Traceable Calibration of Atmospheric Oxidized Mercury Measurements.

Most previous measurements of oxidized mercury were collected using a method now known to be biased low. In this study, a dual-channel system with an oxidized mercury detection limit of 6-12 pg m-3 was deployed alongside a permeation tube-based automated calibrator at a mountain top site in Steamboat Springs Colorado, USA, in 2021 and 2022. Permeation tubes containing elemental mercury and mercury halides were characterized via an International System of Units (SI)-traceable gravimetric method and gas chromatography/mass spectrometry before deployment in the calibrator. The dual-channel system recovered 97 ± 4 and 100 ± 8% (±standard deviation) of injected elemental mercury and HgBr2, respectively. Total Hg permeation rates and Hg speciation from the gravimetric method, the chromatography system, the dual-channel system, and an independent SI-traceable measurement method performed at the Jozef Stefan Institute laboratory were all comparable within the respective uncertainties of each method. These are the first measurements of oxidized mercury at low environmental concentrations that have been verified against an SI-traceable calibration system in field conditions while sampling ambient air, and they show that accurate, routinely calibrated oxidized mercury measurements are achievable.

Application of traceable calibration for gaseous oxidized mercury in air.

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.

Optimization of a pre-concentration method for the analysis of mercury isotopes in low-concentration foliar samples.

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.

Dispersion of airborne mercury species emitted from the cement plant.

The cement industry is the second largest source of anthropogenic mercury (Hg) emissions in Europe, accounting for 11% of global anthropogenic Hg emissions. The main objective of this study was to examine the influence of Hg emissions from the Salonit Anhovo cement plant on Hg levels measured in the ambient air at Vodarna, 1 km downwind from the flue gas chimney. The findings reveal that the plant raw mill operational status plays an important role in Hg concentrations in the flue gas emitted from the plant. Emitted total gaseous mercury was, on average, higher (49.4 µg/m3) when raw mills were in the direct mode (both raw mills-off) and lower (23.4 µg/m3) in the combined mode (both raw mills-on). The average Hg concentrations in Vodarna were 3.14 ng/m3 for gaseous elemental mercury, 53.7 pg/m3 for gaseous oxidised mercury, and 41.9 pg/m3 for particulate bound mercury for the whole measurement period. Atmospheric Hg speciation in Vodarna, coupled with plant emissions and wind data, has revealed that the total gaseous mercury emitted from the cement plant is clearly related to all Hg species measured in Vodarna. Wind blowing from the northeastern quadrant (mostly NE, ENE) is responsible for the elevated Hg levels in Vodarna, where gaseous oxidised mercury levels are highly linked to the cement plant emissions. However, elevated levels of Hg species in the absence of northeastern winds indicate potential inputs from other unknown local sources as well as inputs from regional and global transport mechanisms.

Calibration Approach for Gaseous Oxidized Mercury Based on Nonthermal Plasma Oxidation of Elemental Mercury.

Atmospheric mercury measurements carried out in the recent decades have been a subject of bias largely due to insufficient consideration of metrological traceability and associated measurement uncertainty, which are ultimately needed for the demonstration of comparability of the measurement results. This is particularly challenging for gaseous HgII species, which are reactive and their ambient concentrations are very low, causing difficulties in proper sampling and calibration. Calibration for atmospheric HgII exists, but barriers to reliable calibration are most evident at ambient HgII concentration levels. We present a calibration of HgII species based on nonthermal plasma oxidation of Hg0 to HgII. Hg0 was produced by quantitative reduction of HgII in aqueous solution by SnCl2 and aeration. The generated Hg0 in a stream of He and traces of reaction gas (O2, Cl2, or Br2) was then oxidized to different HgII species by nonthermal plasma. A highly sensitive 197Hg radiotracer was used to evaluate the oxidation efficiency. Nonthermal plasma oxidation efficiencies with corresponding expanded standard uncertainty values were 100.5 ± 4.7% (k = 2) for 100 pg of HgO, 96.8 ± 7.3% (k = 2) for 250 pg of HgCl2, and 77.3 ± 9.4% (k = 2) for 250 pg of HgBr2. The presence of HgO, HgCl2, and HgBr2 was confirmed by temperature-programmed desorption quadrupole mass spectrometry (TPD-QMS). This work demonstrates the potential for nonthermal plasma oxidation to generate reliable and repeatable amounts of HgII compounds for routine calibration of ambient air measurement instrumentation.