Biomedical subjects
Paul F Hoekstra
Publications and source records attributed to Paul F Hoekstra.
Enantiomer-specific accumulation of PCB atropisomers in the bowhead whale (Balaena mysticetus).
Blubber (n = 40) and liver (n = 20) samples from the bowhead whale (Balaena mysticetus) were collected during the 1997-1998 Native (Inuit) subsistence harvests in Barrow, AK. Bowhead tissues and zooplankton were analyzed for polychlorinated biphenyl (PCB) concentrations and the enantiomeric fractions (EFs) of eight chiral PCB congeners (PCB-91, 95, 135, 136, 149, 174, 176, and 183) to quantify the enantiomer-specific accumulation of PCBs in this cetacean. PCB concentrations in bowhead blubber were low (mean +/- 1 SE: 610 +/- 54 ng g(-1) lipid) relative to other cetaceans. The accumulation of several chiral PCBs (PCB-91, 135, 149, 174, 176, and 183) in bowhead blubber was enantiomer-specific relative to bowhead liver and zooplankton, suggesting that biotransformation processes within the bowhead whale are enantioselective. The EFs for PCB-95 and 149 were significantly correlated with body length in male and female whales, while EFs for PCB-91 correlated with length in males only. Despite evidence for enantioselective biotransformation, all three congeners bioaccumulated in the bowhead relative to PCB-153. Results suggest that enantioselective accumulation of PCB-91, 95, and 149 is influenced by PCB concentrations, age, and/or the modification of an uncharacterized stereoselective process (or processes) during sexual maturity.
Enantiomer fractions of chiral organochlorine pesticides and polychlorinated biphenyls in standard and certified reference materials.
Enantiomeric ratios (ERs) and enantiomeric fractions (EFs) of a number of chiral organochlorine pesticides and PCB atropisomers were measured by chiral gas chromatography/mass spectrometry (GC/MS) in five standard (SRM) and certified (CRM) reference materials: SRM 1588a (organics in cod liver oil), SRM 1945 (organics in whale blubber), Marine Mammal Quality Assurance Exercise Control Material IV (NIST IV, organics in whale blubber), CRM trout, and CRM EC-5 (sediment). Target analytes were cis- and trans-chlordane, heptachlor exo-epoxide, oxychlordane, U82, MC5, MC6, MC7, o,p'-DDT, and PCB congeners 91, 95, 136, 149, 174, 176, and 183. Measured ERs and EFs are in close agreement with the few literature values reported for some of these analytes in SRMs and CRMs. Chiral PCB ERs and EFs measured by one-dimensional chiral GC/MS were similar to values measured using multidimensional chiral GC/MS. Non-racemic chiral compositions are in agreement with known uptake and biotransformation in the respective environmental matrices. These values should aid in the quality assurance/quality control methodologies for chiral environmental chemistry using standardized reference materials.
Spatial trends and bioaccumulation of organochlorine pollutants in marine zooplankton from the Alaskan and Canadian Arctic.
Planktonic copepods (Calanus glacialis and C. hyperboreus; n = 37) and water (n = 19) were collected to examine the spatial distribution and bioaccumulation of organochlorine contaminants (OCs) in the Alaskan and Canadian Arctic. The rank order of total OC (sigma OC) group concentrations in Calanus samples was toxaphene > or = sigma polychlorinated biphenyls (PCBs) > sigma hexachlorcyclohexane (HCH) > sigma DDT > sigma chlordane-related compounds (CHLOR) > sigma chlorobenzenes (ClBz). The dominant analyte was alpha-HCH in all water and zooplankton samples. The most abundant toxaphene congener in water and zooplankton samples was the hexachlorobornane B6-923. Organochlorine contaminant group concentrations in Alaskan zooplankton and water samples were lower than those in samples collected from sites in the eastern Canadian Arctic. Comparison of PCB and toxaphene congener profiles in zooplankton and water samples suggests that biotransformation by cytochrome P-4502B isozymes is low in Calanus, and limited phase I metabolism may occur. The log relationship of bioaccumulation factor (log BAF) versus octanol-water partition coefficient (log Kow) relationship was near 1:1 for OCs within the log Kow range of 3 to 6. A curvilinear model provided a better relationship between these two variables when OC compounds with log Kow > 6 were included. These results suggest that hydrophobic OCs (log Kow 3-6) in Calanus species are at equilibrium with the water concentrations and that physical partitioning, rather than biotransformation, is the major factor governing OC profiles in marine zooplankton.