Inter-particle and gas-particle interactions in sampling artifacts of PM2.5 in filter-based samplers

Despite the recent rapid development of real-time measurements of chemical compositions in atmospheric aerosols, filter-based aerosol sampling for an extended period of time with post-sampling chemical analysis is still very common. The collected particles interact with both the in-coming gas and each other. These interactions lead to sampling artifacts. This paper investigates the role of aerosol ionic composition, inter-particle and gas-particle interactions in the sampling artifacts of PM2.5 at high relative humidity. This is achieved by comparing PM2.5 samples collected with and without a denuder/filter pack system at urban and suburban sites in Hong Kong. The samples collected with a denuder/filter pack were used to estimate the artifact-free ambient gas and particulate concentrations. Because of the prevailing high relative humidity (>70%RH) in HK, the collected particles were expected to have deliquesced and form an internal mixture, according to thermodynamic predictions. It was found that an ambient molar particulate [NH4+]/[SO42−] ratio of 1.5 is a critical condition to the sampling artifact characteristics of PM2.5. The urban samples were all ammonium rich (AR; [NH4+]/[SO42−] greater than 1.5) and were characterized by a high nitrate concentration and low strong-acidity. They had a significant strong acidity loss of 73%, roughly half of which was due to the neutralization of acidity by ammonia. The suburban samples were all ammonium poor (AP; [NH4+]/[SO42−] less than or equal to 1.5) and were characterized by a low nitrate concentration and high strong-acidity. Sampling artifacts of the acidity, ammonium and sulfate were not important in the AP samples. In both the AR and AP samples, the individual evaporation of HNO3 and HCl were the primary reactions for the artifacts of nitrate and chloride while the concomitant evaporation of HNO3 and HCl with NH3 was insignificant. In general, the extents of the sampling artifacts of nitrate and chloride increased with increasing gas-to-particulate concentration ratio of these two species. A methodology to estimate the artifact-free ambient concentrations of nitrate and chloride from measurements of filter pack samplers (without any denuders) for deliquesced particles is proposed.