Levels and enantiomeric signatures of methyl sulfonyl PCB and DDE metabolites in livers of harbor porpoises (Phocoena phocoena) from the Southern North Sea

The concentration of 26 methyl sulfonyl metabolites of polychlorinated biphenyls (MeSO2-PCBs) and of p,p'-DDE (MeSO2-DDE) were determined in 19 liver samples from harbor porpoises (Phocoena phocoena) stranded between 1997 and 2000 on the Belgian and French North Sea Coasts. The total concentration of MeSO2-PCBs ranged from 39 to 4221 ng/g lipid weight (lw) and were generally higher in adults (age > 2 yr, range 969-4,221 ng/g lw) than in juveniles (age < 2 yr, range 39-1815 ng/g lw). The concentrations of MeSO2-DDE were generally also higher in adults (21-96 ng/g lw) than in juveniles (0.5-60 ng/g lw). Congeners 3- and 4-MeSO2-CB101 were the dominating metabolites in all samples. Due to their preferential retention in the liver, the MeSO2-PCB congeners could be divided into two groups. The first group was dominated by the 3-MeSO2-PCB congeners and consisted of MeSO2-CB31, -CB49, -CB52, -CB87, and -CB101, which all have a 2,5-chlorine substitution in the phenyl ring containing the methyl sulfonyl group. The second group was dominated by the 4-MeSO2-PCB congeners and consisted of MeSO2-CB64, -CB91, -CB110, and -CB132, which all have a 2,3,6-chlorine substitution. The ratios of sum of PCBs/sum of MeSO2-PCBs and p,p'-DDE/MeSO2-DDE differed greatly between individual subjects and ranged from 15 to 419 and from 17 to 1088, respectively. The ratio between the precursor PCB congeners and their corresponding metabolites ranged from 0.6 (CB49) to 175 (CB174). Enantiomeric fractions (EFs) for MeSO2-PCB atropisomers, which include 3-MeSO2-CB132, 3-MeSO2-CB149, 4-MeSO2-CB149, 3-MeSO2-CB174, and 4-MeSO2-CB174, were also measured in 8 out of the 19 subjects. High enantiomeric excess (EF > 0.73 or EF < 0.23) for the measured chiral MeSO2-PCB congeners was found in all samples. This result may suggest that one atropisomer may be preferentially formed in harbor porpoises or that the atropisomers are retained in a highly selective manner.     

Enantiomeric specificity of methylsulfonyl-PCBs and distribution of bis(4-chlorophenyl) sulfone, PCB, and DDE methyl sulfones in grey seal tissues

PCB methyl sulfones (MeSO2-PCBs) are lipophilic PCB metabolites of which five of the environmentally relevant meta/para pairs are chiral (i.e., exist as atropisomeric pairs). Methylsulfonyl-DDE (MeSO2-DDE) is a DDE metabolite, while bis(4-chlorophenyl) sulfone (BCPS) is a commercial monomer used for thermoplastic production. All these sulfones are well-known environmental contaminants. In this study, liver, lung, and adipose tissue in grey seals (Halichoerus grypus) from the Baltic Sea, naturally exposed to organochlorines via their food, were analyzed for the compounds mentioned. MeSO2-PCBs, 3-MeSO2-DDE, and BCPS were all found in significantly higher concentrations in the liver than in lung and blubber. Their strong liver retention, represented by a median of 42 microg/g l.w. of sigmaMeSO2-PCBs, has previously been mainly neglected in assessments of exposure. The highest concentrations of PCBs and DDE were still found in the grey seal blubber. The atropisomeric composition of MeSO2-PCB congeners was determined, and their enantiomeric fractions were calculated and compared in blubber, liver, and lung tissues. The enantiomeric specificity was equal in all tissues. A notably high abundance (>94%) was observed for one atropisomer in each chiral MeSO2-PCB pair. The first eluting atropisomer (A1) was dominating for all para-substituted MeSO2-PCBs studied, while the second eluting atropisomers (A2) were as dominant in all meta-substituted MeSO2-PCBs in all samples analyzed. In the liver, as much as 50% of sigmaMeSO2-PCBs consisted of the second eluting atropisomer (A2) of 5-MeSO2-CB149. The results imply that the sulfone group is crucial for the specific liver retention of MeSO2-PCBs, 3-MeSO2-DDE, and BCPS.     

