Tissue distribution kinetics of 2,2',4,4',5,5'-hexachlorobiphenyl in ringdoves after oral dosing.

Ring doves were provided contaminated food spiked with [(13)C]-2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153) over a period of 63 days. Animals were sacrificed after 0.33, 0.5, 1, 2, 4, 8, 18, 36 and 63 days following access to contaminated food. At each time point, chemical concentrations in blood, liver, brain, gonad, adipose and remaining whole carcass was determined. Whole body concentrations of PCB 153 increased linearly with time over the experiment indicating that the birds did not reach steady state with their food after 63 days. Tissue/plasma concentration ratios were plotted as a function of time to determine time to inter-tissue steady state for fast and slowly perfused tissues. Liver, brain and gonad achieved steady state concentrations with plasma in less than 3 days, whereas fat and carcass tissues required 9.7 and 11.5 days, respectively. The results indicate that inter-tissue distribution kinetics for PCBs in birds is relatively rapid and completed within a little over a week following exposure to a contaminated diet.

Geographic distribution of selected elements in the livers of polar bears from Greenland, Canada and the United States.

To assess geographic distributions of elements in the Arctic we compared essential and non-essential elements in the livers of polar bears (Ursus maritimus) collected from five regions within Canada in 2002, in Alaska between 1994 and 1999 and from the northwest and east coasts of Greenland between 1988 and 2000. As, Hg, Pb and Se varied with age, and Co and Zn with gender, which limited spatial comparisons across all populations to Cd, which was highest in Greenland bears. Collectively, geographic relationships appeared similar to past studies with little change in concentration over time in Canada and Greenland for most elements; Hg and Se were higher in some Canadian populations in 2002 as compared to 1982 and 1984. Concentrations of most elements in the polar bears did not exceed toxicity thresholds, although Cd and Hg exceeded levels correlated with the formation of hepatic lesions in laboratory animals.

Composition of chlorinated hydrocarbon contaminants among major adipose tissue depots of polar bears (Ursus maritimus) from the Canadian high Arctic.

Monitoring of environmental contaminants in Canadian Arctic polar bears (Ursus maritimus) typically has used superficial adipose tissue samples collected as part of controlled native subsistence hunts. However, little attention has been paid to the compositional difference in contaminants that may exist among the major adipose depots that are routinely collected. To address this knowledge gap, we investigated the profiles and concentrations of chlorinated hydrocarbon contaminants (CHCs), including major polychlorinated biphenyl (PCB) congeners and organochlorine (OC) pesticides and metabolites, in six major adipose depots (i.e. superficial, inter-muscular and intra-abdominal regions) obtained from adult male polar bears in the vicinity of Resolute Bay, Canadian high Arctic. Concentrations and congener patterns of PCBs (20 congeners) and OCs (14 compounds; chlordanes and dichlorodiphenyltrichloroethanes and metabolites, chlorinated benzenes, hexachlorocyclohexane isomers, octachlorostyrene and dieldrin) were found to be relatively uniform throughout the adipose tissue of male polar bears. The only exception was the inter-muscular adipose depot from the cervical region, which was characterized, compared to other major depots routinely sampled, by lower proportions of higher-chlorinated and recalcitrant congeners such as CB170/190, 180, 194 and 206, and higher contribution of the lower-chlorinated PCBs, CB47, 74 and 99. No difference in the OC makeup and concentrations was found among the adipose depots investigated. In view of this, we conclude that the determination of CHCs in adipose tissue of polar bears from any major depots, with the potential exception of the fat under the neck muscles, would give a representative picture of the overall CHC composition and concentrations in polar bear fat for purpose of trend monitoring.

Regional and species specific bioaccumulation of major and trace elements in Arctic seabirds.

