摘要

Measurements of gas/particle partition coefficients for semivolatile organic compounds (SVOCs) using filter-sorbent samplers can be biased if a fraction of gas-phase mass is measured erroneously as particle-phase due to sorption of SVOC gases to the filter, or, if a fraction of particle-phase mass is measured erroneously as gas-phase due to penetration of particles into the sorbent. A fundamental mechanistic model to characterize the air sampling process with filter-sorbent samplers for SVOCs was developed and partially validated. The potential sampling artifacts associated with measurements of gas-particle partitioning were examined for 19 SVOCs. Positive sampling bias (i.e., overestimation of gas/particle partition coefficients) was observed for almost all the SVOCs. For certain compounds, the measured partition coefficient was several orders of magnitude greater than the presumed value. It was found that the sampling artifacts can be ignored when the value of log[K-f/(K-p . C-p,C-a)] is less than 7. By normalizing the model, general factors that influence the sampling artifacts were investigated. Correlations were obtained between the dimensionless time required for the gas-phase SVOCs within the filter to reach steady state (T-s,T-s*) and the chemical V-p values, which can be used to estimate appropriate sampling time. The potential errors between measured and actual gas/particle partition coefficients of SVOCs as a function of sampling velocity and time were calculated and plotted for a range of SVOCs (vapor pressures: 10(-8) similar to 10(-3) Pa). These plots were useful in identifying bias from the sampling in previously-completed field measurements. Penetration of particles into the sorbent may result in significant underestimation of the partition coefficient for particles in the size range between 10 nm and 2 mu m. For most of the selected compounds, backup filters can be used to correct artifacts effectively. However, for some compounds with very low vapor pressure, the artifacts remained or became even larger than they were without the backup filter. Thus, the option of backup filters must be considered carefully in field measurements of the gas/particle partitioning of SVOCs. The results of this work will allow researchers to predict potential artifacts associated with SVOC gas/particle partitioning as functions of compounds, the concentration of particles, the distribution of particle sizes, sampling velocity, and sampling time.