Enantioselective formation of methyl sulfone metabolites of 2,2',3,3',4,6'-hexachlorobiphenyl in rat

Several nonsymmetric polychlorinated biphenyl (PCB) congeners form atropisomers due to steric hindrance of free rotation around the phenyl-phenyl bond. It is evident from the literature that both chiral PCB congeners and their atropisomeric methylsulfonyl-PCB metabolites, formed in higher animals and in humans, are present in biota as nonracemic mixtures. Chiral methylsulfonyl-PCBs are strongly dominated by one of the atropisomers in mammalian tissues. The aim of the present study is to examine enantioselective metabolism, retention, and excretion of 2,2',3,3',4,6'-hexachlorobiphenyl (CB-132) in rat by administration of a CB-132 racemate and pure atropisomers. Chemical analysis of liver, lung, and adipose tissue from the rats showed a strong retention of one of the CB-132 atropisomers and a similar, but even more pronounced, accumulation of one of the atropisomers of the meta- and para-methylsulfonyl-substituted CB-132 metabolites in these tissues. Metabolites with R structures were predominately formed from one of the atropisomers of CB-132. The slower metabolism of the other atropisomer of CB-132 and its pronounced excretion in feces suggest an enantioselective metabolism. The results indicate enantio-selective formation of the methylsulfonyl-CB132 metabolites and confirm the critical role of stereochemistry of chemicals for their metabolism.     

Levels of PCBs and their metabolites in the serum of residents of a highly contaminated area in eastern Slovakia

The over-riding aim of the present investigation was to obtain information concerning exposure that can be used as a basis for studies on the health of individuals residing in the Michalovce area of eastern Slovakia which is heavily contaminated by polychlorinated biphenyls (PCBs). Accordingly, this work focused on determination of serum concentrations of hydroxylated (OH-PCBs) and methylsulfonyl-substituted (MeSO2-PCBs) metabolites of PCBs. One hundred and twenty-two men and women, 20-59 years of age, living in the contaminated area and 175 from the control Stropkov/Svidnik district were selected randomly from 2047 sampled individuals. Following a specially designed cleanup, the levels of various congeners of OH-PCBs and MeSO2-PCBs in their serum were quantitated by gas chromatography and mass spectrometry, with comparison to authentic reference standards. The median concentrations of PCB congeners and their OH-PCB and MeSO2-PCB metabolites were 2-3-fold higher in residents of Michalovce than in the control region. The levels of certain OH-PCB metabolites were in the same high range as those of individual PCB congeners, whereas the MeSO2-PCB levels were significantly lower. The PCB and their metabolites were present at slightly higher concentrations in men than in women, and the serum levels of PCBs and MeSO2-PCBs increased with increasing age. Thus, the environmental contamination resulting from previous industrial production of PCBs has led to elevated concentrations of PCBs and their metabolites in the serum of individuals living in the Michalovce area.     

Factors affecting phase I stereoselective biotransformation of chiral polychlorinated biphenyls by rat cytochrome P-450 2B1 isozyme

In vitro incubations of rat cytochrome P-450 (CYP) 2B1 isozyme with three chiral polychlorinated biphenyl (PCB) congeners (PCBs 45, 95, and 132) were performed to investigate factors affecting phase I stereoselective biotransformation. Rat CYP2B1 preferentially biotransformed the second-eluting atropisomers of PCBs 45 and 95 at low substrate concentration ranges (≤15 μM). Biotransformation competition by different congeners was also observed, with increasing competition at higher chlorination. Competition decreased the biotransformation rates of each congener stereoselectively, affecting atropisomeric composition. No atropisomeric enrichment was observed for PCB 132 upon incubation of the racemate. However, under the same conditions, significant differences in biotransformation kinetics were observed in individual atropisomer incubations, indicating that (+)-PCB 132 and (-)-PCB 132 were competitively biotransformed. Homology modeling and docking studies suggested that each atropisomer had different interactions with rat CYP2B1 and could dock with the isozyme at different locations. This is one possible explanation for stereoselective biotransformation and competition of chiral PCBs at the molecular level. Our results suggest that the lack of predictive capability for stereoselectivity of PCBs and other chiral pollutants in biota may be due to competitive and/or inhibitory activities of different substrates, including individual enantiomers of the same compound.     