Twenty-five essential and nonessential elements were analyzed in Arctic seabirds to study the influence of phylogeny, tissue, Arctic region, and diet on avian element accumulation and to identify co-occurrence among metals. Muscle and liver concentrations were positively correlated, generally being higher in liver than in muscle, and generally did not differ by sex. Zinc showed the highest absolute concentrations in all samples (mean, 11.2-26.7 microg/g in muscle, depending on species and area), followed by copper (5.2-7.5 microg/g), arsenic (0.5-5.4 microg/g), selenium (1.0-5.8 microg/g), rubidium (1.4-2.2 microg/g), and cadmium (0.04-1.2 microg/g). Mercury levels ranged from 0.05 to 0.8 microg/g in muscle. The concentrations varied among species (dovekie [Alle alle], black guillemot [Cepphus grylle], thick-billed murre [Uria lomvia], black-legged kittiwake [Rissa tridactyla], northern fulmar [Fulmaris glacialis], ivory gull [Pagophila eburnean], Thayer's gull [Larus thayeri], and glaucous gull [Larus hyperboreus]), and between the northern Baffin Bay (Canada) and the Barents Sea, depending on the element. Whereas some elements (e.g., mercury and zinc) increased in absolute and standardized concentrations with trophic level in the northern Baffin Bay, most elements showed no relationship with trophic level or other dietary descriptors. In absolute concentrations, nonessential elements differed between regions, whereas essential elements differed among species but not within a species across the two regions. Standardized concentrations (element pattern) of both essential elements and nonessential elements generally did not differ between regions but was highly species specific and, thus, determined by the phylogenetic element regulation capacity. The usefulness of multivariate ordination in element wildlife studies is illustrated, which provides additional insight regarding element co-occurrence in wildlife, allows inclusion of species with low sample number, and reduces the possibility of type II errors created by low sample size.

Does high organochlorine (OC) exposure impair the resistance to infection in polar bears (Ursus maritimus)? Part II: Possible effect of OCs on mitogen- and antigen-induced lymphocyte proliferation.

Previous studies have reported alarmingly high levels of organochlorines (OCs), particularly polychlorinated biphenyls (PCBs), in free-ranging polar bears (Ursus maritimus). In this study plasma concentration of PCBs ranged from 14.8 to 200 ng/g wet weight. The aim of the study was to investigate associations between OCs and lymphocyte proliferation after in vitro stimulation with different mitogens and antigens. In 1998 and 1999, 26 and 30 free-ranging polar bears from Svalbard and Churchill, Canada, respectively, were recaptured 32-40 d following immunization with inactivated tetanus toxoid and hemocyanin from keyhole limpets (KLH) to sensitize lymphocytes. At recapture, blood was sampled for determination of plasma levels of PCBs and organochlorine pesticides (OCPs) and lymphocyte proliferation after in vitro stimulation with specific mitogens--phytohemagglutinin (PHA), pokeweed mitogen (PWM), concanavalin A (Con A), lipopolysaccharide (LPS), and purified protein derivative of Mycobacterium avium subsp. paratuberculosis (PPD)--and antigens: tetanus toxoid and KLH. The combinations of sum(PCBs) (sum of 12 individual PCB congeners), sum(OCPs) (sum of 6 OCPs), and their interactions contributed up to 15% of the variations in the lymphocyte responses. By using multiple regression analyses, followed by classical mathematic function analyses, thresholds for immunomodulation were estimated. Depending on the lymphocyte proliferation response studied, the estimated thresholds for significant immunomodulation were within the concentration ranges 32-89 ng/g wet weight (ww) and 7.8-14 ng/g ww for sum(PCBs) and sum(OCPs), respectively. Thus, this study demonstrated that OC exposure significantly influences specific lymphocyte proliferation responses and part of the cell-mediated immunity, which also is associated with impaired ability to produce antibodies (Lie et al., 2004).

Mercury and other trace elements in a pelagic Arctic marine food web (Northwater Polynya, Baffin Bay).

