Organochlorine pesticides (OCP) were monitored at the Weissfluhjoch site (Switzerland) and the top of Mt. Sonnblick (Austria) with a low volume active air sampler and semipermeable membrane devices (SPMD). The air sampling rates (Rair) of the SPMD for OCP were calculated. Statistical tests showed that there was no significant difference between Rair at the two different sampling sites. Quantitative structure-property relationship (QSPR) models of the Rair of the SPMD were developed for OCP using partial least square (PLS) regression. Quantum chemical descriptors computed by the semi-empirical PM6 method were used as predictor variables. The cumulative variance of the dependent variable explained by the PLS components and determined by cross-validation (Q2cum) was >0.818 for each optimal model. This indicates that the model has good predictive ability and robustness. The Rair of the SPMD for OCP is related to the total energy, the van der Waals area and the total dipole moment of the OCP molecules. The main factors governing Rair values of OCP are intermolecular interactions and the energy required for cavity-formation in dissolution of OCP into triolein of the SPMD. The linear correlation coefficient between predicted and experimental values were all >0.921.
The concentrations of 28 organochlorine pesticides(OCPs)in the urban air of Dalian,China were measured using semipermeable membrane devices(SPMDs)for the first time.Alpha-hexachlorocyclohexane(a-HCH),b-HCH,pentachlorobenzene(PentCB),hexachlorobenzene(HexCB),4,40-dichlorodiphenyltrichloroethane(4,40-DDT),4,40-dichlorodiphenyldichloroethene,endosulfan-I and endosulfan-II were the predominant OCPs in the urban air of Dalian.The concentration of OCPs sequestrated by SPMDs(CSPMD)ranged from undetected to 56,772 pg SPMD-1and had a linear correlation with the reciprocal of the average ambient atmospheric temperature(1/T).The CSPMDof PentCB and HexCB had negative correlations with T,whereas the other detected OCPs had a positive correlation.The source of HCHs,DDTs,HexCB,PentCB,chlordane,and endosulfan in the air were also evaluated.The OCPs in the urban air of Dalian could be attributed to the seasonal usage of pesticides,combustion,volatilization of aged OCPs from soil,water,plants,and long-range atmospheric transport.
PCDD/Fs in the urban air of Dalian,China were monitored with high-volume active sampler from November 2009 to October 2010.The concentration of Cl 4-8 DD/Fs ranged from 3065 to 49538 fg m-3,with an average of 10249 fg m-3.The international toxic equivalents(I-TEQ) value of that was 61.8 1182 fg m-3,with an average of 235 fg m-3,which was comparable to those in the other urban locations around the world.It was found that the Cl 4 8 DD/Fs appeared to be present mainly in the particle phase during winter,spring and autumn,while during summer which were dominantly in gas phase.The ratio of Cl 4-8 DD/Fs present in particle phase increased with the increasing level of chlorination.The concentrations of PCDFs and PCDDs decreased with the increase of chlorinated level,while the concentrations of 2,3,7,8-PCDDs congeners increased with the increase of chlorination level.The homolog profiles of the concentrations of PCDFs presented were higher than those of the PCDDs,which indicated the PCDD/Fs pollution source of the air in Dalian was characteristic for thermal source pollution.The correlation analysis of meteorological parameters with the concentrations of Cl 4-8 CDD/Fs was conducted using SPSS packages,and it was found that the ambient temperature and atmospheric pressure were important factors influence the concentration of PCDD/Fs in the air.The respiratory risk and intake dioxins of the residents around the sampling sites were studied in the paper.It was found that Junge-Pankow model was much more accurate in predicting the gas-particle partitioning behavior of PCDD/Fs homologues during winter,while the Harner-Bidleman model shows better agreement with the measured data during winter and summer.
The concentration of polychlorinated biphenyls （PCBs） in the urban air of Dalian, China was monitored from November 2009 to October 2010 with active high-volume sampler and semipermeable membrane device （SPMD） passive sampler. The concentration of PCBs （particle ＋ gas） （∑PCBs） ranged from 18.6 to 91.0 pg/m3, with an average of 50.9 pg/m3, and the most abundant dioxin-like PCB （DL-PCBs） was PCB118. The WHO-TEQ values of DL-PCBs were 3.6--22.1 fg/m3, with an average of 8.5 fg/m3, and PCB126 was the maximum contributor to ZTEQ. There was a much larger amount of PCBs in the gas phase than in the particulate phase. The dominant PCB components were lower and middle molecular weight PCBs. With increasing chlorination level, the concentration of the PCB congeners in the air decreased. The gas-particulate partitioning of PCBs was different for the four seasons. The gas- particulate partitioning coefficients （logKp） vs. subcooled liquid vapor pressures （logPL~） of PCBs had reasonable correlations for different sampling sites and seasons. The absorption mechanism contributed more to the gas-particulate partitioning process than adsorption. Correlation analysis of meteorological parameters with the concentration of PCBs was conducted using SPSS packages. The ambient temperature and atmospheric pressure were important factors influencing the concentration of PCBs in the air. The distribution pattern of the congeners of PCBs and the dominant contributors to DL-PCBs and TEQ in active samples and SPMDs passive samples were similar. SPMD mainly sequestrated gas phase PCBs.
