A field intercomparison of three passive air samplers for gaseousmercury in ambient air

Abstract. Passive air samplers (PASs), providing time-averaged concentration of gaseous mercury over the time scale of weeks to months, are promising to fill a gap in the monitoring of atmospheric mercury worldwide. Their usefulness will depend on their ease-of-use and robustness under field conditions, their availability and affordability, and most notably, their ability to provide results of acceptable precision and accuracy. Here we describe a comparative evaluation of three PASs with respect to their ability to record precisely and accurately atmospheric background concentrations at sites in both southern Italy and southern Ontario. The study includes the CNR-PAS with gold nanoparticles as a sorbent, developed by the Italian National Research Council, the IVL-PAS using an activated carbon-coated disk, developed by the Swedish Environmental Research Institute, and the MerPAS® using a sulfur-impregnated activated carbon sorbent, developed at the University of Toronto and commercialized by Tekran. Detection limits are deduced from the variability in the amount of mercury quantified in more than 20 field blank samples for each PAS. Analytical and sampling precision is quantified through 22 triplicated deployments for each PAS ranging in length from two to twelve weeks. Accuracy and bias are assessed through comparison with gaseous elemental mercury concentrations recorded by Tekran 2537 automated mercury analyzers operating alongside the PASs at both locations. The performance of the PASs was significantly better in Italy, with all of them providing concentrations that are not statistically significantly different from the average of the active sampling results. In Canada, where weather conditions were much harsher and more variable during the February through April deployment period, differences were observed amongst PASs. At both sites, the MerPAS® is currently the most sensitive, precise and accurate among the three PASs. A key reason for this is the larger size and the radial configuration of the MerPAS®, which results in blank levels that are lower relative to the sequestered amounts of mercury than in the other two PASs, which rely on axial diffusion geometries. Because the blank-correction becomes relatively smaller with longer deployment, sampler performance tends to be better during deployments of 8 and 12 weeks.