Gas chromatographic analysis with chiral cyclodextrin phases reveals the enantioselective formation of hydroxylated polychlorinated biphenyls by rat liver microsomes

Chiral PCB congeners are major components of PCB mixtures and undergo enantioselective biotransformation to hydroxylated (OH-)PCBs by cytochrome P450 enzymes. While it is known that biotransformation results in an enantiomeric enrichment of the parent PCB, it is currently unknown if OH-PCBs are formed enantioselectively. The present study screened seven commercial capillary gas chromatography columns containing modified β- or γ-cyclodextrins for their potential to separate the atropisomers of methylated derivatives of OH-PCB. The atropisomers of 3-, 4- and 5-methoxy derivatives were at least partially separated on one or more columns. A subsequent biotransformation study was performed with rat liver microsomes to assess if hydroxylated metabolites are formed enantioselectively from PCBs 91, 95, 132, and 149. The OH-PCBs were extracted from the microsomal incubations, derivatized with diazomethane and analyzed as the respective methoxylated (MeO-)PCB derivatives using selected columns. The 5-hydroxylated metabolites of PCBs 91, 95, 132, and 149 were the major metabolites, which is consistent with PCB's biotransformation by cytochrome P450 2B enzymes. All 5-hydroxylated metabolites displayed a clear, congener-specific enantiomeric enrichment. Overall, this study demonstrates for the first time that chiral PCBs, such as PCB 91, 95, 132, and 149, are enantioselectively metabolized to OH-PCBs by cytochrome P450 enzymes.     

Determination of the enantiomeric ratios of chiral PCB 95 and 149 in human milk samples by multidimensional gas chromatography with ECD and MS(SIM) detection

 The enantiomeric ratios of the chiral polychlorinated biphenyls 2, 2′, 3, 5′, 6-pentachlorobiphenyl (PCB 95) and 2, 2′, 3, 4′, 5′, 6-hexachlorobiphenyl (PCB 149) were determined in human milk samples by multidimensional gas chromatography, using two different achiral columns for preseparation and a chiral column for enantiomeric separation. Detection was carried out by electron capture detection and by mass spectrometry in the single ion monitoring mode. For PCB 95 a slight enrichment of the first eluted peak was determined whereas PCB 149 is present as racemate. Received: 24 August 1998 / Revised version: 1 December 1998     

Enantiomeric composition of chiral polychlorinated biphenyl atropisomers in aquatic bed sediment

Enantiomeric ratios (ERs) for eight polychlorinated biphenyl (PCB) atropisomers were measured in aquatic sediment from selected sites throughout the United States by using chiral gas chromatography/mass spectrometry. Nonracemic ERs for PCBs 91, 95, 132, 136, 149, 174, and 176 were found in sediment cores from Lake Hartwell, SC, which confirmed previous inconclusive reports of reductive dechlorination of PCBs at these sites on the basis of achiral measurements. Nonracemic ERs for many of the atropisomers were also found in bed-sediment samples from the Hudson and Housatonic Rivers, thus indicating that some of the PCB biotransformation processes identified at these sites are enantioselective. Patterns in ERs among congeners were consistent with known reductive dechlorination patterns at both river sediment basins. The enantioselectivity of PCB 91 is reversed between the Hudson and Housatonic River sites, which implies that the two sites have different PCB biotransformation processes with different enantiomer preferences.     

Target tissue selectivity and burdens of diverse classes of brominated and chlorinated contaminants in polar bears (Ursus maritimus) from East Greenland