Total mercury (THg), methylmercury (MeHg) and 22 other trace elements were measured in ice algae, three species of zooplankton, mixed zooplankton samples, Arctic cod (Boreogadus saida), ringed seals (Phoca hispida) and eight species of seabirds to examine the trophodynamics of these metals in an Arctic marine food web. All samples were collected in 1998 in the Northwater Polynya (NOW) located between Ellesmere Island and Greenland in Baffin Bay. THg and MeHg were found to biomagnify through the NOW food web, based on significant positive relationships between log THg and log MeHg concentrations vs. delta15N muscle and liver . The slope of these relationships for muscle THg and MeHg concentrations (slope=0.197 and 0.223, respectively) were similar to those reported for other aquatic food webs. The food web behavior of THg and delta15N appears constant, regardless of trophic state (eutrophic vs. oligotrophic), latitude (Arctic vs. tropical) or salinity (marine vs. freshwater) of the ecosystem. Rb in both liver and muscle tissue and Zn in muscle tissue were also found to biomagnify through this food web, although at a rate that is approximately 25% of that of THg. A number of elements (Cd, Pb and Ni in muscle tissue and Cd and Li in seabird liver tissue) were found to decrease trophically through the food web, as indicated by significantly negative relationships with tissue-specific delta15N. A diverse group of metals (Ag, Ba, La, Li, Sb, Sr, U and V) were found to have higher concentrations in zooplankton than seabirds or marine mammals due to bioconcentration from seawater. The remaining metals (As, Co, Cu, Ga, Mn, Mo and Se in muscle tissue) showed no relationship with trophic position, as indicated by delta15N values, although As in liver tissue showed significant biomagnification in the seabird portion of the food web.

Chlorinated hydrocarbon contaminants and metabolites in polar bears (Ursus maritimus) from Alaska, Canada, East Greenland, and Svalbard: 1996-2002.

A suite of chlorinated hydrocarbon contaminants (CHCs) including organochlorine pesticides (OCPs) and by-products, polychlorinated biphenyls (PCBs), and methyl sulfone (MeSO2) PCB and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) metabolites were determined in adipose tissue of 107 adult and sub-adult polar bears, almost exclusively females, sampled between 1996 and 2002 from populations spanning Arctic and Subarctic regions of Alaska, Canada, East Greenland, and Svalbard. The East Greenland and Svalbard populations of polar bears were distinguished by higher proportions of dichlorodiphenyldichloroethane (DDT)-related compounds, nonachlors, oxychlordane, and higher-chlorinated and persistent PCB congeners (hepta- to nona-chlorinated). Conversely, Alaska, the westernmost population of the North American Arctic, was characterized by higher proportions of relatively volatile compounds such as hexachlorocyclohexanes (HCHs) and pentachlorobenzene (PnCBz), lower-chlorinated PCB congeners (tri- to penta-chlorinated), and lower proportions of oxychlordane. Geometric mean (GM) with 95% confidence limits (CL) SigmaHCH concentrations were highest in Alaska male polar bear fat samples (GM 593; CL 363-909 ng g-1 lipid weight), SigmaDDT concentration were highest in East Greenland female samples (GM 309; CL 249-490 ng g-1 l.w.), and Sigma42PCB (GM 5972; CL 4637-9129 ng g-1 l.w.) and SigmaMeSO2-PCB (GM 198; CL 162-279 ng g-1 l.w.) concentrations were highest in female samples collected from Svalbard. The distribution of Sigma-chlordane-related compounds (SigmaCHL), SigmaCBz, mirex, and dieldrin was relatively uniform among the populations of polar bears investigated. The present 1996-2002 data of female polar bear fat samples was compared to spatial assessments of female polar bear fat samples collected between 1989 and 1993 from comparable populations. The two-point temporal comparisons showed a general decrease for age-adjusted mean concentrations of SigmaCHL, p,p'-DDE, Sigma42PCB, SigmaMeSO2-PCB and 3-MeSO2-p,p'-DDE over a period of approximately 10 years. However, concentrations of dieldrin were comparatively unchanged. Comparisons of present 2001-2002 concentrations in fat of female polar bears from Western Hudson Bay showed great consistency with temporal trends (1991-1999) previously reported for the same region, i.e. the apparent non-decreasing trend of SigmaCHL, beta-HCH, SigmaHCH and dieldrin, and the apparent declining trend for SigmaPCB. However, present concentrations of alpha-HCH and SigmaCBz were elevated, and SigmaDDT was notably lower in Western Hudson Bay samples compared to the last measurements in fat samples collected in 1999, which was not in accord with reported temporal trends for this region. As a result of their relatively high degree of contamination, East Greenland and Svalbard polar bears are at higher health risk of contaminant exposure among Arctic and Subarctic populations. In addition to continued biomonitoring, further research on health and population status is needed to evaluate the impact from chronic exposure of polar bear populations to CHCs and their metabolites.

