Faculty Bibliography

Technical polychlorinated byphenyl (PCB) preparations--Delors 103, 104, 105, and 106--produced in the former Czechoslovakia were analyzed for their chlorobiphenyl (CB), chloronaphthalene (PCN) and chlorinated dibenzofuran (PCDF) composition and content using high resolution gas chromatography-mass spectrometry techniques. The congener patterns of Delors 103, 104, 105, and 106 resembled Aroclors 1242, 1248, 1254, and 1260. Delors contained PCNs and PCDFs, as impurities, at microgram per gram concentrations. Concentrations of PCNs and PCDFs in Delors were greater than those found in the corresponding Aroclors. The potential for the emissions of PCNs and PCDFs from Delor was estimated to be 3680 and 860 kg, respectively. Non- and mono-ortho PCBs were the major contributors to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents in Delor mixtures.

BACKGROUND:Dichlorodiphenyltrichloroethane (DDT) and polychlorinated biphenyls (PCBs) are ubiquitous environmental contaminants that have been banned in most countries, but considerable amounts continue to cycle the ecosphere. Top trophic level predators, like sea birds and marine mammals, bioaccumulate these lipophilic compounds, reflecting their presence in the environment. RESULTS:We measured concentrations of tDDT (p,p' - DDT + p,p' - DDD + p,p' - DDE) and PCBs in the blubber of dead California sea lions stranded along the California coast. tDDT and PCB concentrations were 150 +/- 257 ug/g lipid weight (mean +/- SD) and 44 +/- 78 ug/g lipid weight, respectively. There were no differences in tDDT or PCB concentrations between animal categories varying in sex or age. There was a trend towards a decrease in tDDT and PCB concentrations from northern to southern California. The lipid content of the blubber was negatively correlated with levels of tDDT and PCBs. tDDT concentrations were approximately 3 times higher than PCB concentrations. CONCLUSIONS:tDDT levels in the blubber of California sea lions decreased by over one order of magnitude from 1970 to 2000. PCB level changes over time were unclear owing to a paucity of data and analytical differences over the years. Current levels of these pollutants in California sea lions are among the highest among marine mammals and exceed those reported to cause immunotoxicity or endocrine disruption.

Total mercury concentrations were determined by cold-vapour atomic absorption spectroscopy (CV-AAS) in 117 samples of caps, 117 of stalks and 47 of whole fruiting bodies of 13 species of wild mushrooms and in 164 underlying soil substrate collected from Zaborski Landscape Park during 1997 and 1998. The study area is a background, forested site with rural landscape and no known local sources of mercury emission. Mean mercury concentrations in mushrooms varied widely (range: 50 +/- 20 to 3700 +/- 1700 ng/g, dry matter) depending on the site and mushroom species investigated. However, mercury concentrations in soil samples varied less (range: 3.0 +/- 3.0 to 43 +/- 17 ng/g dry matter). Fruiting bodies of Common Puffball (Lycoperdon perlatum) and King Bolete (Boletus edulis) contained the greatest concentrations of mercury of 3700 +/- 1700 and 2600 +/- 1200 ng/g dry matter, respectively. A positive correlation existed between mercury concentrations in the caps of Slippery Jack (Suillus luteus) and Fly Agaric (Amanita muscaria) (p < 0.01) and mercury concentrations in corresponding soils. However, concentrations of mercury in The Sickener (Russula emetica) was negatively correlated with its soil substrate (p < 0.01). Bioconcentration factors (BCFs: concentrations ratios of mercury in mushroom to soil) of total mercury in whole fruiting bodies or caps were greatest for Common Puffball (L. perlatum), Larch Bolete (Suillus grevillei) and King Bolete (B. edulis) and varied between 130 +/- 78 and 160 +/- 120, while for the other species BCFs were between 4.0 +/- 6.0 and 61 +/- 20 in caps, and 4.4 +/- 3.1 and 70 +/- 68 in stalks. The concentration ratios of Hg in cap to stalk were from 1.1 +/- 0.5 for Poison Pax (Paxillus involutus) to 2.7 +/- 1.7 in Larch Bolete (S. grevillei).

This study examined the ability of environmentally relevant concentrations of 10 different polybrominated diphenyl ethers (PBDEs) to induce aryl hydrocarbon receptor (AhR)- and estrogen receptor (ER)-mediated gene expression in vitro. It also examined the ability of PBDEs to displace steroid hormones from serum proteins in vitro. At concentrations ranging up to 880 ng/ ml, none of the PBDEs significantly displaced tritiated 17beta-estradiol (E2) or testosterone from hormone-stripped carp serum. At concentrations ranging up to 500 ng/ml, 9 of 10 PBDEs tested failed to induce ER- or AhR-mediated gene expression in MVLN and H4IIE-luc cells, respectively. One congener, 3,3',4,4',5-pentabromodiphenylether (BDE 126), induced significant AhR-mediated gene expression at 500 ng/ml, but the magnitude of induction was only 13% of that caused by 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). Overall, the PBDEs tested were found to be at least 200,000 times less potent than TCDD and 50,000 times less potent than E2 for inducing AhR- and ER-mediated gene expression, respectively.

