The effects of meteorological parameters and diffusive barrier reuse on the sampling rate of a passive air sampler for gaseous mercury

Abstract. Passive air sampling of gaseous mercury (Hg) requires a high level of accuracy to discriminate small differences in atmospheric concentrations. Meteorological parameters have the potential to decrease this accuracy by impacting the sampling rate (SR), i.e., the volume of air that is effectively stripped of gaseous mercury per unit of time. We measured the SR of a recently calibrated passive air sampler for gaseous Hg in the laboratory under varying wind speeds (wind still to 6 m s⁻¹), temperatures (−15 to +35 °C), and relative humidities (44 to 80 %). While relative humidity has no impact on SR, SR increases slightly with both wind speed (0.003 m³ day⁻¹ increase in SR or 2.5 % of the previously calibrated SR for every m s⁻¹ increase for wind speeds  > 1 m s⁻¹, typical of outdoor deployments) and temperature (0.001 m³ day⁻¹ increase in SR or 0.7 % for every 1 °C increase). The temperature dependence can be fully explained by the effect of temperature on the molecular diffusivity of gaseous mercury in air. Although these effects are relatively small, accuracy can be improved by adjusting SRs using measured or estimated temperature and wind speed data at or near sampling sites. We also assessed the possibility of reusing Radiello^® diffusive barriers previously used in the passive air samplers. The mean rate of gaseous Hg uptake was not significantly different between new and previously used diffusive barriers in both lab and outdoor deployments, irrespective of the applied cleaning procedure. No memory effect from Radiellos^® previously deployed in a high Hg atmosphere was observed. However, a loss in replicate precision for the dirtiest Radiellos^® in the indoor experiment suggests that cleaning is advisable prior to reuse.