Enantiomeric fractions of chiral polychlorinated biphenyls provide insights on biotransformation capacity of arctic biota.

Chiral polychlorinated biphenyls (PCBs) were measured in an arctic marine food web from the Northwater Polynya (NOW) in the Canadian Arctic to examine potential biotransformation of chiral PCB atropisomers. Organisms under investigation included pelagic zooplankton, Arctic cod (Boreogadus saida), seabirds, and ringed seals (Phoca hispida). Previous studies using achiral methods (e.g., biomagnification factors) have shown that chiral PCB congeners biomagnified in the NOW food web, but provided little information about biotransformation of PCBs except in extreme cases (i.e., high biotransformation). In this study, highly nonracemic enantiomeric fractions (EFs) were observed in several seabird species and ringed seals, but racemic EFs were found in prey (zooplankton and fish). This suggests stereoselective and species-specific biotransformation of individual PCB stereoisomers by birds and mammals. These results are consistent with previously reported biotransformation activity of chiral organochlorine pesticides, alpha-hexachlorocyclohexane, and chlordane within these organisms. This study demonstrates the utility of using chiral analysis of PCBs to investigate biotransformation within biota of arctic food webs.

Pentachlorophenol and hydroxylated polychlorinated biphenyl metabolites in umbilical cord plasma of neonates from coastal populations in Québec.

Concentrations of polychlorinated biphenyls (PCBs), hydroxylated metabolites of PCBs (HO-PCBs) and octachlorostyrene (4-HO-HpCS), and pentachlorophenol (PCP) were determined in umbilical cord plasma samples from three different regions of Québec. The regions studied included two coastal areas where exposure to PCBs is high because of marine-food-based diets--Nunavik (Inuit people) and the Lower North Shore of the Gulf of St. Lawrence (subsistence fishermen)--and a southern Québec urban center where PCB exposure is at background levels (Québec City). The main chlorinated phenolic compound in all regions was PCP. Concentrations of PCP were not significantly different among regions (geometric mean concentration 1,670 pg/g, range 628-7,680 pg/g wet weight in plasma). The ratio of PCP to polychlorinated biphenyl congener number 153 (CB153) concentration ranged from 0.72 to 42.3. Sum HO-PCB (sigma HO-PCBs) concentrations were different among regions, with geometric mean concentrations of 553 (range 238-1,750), 286 (103-788), and 234 (147-464) pg/g wet weight plasma for the Lower North Shore, Nunavik, and the southern Québec groups, respectively. Lower North Shore samples also had the highest geometric mean concentration of sum PCBs (sum of 49 congeners; sigma PCBs), 2,710 (525-7,720) pg/g wet weight plasma. sigma PCB concentrations for Nunavik samples and southern samples were 1,510 (309-6,230) and 843 (290-1,650) pg/g wet weight plasma. Concentrations (log transformed) of sigma HO-PCBs and sigma PCBs were significantly correlated (r = 0.62, p < 0.001), as were concentrations of all major individual HO-PCB congeners and individual PCB congeners. In Nunavik and Lower North Shore samples, free thyroxine (T4) concentrations (log transformed) were negatively correlated with the sum of quantitated chlorinated phenolic compounds (sum PCP and sigma HO-PCBs; r = -0.47, p = 0.01, n = 20) and were not correlated with any PCB congeners or sigma PCBs. This suggests that PCP and HO-PCBs are possibly altering thyroid hormone status in newborns, which could lead to neurodevelopmental effects in infants. Further studies are needed to examine the effects of chlorinated phenolic compounds on thyroid hormone status in newborns.

Does high organochlorine (OC) exposure impair the resistance to infection in polar bears (Ursus maritimus)? Part I: Effect of OCs on the humoral immunity.

