Airborne PM2.5/PM10-Associated Chlorinated Polycyclic Aromatic Hydrocarbons and their Parent Compounds in a Suburban Area in Shanghai, China

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) have been reported to be formed during incineration processes. Despite dioxin-like toxicities of ClPAHs, little is known on the occurrence of these chemicals in the environment. In this study, concentrations of 24-h airborne PM10 and PM2.5-associated ClPAHs and their corresponding parent PAHs were monitored from October 2011 to March 2012 in a suburban area in Shanghai, China. In addition, daytime and nighttime particle samples were collected for 7 days in April from the same sampling site. Twelve of twenty ClPAH congeners were found in PM10 and PM2.5 at concentrations ranging from 2.45 to 47.7 pg/m(3) with an average value of 12.3 pg/m(3) for PM10, and from 1.34 to 22.3 pg/m(3) with an average value of 9.06 pg/m(3) for PM2.5. Our results indicate that ClPAHs are ubiquitous in inhalable fine particles. The concentrations of Sigma ClPAHs and specific congeners such as 9-ClPhe, 3-ClFlu, 1-ClPyr, 7-ClBaA, and 6-ClBaP in particles collected during nighttime were higher than those collected during daytime, which suggests not only diffusion of ClPAHs in air by atmospheric mixing but also photochemical degradation during daylight hours. Among the individual ClPAHs determined, 6-ClBaP, 1-ClPyr, and 9-ClPhe were the dominant compounds in PM10 and PM2.5. The percent composition of 6-ClBaP, 1-ClPyr, 7-ClBaA, and 3-ClFlu between PM10 and PM2.5 was similar. Significant positive correlations were found between concentrations of ClPAHs and their corresponding parent PAHs, particle mass, and total organic carbon (organic carbon plus elemental carbon), indicating that ClPAHs are sorbed onto carbonaceous matter of PM. Concentrations of parent PAHs predicted by multiple linear regression models with PM mass, total organic carbon, temperature, and relative humidity as variables reflected the measured concentrations with a strong coefficient of determination of 0.917 and 0.946 for PM10 and PM2.5, respectively. However, the models generated to predict ClPAH concentrations in PM did not yield satisfactory results, which suggested the differences in physical-chemical properties and formation processes between ClPAHs and their corresponding parent PAHs. 7-ClBaA and 6-ClBaP collectively accounted for the preponderance of the total dioxin-like TEQ concentrations of ClPAHs (TEQ(ClPAH)) in PM samples. Exposure to toxic compounds such as ClPAHs and PAHs present in PM2.5 can be related to adverse health outcomes in people.