Combined microwave-assisted extraction and gel permeation chromatography for the determination of chlorinated hydrocarbons in seal blubber and cod livers.

A fast and effective sample clean-up procedure for the quantitation of chlorinated hydrocarbons in seal blubber and cod livers is presented. Lipophilic sample ingredients are extracted by application of microwave energy. Microwave-assisted extraction (MAE) was performed with ethyl acetate and cyclohexane as solvent. Without exchange of the solvent, the organochlorine compounds are separated from matrix coextractives by gel permeation chromatography. Traces of matrix remainders were separated on deactivated silica prior to GC/ECD analysis. In this study we focused on quantification of PCB 153, PCB 138, PCB 180, HCB, and p,p'-DDE. In seal blubber, the recovery rates for these organochlorines were > 90% for the complete sample clean-up procedure. The standard deviation of the overall-method was within 5%. MAE of cod livers required softer conditions. After optimization of the MAE the organochlorine levels in cod liver were almost identical with those determined with another independent clean-up method.

Bisphenolic compounds that enhance cell cation transport are found in commercial phenol red.

We have isolated two bisphenolic compounds (4 and 5) that have a marked effect on K+ and Na+ concentrations in human cells from commercial preparations of the pH indicator dye phenol red (phenolsulfonphthalein). We used a bioassay to identify active chromatographic fractions from the lipophilic impurities present in phenol red, and we determined the structure of two active components (4 and 5) by 1H and 13C NMR and mass spectrometry. When added to human fibroblasts in serum-free medium, the bisphenol fluorene derivative 9,9-bis(4'-hydroxyphenyl)-3-hydroxyfluorene (5) produced a rapid loss of K+ and a gain of Na+, at low concentrations, with an EC50 between 30 and 60 ng/mL (80-160 nM). The 2- and 4-hydroxy isomers of the fluorene 5 (i.e., compounds 6 and 7), prepared by synthesis, had similar activity, although compound 6 was somewhat less potent. The bisphenol xanthene derivative 9,9-bis(4'-hydroxyphenyl)xanthene (4) elicited a similar biological response but was less potent than 5-7; it also had a strong effect on cell adhesion, causing release of cells from the plastic substrate at concentrations as low as 2-5 microg/mL (5.5-14 microM). The structures of xanthene (4) and fluorene (5) bisphenols have been confirmed by synthesis from xanthone and hydroxyfluorenone, respectively, by Friedel-Crafts alkylation with phenol. In the latter case, the desired 3-hydroxyfluorene isomer was formed in situ by rearrangement of the 1-hydroxy isomer.

Levels of alpha-HCH, lindane, and enantiomeric ratios of alpha-HCH in marine mammals from the northern hemisphere.

The enantiomeric ratios of alpha-HCH were determined by chiral gas chromatography in blubber of marine mammals from regions of the northern hemisphere (North Sea, Baltic Sea, Arctic and Iceland). Cetaceans (harbour porpoises and white-beaked dolphins) showed a preferential accumulation of (+)-alpha-HCH. In blubber of harbour seals, grey seals and harp seals (+)-alpha-HCH was also more abundant than (-)-alpha-HCH. Hooded seals formed an exception with a (+/-) enantiomeric ratio of alpha-HCH < 1.

Organochlorine residues in two seal species from western Iceland.

Harbour seals and grey seals from Faxaflói (Western Iceland) were analyzed for contamination with organochlorines (HCB, PCBs, p,p'-DDT,p,p'-DDE, chlordanes and the enantiomers of alpha-HCH). Although the values strongly varied, both harbour seals and grey seals on averaged showed comparable levels of PCBs, p,p'-DDT, p,p'-DDE and alpha-HCH, as well as chlordanes (sigma CD). Differences were measured in the HCB content of the seal species. The HCB/alpha-HCH ratio in harbour seals was < 1 and in grey seals > 1. The results from seals on Iceland were compared with data derived from seal samples of the Antarctic, the Arctic (Spitzbergen) and the North Sea (Germany) in order to give an insight into the global distribution of pollution with chlorinated organics.

Determination of levels of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and pesticides in harp seals from the Greenland Sea.

The levels of polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF), biphenyls (PCB) and compounds of the DDT group were determined in individual seal blubber and brain samples from ten male and one female harp seals caught in the Greenland Sea. No data from this region and from harp seals have been reported before. The age of the animals varied between 1 and 18 years. PCDD/PCDF concentrations in the blubber (4-10 pg/g TEQ wet weight (w.w.), Nordic model) were somewhat lower than in ringed seals from the Arctic. Non-ortho substituted PCB (CB 77,126 and 169) showed TEQ levels in the blubber which were about 4-10-times higher. CB 77 dominated in most samples, but in a few cases CB 169 was the most abundant congener. p,p'-DDE (average 760 ng/g w.w.) and di-ortho substituted PCB concentrations (2560 ng/g w.w. expressed as sigma PCB) in the blubber were comparable to those found in ringed seals from the European and Canadian Artic. Levels of PCDD/PCDF in brain correspond to the detection limit (about. 0.1-0.6 pg/g w.w.) for most congeners. With one exception, PCB amounts in brain (w.w.) were one to two orders of magnitude lower. A highly significant correlation was found between age, p,p-DDE and di-ortho PCB as well as between single PCDD and coplanar PCB congeners. No relationship was observed between levels of PCDD/PCDF, age and di-ortho-PCB.