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Polychlorinated biphenyls (PCBs) are still of serious concern as a potential health hazard due to their persistency and bioacumulation. Of 209 possible PCB congeners, with varying number and position of chlorine atom(s), 19 are chiral. These are mostly highly chlorinated and tend to remain longer against the biological decompositions, suffering biological deracemization in the environment. In this work, we have unequivocally determined the absolute configurations of important chiral PCBs 183 and 171, as well as 132, through the combined theoretical and experimental investigations of the chiroptical properties (circular dichroism and optical rotation), which will be valuable in elucidating the mechanism of biological enantiomer enrichment of PCBs in the environment.

Current theory of the uptake of semivolatile organic compounds in passive air samplers (PAS) assumes uniform chemical distribution and no kinetic resistance within the passive sampling media (PSM) such as polystyrene-divinylbenzene resin (XAD) and polyurethane foam (PUF). However, these assumptions have not been tested experimentally and are challenged by some recently reported observations. To test the assumptions, we performed kinetic uptake experiments indoors using cylindrical PSM that had been concentrically segmented into three layers. Both XAD and PUF were positioned in the same type of sampler housing to eliminate the variation caused by the different housing designs, which enabled us to quantify differences in uptake caused by the properties of the PSM. Duplicated XAD (PUF) samples were retrieved after being deployed for 0, 1 (0.5), 2 (1), 4 (2), 8 (4), 12 (8), and 24 (12) weeks. Upon retrieval, the PSM layers were separated and analyzed individually for PCBs. Passive sampling rates (R) were lower for heavier PCB homologues. Within a homologue group, R for XAD was higher than that for PUF, from which we infer that the design of the "cylindrical can" housing typically used for XAD PAS lowers the R compared to the "double bowl" shelter commonly used for PUF-disk PAS. Outer layers of the PSM sequestered much higher levels of PCBs than inner layers, indicative of a kinetic resistance to chemical transfer within the PSM. The effective diffusivities for chemical transfer within PSM were derived and were found negatively correlated with the partition coefficients between the PSM and air. Based on the results, we conclude that the PSM-side kinetic resistance should be considered when investigating factors influencing R and when deriving R based on the loss of depuration compounds.