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.

A Unique Interactive Nanostructure Knitting based Passive Sampler Adsorbent for Monitoring of Hg2+ in Water.

This work reports the development of ultralight interwoven ultrathin graphitic carbon nitride (g-CN) nanosheets for use as a potential adsorbent in a passive sampler (PAS) designed to bind Hg2+ ions. The g-CN nanosheets were prepared from bulk g-CN synthesised via a modified high-temperature short-time (HTST) polycondensation process. The crystal structure, surface functional groups, and morphology of the g-CN nanosheets were characterised using a battery of instruments. The results confirmed that the as-synthesized product is composed of few-layered nanosheets. The adsorption efficiency of g-CN for binding Hg2+ (100 ng mL-1) in sea, river, rain, and Milli-Q quality water was 89%, 93%, 97%, and 100%, respectively, at natural pH. Interference studies found that the cations tested (Co2+, Ca2+, Zn2+, Fe2+, Mn2+, Ni2+, Bi3+, Na+, and K+) had no significant effect on the adsorption efficiency of Hg2+. Different parameters were optimised to improve the performance of g-CN such as pH, contact time, and amount of adsorbent. Optimum conditions were pH 7, 120 min incubation time and 10 mg of nanosheets. The yield of nanosheets was 72.5%, which is higher compared to other polycondensation processes using different monomers. The g-CN sheets could also be regenerated up to eight times with only a 20% loss in binding efficiency. Overall, nano-knitted g-CN is a promising low-cost green adsorbent for use in passive samplers or as a transducing material in sensor applications.