The tissue-specific composition of sum classes of brominated and chlorinated contaminants and metabolic/degradation byproducts was determined in adult male and female polar bears from East Greenland. Significantly (p < 0.05) higher concentrations of sigma-PCBs, various other organochlorines such as sigma-CHL, p,p'-DDE, sigma-CBz, sigma-HCHs, octachlorostyrene (OCS), sigma-mirex, dieldrin, the flame retardants sigma-PBDEs, and total-(alpha)-hexabromocyclododecane (HBCD), sigma-methylsulfonyl (MeSO2)-PCBs and 3-MeSO2-p,p'-DDE, were found in the adipose and liver tissues relative to whole blood and brain. In contrast, sigma-hydroxyl (OH)-PCB, 4-OH-heptachlorostyrene and sigma-OH-PBDE concentrations were significantly highest (p < 0.05) in whole blood, whereas the highest concentrations of sigma-OH-PBBs were found in the adipose tissue. Based on the total concentrations of all organohalogens in all three tissues and blood, the combined body burden was estimated to be 1.34 +/- 0.12 g, where > 91% of this amount was accounted for by the adipose tissue alone, followed by the liver, whole blood, and brain. These results show that factors such as protein association and lipid solubility appear to be differentially influencing the toxicokinetics, in terms of tissue composition/ localization and burden, of organohalogen classes with respect to chemical structure and properties such as the type of halogenation (e.g., chlorination or bromination), and the presence or absence of additional phenyl group substituents (e.g., MeO and OH groups). The tissue- and blood-specific accumulation (or retention) among organohalogen classes indicates that exposure and any potential contaminant-mediated effects in these polar bears are likely tissue or blood specific.     

Changes in enantiomeric fractions during microbial reductive dechlorination of PCB132, PCB149, and araclor 1254 in Lake Hartwell sediment microcosms

The enantioselectivity of microbial reductive dechlorination of chiral PCBs in sediments from Lake Hartwell, SC, was determined by microcosm studies and enantiomer-specific GC analysis. Sediments from two locations in the vicinity of the highest levels of PCB contamination were used as inocula. Dechlorination activity was monitored by concentration decreases in the spiked chiral PCBs and formation of dechlorination products using both achiral and chiral chromatography. Live microcosms spiked with PCB132 (234-236) exhibited dechlorination of PCB132 to PCB91 (236-24) and PCB51 (24-26). Meta dechlorination was the dominant mechanism. Microcosms spiked with PCB149 (245-236) exhibited preferential para dechlorination of PCB149 to PCB95 (236-25), followed by meta dechlorination to PCB53 (25-26) and subsequently PCB19 (26-2). Dechlorination of chiral PCB132 and PCB149 was not enantioselective. In Aroclor 1254-spiked microcosms, reductive dechlorination of PCB149 also was nonenantioselective. These results suggest that dechlorinating enzymes responsible for the dehalogenation of the chiral PCB132 and PCB149 congeners bind the two enantiomers equally. Reductive dechlorination of PCB91 and PCB95, however, occurred in an enantioselective manner, indicating that the dechlorinating enzymes for these PCBs are enantiomer-specific. The chlorine substitution pattern on the biphenyl ring appears to influence whether reductive dechlorination of chiral PCB congeners is enantioselective. Enantioselective PCB dechlorination by the microbial population of Lake Hartwell sediments occurs for select chiral PCBs; thus, certain chiral PCBs might be useful as markers for in situ reductive dechlorination.     

Distribution of chiral PCBs in selected tissues in the laboratory rat

The enantiomeric enrichment of polychlorinated biphenyl (PCB) atropisomers has been reported in both wildlife and in humans. The biological processes causing this enrichment are only poorly investigated, a fact that limits the use of enantiomeric fractions (EFs) as a tool to study various processes of environmental relevance. To further understand these enantioselective processes, this study investigates the tissue distribution and EFs of some PCB atropisomers after administration of PCB mixtures to immature male Sprague-Dawley rats. The mixtures selected for this study, Aroclor 1254 and an environmental mixture extracted from Chlorofen-contaminated soil, are qualitatively different and are known to induce different groups of hepatic enzymes. Animals were sacrificed 6 days after dosing, PCBs were extracted, and, whenever possible, the EFs of PCBs 84, 91, 95, 149, 174, and 176 were determined by chiral gas chromatography. The EFs of PCB 95 (adipose tissue, liver, and skin) and PCB 149 (adipose tissue, liver, skin, and blood) in tissues from Aroclor 1254-treated animals differed significantly from EFs in the Aroclor standard, while only EFs of PCB 95 (blood) and PCB 174 (adipose tissue) in tissues from soil-extract-treated animals were different from those of the Chlorofen soil extract. PCB 149 in tissues from soil-extract-treated animals underwent no statistically significant enantiomeric enrichment. These differences in the EFs clearly suggest that the enantioselective enrichment of PCB atropisomers may correlate with exposure history, and with the induction of hepatic enzymes, and that EFs may be useful chemical markers of physiologic and biochemical changes following exposure to PCBs.     