This study was undertaken to assess if high levels of organochlorines (OCs) are associated with decreased ability to produce antibodies in free-ranging polar bears (Ursus maritimus) and thus affect the humoral immunity. In 1998 and 1999, 26 and 30 polar bears from Svalbard, Norway, and Churchill, Canada, respectively, were recaptured 32-40 d following immunization with inactivated influenza virus, reovirus, and herpes virus and tetanus toxoid. Blood was sampled at immunization and at recapture for determination of plasma levels of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), serum immunoglobulin G (IgG) concentrations, and specific antibodies against influenza virus, reovirus, and herpes virus, tetanus toxoid, and Mannheimia haemolytica. The OCs alone contributed with up to 7% to the variations in the immunological parameters. The combination of sigma PCBs (sum of 12 individual PCB congeners), sigma OCPs (sum of 6 OCPs), and biological factors accounted for 40-60% of the variation in the immunological parameters. Negative associations were found between sigma PCBs and serum immunoglobulin G (IgG) levels and between sigma PCBs and increased antibody titers against influenza virus and reovirus following immunization. In contrast, a positive association was registered between sigma PCBs and increased antibodies against tetanus toxoid. sigma OCPs also contributed significantly to the variations in the immunological responses. OCs did not have the same impact on the antibody production against M. haemolytica. The present study demonstrated that high OC levels may impair the polar bears ability to produce antibodies and thus may produce impaired resistance to infections.

Examination of the bioaccumulation of halogenated dimethyl bipyrroles in an Arctic marine food web using stable nitrogen isotope analysis.

Concentrations of four possibly naturally produced organohalogens--1,1'-dimethyl-3,3',4-tribromo-4,5,5'-trichloro-2,2'-bipyrrole (DBP-Br3Cl3), 1,1'-dimethyl-3,3',4,4'-tetrabromo-5,5'-dichloro-2,2'-bipyrrole (DBP-Br4Cl2), 1,1'-dimethyl-3,3',4,4',5-pentabromo-5'-chloro-2,2'-bipyrrole (DBP-Br5Cl) and 1,1'-dimethyl-3,3',4,4',5,5'-hexabromo-2,2'-bipyrrole (DBP-Br6)--were quantitated and the extent of their magnification through an entire Arctic marine food web [measured as integrated trophic magnification factors (TMFs)] were calculated. The food web consisted of three zooplankton species (Calanus hyperboreus, Mysis oculata, and Sagitta sp.), one fish species [Arctic cod (Boreogadus saida)], four seabird species [dovekie (Alle alle), black guillemot (Cepphus grylle), black-legged kittiwake (Rissa tridactyla), and glaucous gull (Larus hyperboreus)], and one marine mammal species [ringed seal (Phoca hispida)]. Trophic levels in the food web were calculated from ratios of stable isotopes of nitrogen (15N/14N). All halogenated dimethyl bipyrrole (HDBP) congeners were found to significantly (P<0.02) biomagnify, or increase in concentration with trophic level in the invertebrate--fish--seabird food web. DBP-Br4Cl2 (TMF= 14.6) was found to biomagnify to a greater extent than DBP-Br3Cl3 (TMF = 5.2), DBP-Br5Cl (TMF = 6.9), or DBP-Br6 (TMF = 7.0), even though the Kow of DBP-Br4CI2 was predicted to be lower than those of DBP-Br5Cl and DBP-Br6. None of the four HDBP congeners in ringed seals followed the general trend of increasing concentration with trophic level, which was possibly due to an ability of the seals to metabolize HDBPs.

Organochlorine contaminants in seven species of Arctic seabirds from northern Baffin Bay.

Organochlorine contaminants (OCs) were determined in liver and fat of seven species of seabirds (Alle alle, Uria lomvia, Cepphus grylle, Rissa tridactyla, Pagophila eburnea, Larus hyperboreus, and Fulmaris glacialis) collected in May/June 1998 from the Northwater Polynya in northern Baffin Bay. OC concentrations ranged over an order of magnitude between seabird species and OC groups, with PCBs having the highest concentrations followed by DDT, chlordane, HCH and ClBz. Positive relationships between delta15N (estimator of trophic level) and OC concentrations (lipid basis) were found for all OC groups, showing that trophic position and biomagnification significantly influence OC concentrations in Arctic seabirds. Concentrations of a number of OCs in particular species (e.g., HCH in P. eburnean) were lower than expected based on delta15N and was attributed to biotransformation. P. eburnea and F. glacialis, which scavenge, and R. tridactyla, which migrate from the south, were consistently above the delta15N-OC regression providing evidence that these variables can elevate OC concentrations. Stable isotope measurements in muscle may not be suitable for identifying past scavenging events by seabirds. OC relative proportions were related to trophic position and phylogeny, showing that OC biotransformation varies between seabird groups. Trophic level, migration, scavenging and biotransformation all play important roles in the OCs found in Arctic seabirds.

