dramatically when they are reused. The results of the stability test showed 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. GOM losses should be taken into account when using KCl sorbent traps for atmospheric Hg speciation, especially at low ambient GOM concentrations. KCl trapping solutions have also been considered as a selective trapping media for GOM in atmospheric samples. A dimensionless Henry’s 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 GC-AFS. 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.

Mercury Speciation in Natural and Mining-Related Systems

Mercury speciation and the composition of mercury phases in natural and mining-related environments is studied by the thermal release analysis combined with electrothermal atomic absorption spectroscopy (TA-ET-AAS), as well as scanning electron microscopy with energy-dispersive X-ray microanalysis (SEM-EDS). The analyses are applied to laboratory-made samples bearing mercury selenide and to field samples from sites known for relatively high natural or industrially induced Hg background. They are, namely, material from the dispersion train of the Ursk sulfide tailings (Ursk Village, Kemerovo region) and debris precipitated from snow sampled in the Kurai mercury zone (Aktash Village, Gorny Altai). The TA-ET-AAS method works well in discrimination and identification of Hg sulfide and Hg selenide provided that the samples contain sufficient amounts of both compounds, but the sum HgS + HgSe can be determined at any contents of the two compounds. The presence of both mercury sulfide and mercury selenide in the samples has been confirmed by SEM-EDS microanalysis. The temperature ranges for the mercury species (Hg2+; HgS+HgSe mixture; mercury bound with organic matter (Hg-OM), including CH3Hg+) are identical in the laboratory and field samples. Therefore, the suggested approach can ensure fast and reliable detection of Hg phases in rocks exposed to supergene alteration