RESUMO
BACKGROUND: The current speciation methods for mercury (Hg) measurements are fraught with considerable uncertainty, from sample collection to calibration. High reactivity of gaseous oxidized Hg (GOM) species and their ultra-trace level presence makes them difficult to sample and calibrate. Given that improper calibration may lead to measurement biases, reliable and metrologically traceable calibration methods are required for accurately quantifying GOM in air. In the present study, we applied the recently developed calibration method based on non-thermal plasma oxidation of elemental Hg, to a commercially available Hg air speciation system for actual environmental measurements of GOM for the first time. RESULTS: Hg species such as HgO, HgCl2, and HgBr2 were produced with trace amounts of reactant gases (oxygen and electrolytically produced chlorine and bromine) and the production was driven by plasma-assisted oxidation. The plasma oxidation efficiency of elemental Hg with oxygen was 98.5 ± 7.5 % (k = 2), while that for chlorine and bromine was 96.8 ± 6.9 % (k = 2) and 97.4 ± 9.6 % (k = 2), respectively. The calibration method was tested against the internal permeation (Hg0) source of the Tekran 2537B Hg analyzer on-field by loading HgO to different KCl-coated denuders using the plasma. GOM concentrations were measured using the Tekran speciation system. With internal calibration, concentrations were up to 9.1 % lower than those in plasma calibration, thereby emphasizing the importance of the calibration strategy. Measurement uncertainty (k = 2) further emphasizes this distinction. Internal calibration measurement uncertainty was 36.8 %, while plasma calibration boasted lower uncertainty at 13.8 %. SIGNIFICANCE: The non-thermal plasma calibration strategy, as a unique and discrete calibration method traceable to the NIST SRM 3133 for ambient air GOM measurements, provide a higher level of confidence in the accuracy of GOM measurements with several advantages over other methods. Calibrations at extreme low concentrations (<100 pg) are possible with this method relevant to ambient air GOM concentrations.
RESUMO
Hg isotope analysis in samples from background regions is constrained by the presence of low Hg concentration and therefore requires a pre-concentration method. Existing Hg pre-concentration methods are constrained by long sample processing time and limited sample loading capacity. Using foliar samples as a test case, an optimized Hg pre-concentration method is presented that involves the microwave-assisted digestion of samples for Hg isotope analysis with the addition of a pre-digestion step. Microwave-digested foliar samples and CRMs were transferred to an impinger, reduced with SnCl2, and collected in a 2.25 mL concentrated inverse aqua regia (3:1 HNO3:HCl, v/v). This resulted in an optimal acid concentration in the solution ideal for analysis on MC-ICP-MS. The time for purging with Hg-free N2 was optimized to 30 min and the efficiency of the pre-concentration method was tested using a combination of approaches. Tests performed on pure reagents and matrix of foliar samples spiked with 197Hg radiotracer showed recoveries averaging 99 ± 1.7% and 100 ± 3.0%, respectively. Mercury at concentrations as low as 1.83 ng g-1 was pre-concentrated by digesting aliquots of foliage samples in individual digestion vessels. Recoveries following their pre-concentration averaged 99 ± 6.0%, whereas recoveries of 95 ± 4.7% and 95 ± 2.5% were achieved for NIST SRM 1575a (pine needle) and reagents spiked with NIST SRM 3133, respectively. Analysis using multicollector-ICP-MS showed low fractionation of δ202Hg during sample pre-concentration with no significant mass-independent fractionation. The proposed method is a relatively simple and robust way to prepare Hg samples for Hg isotopic analysis and is suitable even for complex biological matrices.