Enantioselective biotransformation of chiral PCBs in whole poplar plants

Chiral PCBs have been used as molecular probes of biological metabolic processes due to their special physical, chemical, and biological properties. Many animal studies showed the enantioselective biotransformation of chiral PCBs, but it is unclear whether plants can enantioselectively biotransform chiral PCBs. In order to explore the enantioselectivity of chiral PCBs in whole plants, poplars (Populus deltoides × nigra, DN34), a model plant with complete genomic sequence, were hydroponically exposed to 2,2',3,5',6-pentachlorobiphenyl (PCB95) and 2,2',3,3',6,6'-hexachlorobiphenyl (PCB136) for 20 days. PCB95 and PCB136 were shown to be absorbed, taken-up and translocated in whole poplars, and they were detected in various tissues of whole poplars. However, the enantioselectivity of poplar for PCB95 and PCB136 proved to be quite different. The first eluting enantiomer of PCB95 was enantioselectively removed in whole poplar, especially in the middle and bottom xylem. It was likely enantioselectively metabolized inside poplar tissues, in contrast to racemic mixtures of PCB95 remaining in hydroponic solutions in contact with plant roots of whole and dead poplars. Unlike PCB95, PCB136 remained nearly racemic in most parts of whole poplars after 20 days exposure. These results suggest that PCB136 is more difficult to be enantioslectively biotransformed than PCB95 in whole poplars. This is the first evidence of enantioselectivity of chiral PCBs in whole plants, and suggests that poplars can enantioselectively biotransform at least one chiral PCB.     

Long-term recovery of PCB-contaminated sediments at the Lake Hartwell superfund site: PCB dechlorination. 1. End-member characterization

Under anaerobic conditions, such as those typically found in buried sediments, the primary metabolic pathway for polychlorinated biphenyls (PCBs) is reductive dechlorination in which chlorine removal and substitution with hydrogen by bacteria result in a reduced organic compound with fewer chlorines. Vertical sediment cores were collected from Lake Hartwell (Pickens County, SC) and analyzed in 5-cm intervals for 107 PCB congeners in a total of more than 280 samples from 18 sediment cores and surface samples. This paper reports on extensive PCB dechlorination measured in Lake Hartwell sediments and the characterization of dechlorination end-member (EM) patterns using chemical forensic methods. PCB congener fingerprinting and a multivariate receptor modeling method, polytopic vector analysis (PVA), were used for identification and characterization of weathered and dechlorinated PCB congener patterns. Dechlorination resulted in a substantial shift in buried sediments from tetra- through decachlorobiphenyl congeners to mono- through trichlorobiphenyl congeners. Mono- through trichlorobiphenyls comprised approximately 80% of the PCBs in buried sediments that underwent maximum dechlorination as compared to approximately 20% in surface sediments. The major concentration decreases were seen in the tetra- through hexachlorobiphenyl homologues, which accounted for over 90% of the dechlorination. Octa- through decachlorobiphenyl congeners also were dechlorinated, but their overall contribution to dechlorination was relatively small due to their low initial concentrations (< 5%). The net accumulation of 2-CB, 2,2'/2,6-DCBs, 2,4'-DCB, 2,2',4-TCB, and 2,2',6-TCB at Lake Hartwell matched characteristic PCB dechlorination products reported in the literature, such as those for Processes M, Q, and C; and the persistence of tetrachlorobiphenyls (TeCBs) that contained 24- and 25-congener groups resembled dechlorination Processes H or H'. Although dechlorination tended to be very extensive in most of the cores, it was not always consistent from core to core or at various depth intervals within a single core. The reason for this variability in dechlorination extent could not be determined from the existing data and did not appear to correlate with such factors as PCB concentration, total organic carbon, or age. The authors used fingerprinting analysis and a PVA multivariate receptor model as exploratory data analysis tools to characterize PCB sources and their alteration patterns. Dominant sources and alteration patterns were determined in this large data set by comparing PVA EM patterns with known source patterns (i.e., Aroclors or Aroclor mixtures) and literature-reported alteration patterns. PVA also afforded an opportunity to characterize the vertical and lateral distributions of the weathered and unweathered PCB source patterns and dechlorination patterns, a task that would have been much more difficult to accomplish through comparison of chromatograms alone.     