PCBs and organochlorine pesticides in blubber biopsies from free-ranging St. Lawrence River Estuary beluga whales (Delphinapterus leucas), 1994-1998.

For the first time, organochlorine (OC) contaminants were measured in blubber biopsies from free-ranging St. Lawrence River Estuary beluga whales (Delphinapterus leucas), to compare contaminant levels to those previously measured in dead stranded belugas. PCBs, DDTs, toxaphene and chlordane-related compounds were the major OC contaminants detected in 44 belugas biopsied in 1994-1998. SigmaPCB (the sum of 104 congeners) ranged from 2080 to 128,000 ng/g lipid in males (n=34; minimum estimated ages 8-22 years), and from 148 to 44,100 ng/g lipid in females (n=10; minimum estimated ages 7-22 years). The concentrations of PCBs and OC pesticides in the blubber of these whales overlapped those observed in stranded belugas from an earlier study, and demonstrated comparable age and sex-related trends. However, lower proportions of mirex, HCB, DDTs, and many of the highly chlorinated PCBs occurred in the biopsy samples compared to results for blubber from stranded carcasses. Most major OC compounds were present at lower concentrations in the biopsies, but this does not appear to be solely related to age differences between the two groups, or to emaciation in the stranded whales. Nor does it appear to be associated with the use of superficial biopsies, and the possible stratification of lipids and OCs in the blubber layer. Nevertheless, given these possible confounding factors, and the uncertainty in age estimates for the biopsied whales, the results point to the need for careful interpretation of biopsy results when comparing with data taken from the full depth of the blubber mantle in stranded whales. Taken together, results from both biopsied whales and previously studied stranded belugas indicate that PCB and OC pesticide contamination of St. Lawrence beluga whales may occur across a broader range of levels than previously thought, at least for males which formed the largest group in this study, possibly due to different degrees of dietary exposure. It also appears that measuring contaminant concentrations only in stranded whales, may overestimate OC levels in the population as a whole, especially for highly chlorinated OCs.

Structure elucidation of four possible biogenic organohalogens using isotope exchange mass spectrometry.

The molecular structures of four unknown bioaccumulating halogenated compounds, C10H6N2Br3Cl3, C10H6N2Br4Cl2, C10H6N2Br5Cl, and C10H6N2Br6 were characterized using isotope exchange positive chemical ionization (IE-PCI) mass spectrometry (MS) and identified by comparison to synthesized standards. NH3 and ND3 were used as reagent gases for the IE-PCI-MS experiment. The shift in mass of the quasimolecular ion between the NH3 and ND3 PCI obtained spectra indicated the number of exchangeable hydrogens attached to the two nitrogen atoms in C10H6N2Br4Cl2, and thus the type of amines present (primary, secondary, or tertiary). 19 compounds (13 amines of varying degree of substitution; six containing no nitrogen) were used as reference compounds and controls in the experiment to validate the IE-PCI technique. The results of the IE-PCI-MS indicated the presence of two tertiary amine functional groups. The molecular structures of the four hexahalogenated compounds were then proposed to be 1,1'-dimethyl-3,3',4,-tribromo-4',5,5'-trichloro-2,2'-bipyrrole, 1,1'-dimethyl-3,3',4,4'-tetrabromo-5,5'-dichloro-2,2'-bipyrrole, 1,1'-dimethyl-3,3',4,4',5-pentabromo-5'-chloro-2,2'-bipyrrole, and 1,1'-dimethyl-3,3',4,4',5,5'-hexabromo-2,2'-bipyrrole and subsequently synthesized. Comparison of retention times and electron capture negative ionization (ECNI) full scans on various gas chromatography (GC) columns between the synthesized bipyrroles and the corresponding unknown compounds in biota indicated that three of the unknown compounds--possible marine natural products--were the proposed halogenated dimethyl bipyrroles. The placement of the halogen atoms on the fourth compound, C10H6N2Br3Cl3 could not be unequivocally determined since the synthesized standard could not be fully characterized.