Livers of birds collected from Japan and Korea (n = 83) were analyzed to determine the concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanesulfonamide (FOSA), perfluorooctanoic acid (PFOA) and perfluorohexanesulfonate (PFHS). PFOS was found in the livers of 95% of the birds analyzed at concentrations greater than the limit of quantitation (LOQ) of 10 ng/g, wet weight. The greatest concentration of PFOS of 650 ng/g, wet weight, was found in the liver of a common cormorant from the Sagami River in Kanagawa Prefecture. Concentrations of PFOS in bird livers from Japan and Korea were within the ranges of values reported for those from the United States and certain European countries. PFOA and PFHS were found in 5-10% of the samples analyzed. The greatest concentrations of PFOA and PFHS in bird livers were 21 and 34 ng/g, wet weight, respectively. FOSA was found in all the samples (n = 10) of cormorants collected from the Sagami River in Japan. The greatest concentration of FOSA in cormorant liver was 215 ng/g, wet weight. There was no significant correlation between the concentrations of PFOS and FOSA in cormorants collected from the Sagami River. These results suggested that the distribution of FOSA is localized. No age- or gender-specific differences in fluorochemical concentrations could be discerned in birds.

Adult female rainbow trout were exposed to dietary 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) at concentrations of 1.8, 18 and 90 ng TCDD/kg (ww) food for up to 300 day. At the end of the exposure fish were spawned and the reproductive outcomes were assessed. TCDD was accumulated into tissues and eggs in a dose-dependent manner with steady state being achieved after 50-100 day of exposure. Biochemical and hematological parameters were monitored at 50, 100, 150, and 200 day after the beginning of exposure. The survival of adult female trout was reduced in a dose-dependent manner by exposure to TCDD in the diet. Fish fed 1.8 ng TCDD/kg, moist weight of diet, showed significantly reduced survival compared with those fed the control diet. TCDD also affected survival of fry from females fed 1.8 ng TCDD/kg. Observed adverse effects in adult fish were as sensitive as early life-stage endpoints. Liver EROD activity was only moderately increased in all exposure groups after 250+ day of exposure. Low rates of edema and deformities were observed in fry from all treatment groups including controls. This study has demonstrated adverse effects of TCDD to both adults and fry at concentrations comparable to current environmental concentrations. This suggests that direct adult toxicity as well as reproductive endpoints need to be incorporated in the current risk assessment paradigm for these compounds.

Soil samples were collected from Changwon and Masan Cities, Korea, and analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs). Nearly all tetra- through octachlorinated PCDDs/DFs including the 17 2,3,7,8-substituted PCDDs/DFs were detected in all samples. Total concentrations of PCDDs/DFs and of 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TeCDD) equivalents (TEGs) in soils ranged from 35 to 121,400 pg/g, dry weight, and from 0.2 to 3720 pg of I-TEQ/g, respectively. On the basis of guidelines for TEQ concentrations established in Germany and the United States, 9 of 23 soil samples (39% of the total samples analyzed) could not be expected to pose human health hazards. The rest of 61% of soils need measures such as investigations of source identification, soil decontamination, and/or soil removal. Total concentrations of PCDDs/DFs were greater at or near four industrial sites, which are concerned with the steel industry, petrochemical-related industry, and industrial waste incineration, than other areas. This indicates the presence of potential source areas. Soil collected from a site 50 m from an open-burning industrial waste incinerator in an industrial complex was heavily contaminated, containing a total concentration of PCDDs/DFs of 121,400 pg/g, dry weight. PCDDs/DFs were also detected in soils from the top of a 200 m mountain indicating a wide dispersal of PCDDs/DFs by atmospheric transport from point source areas. The congener pattern and relative proportions of PCDFs in soils suggest that commercial PCB preparations such as Kanechlors may be one of the sources. The wide range of PCDD/DF isomers detected in soils from many locations also suggests a multitude of sources, in addition to commercial PCBs, such as incineration of industrial wastes such as car tires, scrap wires, plastics, papers, and emission of automobile exhaust.