Levels of specific polychlorinated biphenyl congeners in fatty foods from five Canadian cities between 1986 and 1988.

A total of 155 fatty food composites from five major Canadian cities were analysed for 36 selected polychlorinated biphenyl (PCB) congeners. Total PCB congener levels of more than 1 ng/g (wet weight) were found in fresh water fish, canned fish, butter, marine fish and cheese, with fresh water fish (18.7 ng/g) containing 5 to 10 times more total PCBs than the other four food commodities. Milk (2%), cooking oils/salads and canned meat soup contained less than 0.1 ng/g (wet weight). The observed total PCB residue levels in fatty foods were well within the Canadian guidelines for fish, dairy products, poultry, eggs and beef. The most predominant congeners found in fish, butter, cheese, meat and poultry were the 2,2',4,4',5-, 2,3',4,4', 5-pentachloro-, 2,2',3,4,4',5'-, 2,2',4,4',5,5'-hexachloro- and 2,2',3,4,4',5,5'-heptachlorobiphenyls. The predominant congener pattern was not always evident in other dairy products (e.g. ice cream) and processed foods (e.g. canned meat soup). An attempt was made to relate the intake of PCB congeners from fatty foods with congener levels found in adipose tissue of Canadians. The estimated daily intake of some specific PCB congeners from fatty foods, in most cases accounted for more than half the total deposit of these congeners in adipose tissue of Canadians.     

Chorioallantoic membranes indicate avian exposure and biomarker responses to environmental contaminants: a laboratory study with White Leghorn chickens (Gallus domesticus)

PCB and endosulfan concentrations in the chorioallantoic membrane (CAM) of white leghorn chickens (Gallus domesticus) were evaluated as indicators of hepatic cytochrome P450 isozyme activity in hens and chicks as well as toxicant concentrations in eggs and hens. Sixteen hens were randomly divided into four groups of four and dosed with a mixture of PCB105 (2,3,3',4,4'-pentachlorobiphenyl), PCB156(2,3,3',4,4',5-hexachlorobiphenyl), PCB189 (2,3,3',4,4',5,5'-heptachlorobiphenyl), and technical grade endosulfan (3:1 ratio of alpha and beta isomers) at three different dose groups. The first 10 fertile eggs laid by each hen were collected, the even-numbered eggs incubated until hatched, and the odd numbered eggs were analyzed for test chemicals. Strong (r2), significantly positive (p value) relationships were found between total PCB mass (ng) in CAMs and both total PCB concentrations (ng/g wet wt) in adults (r2 = 0.91, p = 0.0001) and eggs (r2 = 0.87, p = 0.0001). The relationship between total PCB mass in CAMs and hepatic cytochrome p450 isozyme activity in chicks (r2 = 0.49, p = 0.0001) and hens (r2 = 0.45, p = 0.014) was also significant but not as strong. This study shows that CAMs can be used to estimate avian exposure to PCBs and resultant biological response.     

Polychlorinated biphenyls (PCB) in fish from hatcheries and clarifying ponds

The concentrations of six selected single polychlorinated biphenyl (PCB) congeners, for which legal tolerance levels became valid in 1988, and the congener no. 49 (2,2',4,5'-tetrachlorobiphenyl) were determined in the muscle tissue of 58 fishes from fish hatcheries and in 17 fishes from settle ponds. The fish were taken from flowing waters in the years 1986 and 1987. High and low chlorinated biphenyls were present in each sample, but the concentration of the low chlorinated biphenyls was distinctly lower than that of the higher chlorinated ones. Nevertheless these results demonstrate the intake of components of low chlorinated technical PCB mixtures in the environment and food chains. Compared with the investigations carried out in 1980/81 in fishes from fish hatcheries, a decrease of PCB contamination in the muscle tissues with regard to the technical mixture Clophen A 60 was observed. This is in accordance with the results our team obtained a short time previously in muscle tissue from foxes and in food-stuffs. The concentration of all PCB congeners determined in the muscle tissue from fish of settle ponds was significantly higher than in the tissue from fish taken from hatcheries. Thus, the PCB content depends on the PCB load in different environments. Therefore, fishes can be useful as bioindicators for the intake of low and high chlorinated PCB congeners in aquatic ecosystems.     