Vapour pressures, aqueous solubilities, Henry's Law constants, and octanol/water partition coefficients of a series of mixed halogenated dimethyl bipyrroles.

Basic physical-chemical properties of five bromine and chlorine containing mixed halogenated dimethyl bipyrroles (HDBPs) were determined using established methods. Subcooled liquid vapour pressures (P(o)(L,25)), aqueous solubilities (S(w,25)), and octanol/water partition coefficients (K(ow)) were determined using the gas chromatography-retention time, generator column, and slow-stirring methods, respectively. Henry's Law constants (H25) were estimated using experimentally-derived P(o)(L) and S(w,25) data. Values of all four properties were generally similar to those reported for other polyhalogenated aromatic compounds [P(o)(L,25) = (7.55-191) x 10(-6) Pa; S(w,25) = (1.0-1.9) x 10(-5) g/l; log K(ow) = 6.4-6.7; H25 = 0.0020-0.14 Pa m3/mol]. The effect of replacing a chlorine with a bromine atom significantly decreased P(o)(L,25) (log P(o)(L,25) = -0.4197 (# bromine atoms) - 2.643, p<0.01) and H25 (log H25 = -0.508 (# bromine atoms) + 0.394, p<0.02). There were no significant effects of bromine/chlorine substitution on S(w,25) or K(ow). A simple Level I equilibrium partitioning model predicted the environmental behaviour of HDBPs to be similar to a tetrabrominated diphenyl ether. Only slight differences in behaviour amongst HDBP congeners were predicted since substitution of a bromine for a chlorine (Cl/Br substitution) atom had less effect than H/Cl or H/Br substitution on P(o)(L,25), S(w,25), H25, and K(ow).

Reproductive and morphological effects of halogenated dimethyl bipyrroles on captive American kestrels (Falco sparverius).

Sixty-four adult captive American kestrels (Falco sparverius) were exposed to a dietary source of halogenated dimethyl bipyrroles (HDBPs), a group of organohalogens proposed to have a natural origin. Adult kestrels were assigned to four treatment groups that were administered a different dose of HDBPs [high, 140 microg/(bird x d); medium, 4.3 microg/(bird x d); low, 0.13 microg/(bird x d); control, 0 microg/(bird x d)]. Exposure began prior to pairing and continued during breeding until approximately 28 d after hatching of the final eggs. Juvenile and adult kestrels accumulated HDBPs in carcass tissue, plasma, and liver. In addition, HDBPs were transferred to yolks during egg development. Low dietary absorption efficiencies (0.011-0.029) indicated that HDBPs were effectively cleared from kestrels either from increased elimination, metabolism, or a combination of the two processes. Reproductive and morphological endpoints examined for HDBP-induced changes included egg volume, egg mass, eggshell thickness, egg fertility, clutch size, liver and whole body mass, antebrachium, central retrice, tarsus, ninth primary, and wing cord lengths. Few statistically significant dose-dependent effects were observed. Hepatic tissue samples from selected individuals underwent histomorphological evaluation. Although the hepatic function was not evaluated specifically in these birds, no clinical signs suggestive of liver disease or gross hepatic anomalies were observed. Only minor histomorphological changes were detected in the hepatic tissue. The lack of serious effects suggests that HDBPs are not an acute reproductive threat to avian populations.

Naturally produced halogenated dimethyl bipyrroles bind to the aryl hydrocarbon receptor and induce cytochrome P4501A and porphyrin accumulation in chicken embryo hepatocytes.

