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 Hg II species, which are reactive and their ambient concentrations are very low, causing difficulties in proper sampling and calibration. Calibration for atmospheric Hg II exists, but barriers to reliable calibration are most evident at ambient Hg II concentration levels. We present a calibration of Hg II species based on nonthermal plasma oxidation of Hg 0 to Hg II . Hg 0 was produced by quantitative reduction of Hg II in aqueous solution by SnCl 2 and aeration. The generated Hg 0 in a stream of He and traces of reaction gas (O 2 , Cl 2 , or Br 2 ) was then oxidized to different Hg II species by nonthermal plasma. A highly sensitive 197 Hg 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 HgCl 2 , and 77.3 ± 9.4% ( k = 2) for 250 pg of HgBr 2 . The presence of HgO, HgCl 2 , and HgBr 2 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 Hg II compounds for routine calibration of ambient air measurement instrumentation.