Persistent organic pollutants and alkylphenols (APs) were determined in sediment and water samples from Onsan Bay, Korea, by using instrumental analysis and in vitro gene expression cell bioassay. Polycyclic aromatic hydrocabons (PAHs) were the predominant compounds in sediments with concentrations as great as 573 ng/g dry weight. The PAH concentrations were elevated in sediment from inland rivers that flow through Onsan City (mean: 116 ng/g dry wt) and discharge into Onsan Bay. Concentrations of polychlorinated biphenyls (PCBs) in sediments ranged from <1.00 to 56.2 ng/g dry weight. Among different organochlorine (OC) pesticides analyzed (hexachlorobenzene, hexachlorocyclohexanes, chlordanes, and DDTs), DDT concentrations were the greatest, ranging from <0.01 to 7.58 ng/g dry weight. The spatial gradient of contaminant concentrations suggested that streams and rivers are the major sources of PCBs, PAHs, and APs to the bay. Maximum concentrations of nonylphenol, octylphenol, and bisphenol A in sediments were 860, 11, and 204 ng/g dry weight, respectively. Screening of Onsan Bay sediment samples for dioxinlike activity with the H4IIE-luc in vitro cell bioassay revealed that 17 of 22 samples contained significant dioxinlike activity. Further fractionation of sediment extracts indicated that mid-polar and more polar fractions were responsible for the significant dioxinlike activity. Based on a mass balance analysis, PAHs apparently accounted for only a small portion of dioxinlike responses elicited by sediment extracts. Only one raw extract of sediment elicited a significant estrogenic response by MVLN cells. The combination of instrumental analysis and in vitro bioassay was useful to assess sediment quality and characterize the causative agents or potential toxic compounds present.

Here we report accumulation patterns of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and pesticides (HCB, p,p'DDE) in polar organisms (polar bear from Alaskan Arctic and krill, sharp-spined notothen, crocodile icefish, Antarctic silverfish, Adélie penguin, South polar skua, and Weddell seal from the Ross Sea, Antarctica). PCNs, found in most of the samples, ranged from 1.5 pg/g in krill to 2550 pg/g in South polar skua on a wet weight basis. Lower chlorinated PCNs were the predominant congeners in organisms except skua and polar bear that showed similar PCN homologue patterns. PCDD/F concentrations were <90 pg/g wet wt in polar organisms; PCDD congeners showed peculiar accumulation patterns in different organisms. Correlation existed between PCN and PCB concentrations. PCB, HCF, and p,p'DDE levels were the highest in skua liver (11,150 ng/g wet wt, 345 ng/g wet wt, and 300 ng/g wet wt, respectively). Contribution of PCNs to 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ) was negligible (<0.1%) because of the lack of most toxic congeners. The highest TEQ was found in South polar skua liver (45 pg/g, wet weight). This is the first study to document the occurrence of PCNs in Antarctic organisms. High levels of dioxin-like chemicals in skua suggest the importance of intake via diet and migration habits, thus POP detection can be useful to trace migration behavior. Moreover, POP concentrations in penguin and skua eggs prove their transfer from the mother to eggs.

Perfluorooctanesulfonate (PFOS; C8F17SO3-), perfluorooctanesulfonamide (FOSA; C8F17SO2NH2), perfluorohexanesulfonate (PFHxS; C6F13SO3-), and perfluorooctanoate (PFOA; C7F15CO2-) were detected in 175 samples of liver and blood of bluefin tuna (Thunnus thynnus), swordfish (Xiphias gladius), common cormorants (Phalacrocorax carbo), bottlenose dolphins (Tursiops truncatus), striped dolphins (Stenella coeruleoalba), common dolphins (Delphinus delphi), fin whales (Balenoptera physalus), and long-finned pilot whales (Globicephala melas) from the Italian coast of the Mediterranean Sea and in livers of ringed seals (Phoca hispida), gray seals (Halichoerus grypus), white-tailed sea eagles (Haliaeetus albicilla), and Atlantic salmon (Salmo salar) from coastal areas of the Baltic Sea. PFOS was detected in all of the wildlife species analyzed. Concentrations of PFOS in blood decreased in order of bottlenose dolphins > bluefin tuna > swordfish. Mean PFOS concentrations (61 ng/ g, wet wt) in cormorant livers collected from Sardinia Island in the Mediterranean Sea were less than the concentrations of PFOA (95 ng/g, wetwt). PFOS concentrations in cormorant livers were significantly correlated with those of PFOA. FOSA was found in 14 of 19 livers or blood samples of marine mammals from the Mediterranean Sea. The highest concentration of 878 ng FOSA/g, wet wt, was found in the liver of a common dolphin. Livers of ringed and gray seals from the Bothnian Bay in the Baltic Sea contained PFOS concentrations ranging from 130 to 1,100 ng/g, wet wt. No relationships between PFOS concentrations and ages of ringed or gray seals were observed. Concentrations of PFOS in livers of seals were 5.5-fold greater than those in corresponding blood. A significant positive correlation existed between the PFOS concentrations in liver and blood, which indicates that blood can be used for nonlethal monitoring of PFOS. Trend analysis of PFOS concentrations in livers of white-tailed sea eagles collected from eastern Germany and Poland since 1979 indicated an increase in concentrations during the 1990s. Livers of Atlantic salmons did not contain quantifiable concentrations of any of the fluorochemicals monitored. PFOS is a widespread contaminant in wildlife from the Baltic and the Mediterranean Seas, while FOSA and PFOA were detected only in certain locations indicating their sporadic spatial distribution.