Halogenated dimethyl bipyrroles (HDBPs) recently have been identified as a group of environmentally persistent naturally produced bioaccumulative organohalogens. The ability of these compounds to activate the aryl hydrocarbon receptor (AhR) signaling pathway in vitro was examined. Induction of cytochrome P4501A (CYP1A), measured as ethoxyresorufin-O-deethylase (EROD) activity, and porphyrin accumulation were monitored after exposure of chick embryo hepatocytes to three individual HDBP congeners and two HDBP mixtures. All HDBP congeners and mixtures tested caused induction of EROD activity. Induction equivalency factors, calculated as the ratio of the effective concentration of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) to induce 10 and 50% of the maximal EROD induction to that of the HDBP congener or mixture ranged from 0.0004 to 0.05. Halogenated dimethyl bipyrroles also caused porphyrin accumulation, which increased with exposure time of the hepatocytes and molar bromine content of the HDBP congener or mixture. Heptacarboxylporphyrin III and corproporphyrinogen III were the most abundant porphyrins observed after an exposure period of 48 h. The individual HDBP congeners and mixtures also inhibited binding of [3H]TCDD to chicken and mouse AhR. Binding of [3H]TCDD to chicken AhR was inhibited approximately 20% by tetra- to hexabrominated congeners at concentrations of 20 to 40 microM; binding to mouse AhR was inhibited 40 to 50% by tri- and tetrabrominated dimethyl bipyrroles (DBPs) at 10 microM. The relative affinity of the hexabrominated DBP congener (vs TCDD) for binding to chicken AhR was estimated to be 0.000017. The results of this work illustrate that HDBPs act as agonist ligands for the AhR in the same manner as many anthropogenic organohalogens.

Persistence of organochlorine chemical residues in fish from the Tombigbee River (Alabama, USA): Continuing risk to wildlife from a former DDT manufacturing facility.

Organochlorine pesticide and total polychlorinated biphenyl (PCB) concentrations were measured in largemouth bass from the Tombigbee River near a former DDT manufacturing facility at McIntosh, Alabama. Evaluation of mean p,p'- and o,p'-DDT isomer concentrations and o,p'- versus p,p'-isomer proportions in McIntosh bass indicated that DDT is moving off site from the facility and into the Tombigbee River. Concentrations of p,p'-DDT isomers in McIntosh bass remained unchanged from 1974 to 2004 and were four times greater than contemporary concentrations from a national program. Total DDT in McIntosh bass exceeded dietary effect concentrations developed for bald eagle and osprey. Hexachlorobenzene, PCBs, and toxaphene concentrations in bass from McIntosh also exceeded thresholds to protect fish and piscivorous wildlife. Whereas concentrations of DDT and most other organochlorine chemicals in fish have generally declined in the U.S. since their ban, concentrations of DDT in fish from McIntosh remain elevated and represent a threat to wildlife.

ABAM, a model for bioaccumulation of POPs in birds: validation for adult herring gulls and their eggs in Lake Ontario.

An Avian BioAccumulation Model (ABAM) of persistent organic pollutant (POP) uptake and elimination in adult life-stage of birds was validated by simulation of concentrations of DDE, dieldrin, mirex, and HCB in herring gull eggs in Lake Ontario for the years 1985, 1990, and 1992. These chemicals represented a range of whole-body half-lives of 82-265 days in the gull. Dietary intake of POPs by a female gull was simulated by a dynamic bioenergetics model which included dependence on temperature, photoperiod, egg production, and feeding chicks. Concentrations in the two main prey fish of the gull in Lake Ontario were used for POP exposure. Clearance from the female was based on a two compartment toxicokinetic model. Egg concentrations were estimated from egg/whole body female concentration ratios. Simulated concentrations were compared to measured concentrations in gull eggs from 4 different colonies in the northern part of Lake Ontario. Simulations using a diet of 81% fish and 19% uncontaminated food resulted in the best fit with least variance among predicted and measured data. The mean ratio of predicted to measured concentrations in eggs was 1.0 +/- 0.27 among chemicals, years, and colonies for this exposure scenario. This result was in excellent agreement with field assessments of herring gull diet composition in Lake Ontario of 80-82% fish. The ability to perform accurate a priorisimulations for the range of test conditions employed in the validation constituted a rigorous test of the soundness of the model's structure and parameterization. With species-specific adjustments, ABAM can be regarded as a general model for lipophilic POPs bioaccumulation in birds.