Effect of sorbate planarity on environmental black carbon sorption

Soot and charcoal, collectively termed "black carbon" or BC, can exhibit extremely strong sorption of many hydrophobic organic compounds. In order to include BC sorption in fate models, it is important to know BC nanopore surface areas. In addition, it is useful to know for which compounds BC sorption can be expected to be important. By nitrogen adsorption measurements at ultralow pressures on sediment that was strongly enriched in BC by HF treatment and/or chemothermal oxidation at 375 degrees C, we found that environmental BC has nanoporosity in the <4-10 A size range. The nanopore surface area (<50 A) of BC in Lake Ketelmeer (The Netherlands) sediment was approximately 58 m2/g. We measured sorption isotherms over a wide concentration interval for four compounds with the same Kow (10(46+/-0.1): planar anthracene (ANT), phenanthrene (PHE), and 4-chlorobiphenyl (4-PCB) along with nonplanar 2,2'-dichlorobiphenyl (2,2'-PCB). The environmental BC sorption coefficients of these iso-Kow compounds decreased in the order ANT > PHE approximately 4-PCB > 2,2'-PCB and spanned a factor of 50-200, depending on concentration. Nonplanar 2,2'-PCB showed much more linear BC sorption (nF = 0.92) than the planar compounds (nF = 0.54-0.70). This shows that steric hindrance strongly attenuates BC-sorbate interactions for a nonplanar PCB. Thus, BC is more important for environmental sorption of planar compounds (>50% sorbed to BC in the nanogram per liter range) than for nonplanar ones (<10-20%). Using the measured BC nanopore surface area, a close agreement between modeled and measured BC sorption data could be found.     

Polychlorinated biphenyls: determination of individual components in raw milk and contaminated fodder

Since 1980, 2145 samples of raw milk from producers in the district of Freiburg have been analysed for polychlorinated biphenyls (PCB) during a monitoring programme. In 1983, we started to search for the source of PCB, whenever milk was contaminated above the average value (above 0.2 mg/kg fat, calculated as Clophen A60). In 7 cases, previous coats of paint in the silos proved to be the cause of the PCB contamination. Five samples of milk and 4 corresponding silages as well as 1 sample of wood (from a cowshed) were investigated for all of the individual PCB components included in the technical mixtures of Clophen A30 and A60. Two samples of silages contained both low and high chlorinated biphenyls, whereas low chlorinated biphenyls (di-, tri-, and tetrachlorinated biphenyls) were not detected in the corresponding milk samples. Pentachlorinated biphenyls were only detected in the range of 1%-2%. In the samples of wood and corresponding milk, a different PCB pattern appeared. There were remarkably high percentages of hepta- and octachlorinated biphenyls as well as a lower percentage of hexachlorinated biphenyls. The exact PCB content of the milk, determined by the addition of all single components, proved to be approximately half the value obtained by the usual calculation based on the evaluation of the three main peaks of the technical PCB mixture (Clophen A60). During 1984-1987, 607 samples of raw milk were analysed for six single PCB components, for which legal tolerance levels became valid in 1988.(ABSTRACT TRUNCATED AT 250 WORDS)     

Polychlorierte Biphenyle: Bestimmung der Einzelkomponenten in Rohmilch und kontaminierten Futtermitteln

