Enantiospecific Analysis and Environmental Behavior of Chiral Persistent Organic Pollutants (POPs)

Many persistent organic pollutants (POPs) are chiral. These pollutants are generally released into the environment as racemates, but frequently undergo alterations in enantiomeric composition as soon as they are subjected to life chemistry processes. Enantiospecific analysis of chiral POPs is important since enantiomers of chiral compounds often exhibit differences in biological activity, and most biochemical processes in nature are stereospecific. For abiotic processes, such as air-water gas exchange, deposition and long-range air transport, enantiomeric patterns of POPs may be used as chemical markers. The aim of the work described in this thesis was to improve our knowledge about the presence and fate of enantiomers of chiral POPs in the environment to provide a sound basis for accurate risk assessment. The compounds included were organochlorine (OC) pesticides (α-HCH, chlordanes and o,p’-DDT), atropisomeric PCBs and some of their respective metabolites (heptachlor-exo-epoxide, oxychlordane and MeSO2PCBs). Analytical methods for chiral PCBs were developed, and the elution sequences of (+) and (−)-enantiomers were determined. Enantiomeric fraction (EF) was proposed as a better reflector of chiral composition than the conventional enantiomeric ratio (ER). Enantioselective bioprocessing in various compartments was studied, with the main emphasis on factors controlling chiral composition in biota Correlations were detected between changes in EFs and differences in trophic levels. The changes were, however, not consistent for all compounds. Instead, the enantiomeric composition was found to be species-specific in the polar bear food chain and in aquatic species from the Baltic Sea. The EFs of some POPs in Baltic seals were related to nutritional status and biotransformation capacity. Enantiomeric and isomeric patterns were used to investigate abiotic processes in the southern Baltic Sea environment and EFs were used to study soil as a source of atmospheric heptachlor-exo-epoxide.