Zusammenfassung Im Rahmen eines Milchkataster-programmes wurden im Regierungsbezirk Freiburg seit 1980 2145 Rohmilchproben auf polychlorierte Biphenyle (PCB) untersucht. Bei erhöhten PCB-Gehalten (über 0,2 mg/kg Fett, ber. als Clophen A60) wurde 1983 erstmals nach den Quellen der Kontamination geforscht. Dabei erwiesen sich in 7 Fällen PCB-haltige Altanstriche in den Futtersilos als Ursache. Bei 5 Milchproben und 4 zugehörigen Futtermitteln sowie einer Holzprobe aus dem Stall wurden sämtliche PCB-Einzelkomponenten vom Typ Clophen A30 und A60 bestimmt. In 2 Futtermittelproben lagen nieder- und höherchlorierte Biphenyle nebeneinander vor, während in den zugehörigen Milchproben keine niederchlorierten (Di-, Tri- oder Tetrachlor-)Biphenyle nachweisbar waren. Pentachlorbiphenyle wurden in der Milch nur zu 1–2% gefunden. Das Holz und die zugehörige Milch wiesen eine von den anderen Proben abweichende Verteilung im PCB-Muster auf. Auffallend waren in der Milch die höheren Anteile an Hepta-und Octachlorbiphenylen sowie ein geringerer Prozentgehalt an Hexachlorbiphenylen. Der wahre PCB-Gehalt als Summe aller Einzelkomponenten lag in den Milchproben um etwa 50% niedriger als der über die 3 Hauptkomponenten berechnete Clophen A60-Gehalt. Die Untersuchung von 607 Rohmilchproben aus den Jahren 1984–1987 auf die in der Schadstoff-Höchstmengen-Verordnung von 1988 angegebenen PCB-Einzelkomponenten bestätigte das Fehlen von Tri- und Tetrachlorbiphenylen sowie den geringen — meist nicht nachweisbaren — Pentachlorbiphenyl-Gehalt. Die Lebensmittel-rechtliche Situation wird dargestellt.

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Polychlorinated biphenyls: Determination of the individual components in raw milk and contaminated silages

Summary Since 1980, 2145 samples of raw milk from producers in the district of Freiburg have been analysed for polychlorinated biphenyls (PCB) during a monitoring programme. In 1983, we started to search for the source of PCB, whenever milk was contaminated above the average value (above 0.2 mg/kg fat, calculated as Clophen A60). In 7 cases, previous coats of paint in the silos proved to be the cause of the PCB contamination. Five samples of milk and 4 corresponding silages as well as 1 sample of wood (from a cowshed) were investigated for all of the individual PCB components included in the technical mixtures of Clophen A30 and A60. Two samples of silages contained both low and high chlorinated biphenyls, whereas low chlorinated biphenyls (di-, tri-, and tetrachlorinated biphenyls) were not detected in the corresponding milk samples. Pentachlorinated biphenyls were only detected in the range of 1%–2%. In the samples of wood and corresponding milk, a different PCB pattern appeared. There were remarkably high percentages of hepta- and octachlorinated biphenyls as well as a lower percentage of hexachlorinated biphenyls. The exact PCB content of the milk, determined by the addition of all single components, proved to be approximately half the value obtained by the usual calculation based on the evaluation of the three main peaks of the technical PCB mixture (Clophen A60).During 1984–1987, 607 samples of raw milk were analysed for six single PCB components, for which legal tolerance levels became valid in 1988. As a result, the lack of tri- and tetrachlorinated biphenyls in milk was confirmed, as well as the low, often not detectable content of pentachlorinated biphenyls. The German laws regarding PCB are discussed.

     

Organochlorine compounds in Lake Superior: chiral polychlorinated biphenyls and biotransformation in the aquatic food web

The enantiomeric composition of seven chiral PCB congeners was measured in the Lake Superior aquatic food web sampled in 1998, to determine the extent of enantioselective biotransformation in aquatic biota. All chiral PCB congeners studied (CBs 91, 95, 136, 149, 174, 176, and 183) biomagnified in the Lake Superior aquatic food web, based on biomagnification and food web magnification factors greater than unity. PCB atropisomers were racemic in phytoplankton and zooplankton, suggesting no biotransformation potential toward PCBs for these low trophic level organisms. However, Diporeia and mysids had significantly nonracemic residues for most chiral congeners studied. This observation suggests that these macrozooplankton can stereoselectively metabolize chiral congeners. Alternatively, macrozooplankton obtained nonracemic residues from feeding on organic-rich suspended particles and sediments, which would imply that stereoselective microbial PCB biotransformation may be occurring in Lake Superior sediments at PCB concentrations far lower than that previously associated with such activity. Widely nonracemic PCB residues in forage fish (lake herring, rainbow smelt, and slimy sculpin) and lake trout suggest a combination of both in vivo biotransformation and uptake of nonracemic residues from prey for these species. Minimum biotransformation rates, calculated from enantiomer mass balances between predators and prey, suggest metabolic half-lives on the order of 8 yr for CB 136 in lake trout and 2.6 yr for CB 95 in sculpins. This result suggests that significant biotransformation may occur for metabolizable PCB congeners over the lifespan of these biota. This study highlights the potential of chiral analysis to study biotransformation processes in food webs.