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Biomedical subjects

Derek C G Muir

Publications and source records attributed to Derek C G Muir.

At least 55 records · Page 3Linked to original sources

Perflouroalkyl contaminants in liver tissue from East Greenland polar bears (Ursus maritimus).

Perfluoroalkyl substances were determined in polar bears (Ursus maritimus) collected in East Greenland (69 degrees 00'N to 74 degrees 00"N) to compare with other populations and to examine effects of age and gender on concentrations of these contaminants. Hepatic tissue (n = 29) was analyzed for perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorohexane sulfonate, heptadecafluorooctane sulfonamide (PFOSA), and perfluoroalkyl carboxylates (PFCAs) with C9-C15 perfluorinated carbon chains by liquid chromatography tandem mass spectrometry. Concentrations of PFOS found in samples from East Greenland (mean = 2,470+/-1,320 ng/g wet weight) were similar to Hudson Bay, Canada, and both populations had significantly greater concentrations than those reported for Alaska, suggesting a spatial trend. Male bears showed a significant increase in concentration up to age six for PFCAs with C10-C14 carbon chains (r2 > or = 0.50, p < or = 0.05). Significant correlations were found between adjacent chain length PFCAs, (e.g., PFNA to PFDA: p < 0.05; r2 = 0.90). This may indicate a common source for these chemicals, although the specifics of source and mode of transport are unknown. No significant correlations were found between concentrations of PFCAs in liver tissue and previously reported polychlorinated biphenyl (PCB) congeners analyzed in fat samples from the same bears.

Adipose Tissue↗

New organochlorine contaminants and metabolites in plasma and eggs of glaucous gulls (Larus hyperboreus) from the Norwegian Arctic.

The present study investigated new or lesser-studied and legacy organochlorine (OC) contaminants and metabolites in plasma and eggs of glaucous gulls (Larus hyperboreus) collected from major breeding colonies on Bear Island in the Norwegian Arctic. Hexachlorobutadiene was below the method limit of detection (< 0.07 ng/g lipid wt) in all samples. The sum (sum) of 20 chlorobornane congener concentrations ranged between 294 and 986 ng/g lipid weight and 104 and 1,121 ng/g lipid weight in plasma and eggs, respectively, whereas those of sum 20polychlorinated naphthalene ranged between 1.34 and 126 ng/g lipid weight in plasma and 1.82 and 162 ng/g lipid weight in eggs. Bis(4-chlorophenyl) sulfone concentrations ranged between 5.24 and 143 ng/ g lipid weight plasma, which is the first report of this contaminant in arctic biota north of Sweden. Based on 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs), partial dioxin-like toxicity varied between 3.04 and 20.8 ng TEQ/g lipid weight in plasma and 0.94 and 46.5 ng TEQ/g lipid weight in eggs, and largely was due to concentrations of non-ortho polychlorinated biphenyls (PCBs), with a very minor contribution from mono-ortho PCBs and polychlorinated naphthalenes. The major aryl sulfone metabolite in plasma was an unidentified hexachlorinated MeSO2-PCB congener (range: 13.5-551 ng/g lipid wt), whereas the pentachlorinated congeners 3'- and 4'-MeSO2-CB101 (range: 4.49-38.1 ng/g lipid wt) dominated in eggs. The predominant halogenated phenolic compound (HPC) in plasma was consistently the PCB metabolite 4-OH-CB187 (range: 0.29-17.5 ng/g wet wt), whereas in eggs, detectable HPCs were at very low and transient concentrations. As part of a complex profile of contaminant exposure, these chemical classes and metabolites may be contributing factors to enhance physiological stress in breeding glaucous gulls.

Animals↗

Concentrations of selected persistent organochlorine contaminants in store-bought foods from northern Alaska.

OBJECTIVES: We address marine and terrestrial mammal blubber, liver, muscle, kidney, heart, tongue, maktak and maktaaq (epidermis and blubber from bowhead, beluga whales, respectively), and fish muscle and livers, as commonly consumed tissues in subsistence communities across northern Alaska in the context of organochlorine (OC) contamination of store-bought foods. Human exposure to contaminants from biota, as part of a subsistence diet, has been superficially evaluated in numerous studies (focused on liver and blubber), but are limited in the type of tissues analyzed, and rarely consider the contaminants in the alternatives (i.e., store-bought foods). STUDY DESIGN: Concentrations from published literature on selected persistent organochlorine contaminants (OCs) in eight tissues of the bowhead whale and other biota (1) were compared to store-bought foods evaluated in this study. RESULTS: As expected, store-bought foods had lower concentrations of OCs than some tissues of the marine mammals (especially blubber, maktak, and maktaaq). However, blubber is rarely eaten alone and should not be used to give consumption advice unless considered as a portion of the food item (i.e., maktak). This study indicates that the store-bought food alternatives have detectable OC concentrations (e.g., < 0.01 to 22.5 ng/g w.w. for hexachlorobenzene) and, in many cases, have greater OC concentrations than some subsistence food items. Many wildlife tissues had OC concentrations similar to those quantified in local store-bought food. CONCLUSIONS: Switching from the traditional diet to western store-bought foods will not always reduce exposure to OCs. However, raw blubber-based products are clearly more contaminated with OCs due to lipid content. A detailed profile of traditional/country foods and western foods consumed by subsistence communities of northern Alaska is required to address chronic exposure in more detail for the diverse sources of foods (subsistence use and commercially available) and the widely varying concentrations of contaminants reported therein. This should be combined with biomonitoring people dependent upon subsistence foods. Further assessment of essential and non-essential elements, emerging contaminants (e.g. brominated flame retardants), etc. should be conducted in order to improve our understanding of the differences and similarities between wildlife and store-bought foods.

Alaska↗

Perfluoroalkyl contaminants in a food web from Lake Ontario.

Perfluorooctane sulfonate (PFOS) is a persistent and bioaccumulative perfluorinated acid detectable in humans and wildlife worldwide that has alerted scientists to examine the environmental fate of other fluorinated organic contaminants. Recently a homologous series of perfluoroalkyl carboxylates (PFCAs) was detected in the Arctic, yet little is known about their sources, breadth of contamination, or environmental distribution. In this study we analyzed for PFOS, the homologous series of PFCAs ranging from 8 to 15 carbons in chain length, and the PFOS-precursor heptadecafluorooctane sulfonamide (FOSA) in various organisms from a food web of Lake Ontario. The sampled organisms included a top predator fish, lake trout (Salvelinus namaycush), three forage fish species including rainbow smelt (Osmerus mordax), slimy sculpin (Cottus cognatus), and alewife (Alosa pseudoharengus), and two invertebrates Diporeia (Diporeia hoyi) and Mysis (Mysis relicta). A striking finding was that the highest mean concentration for each fluorinated contaminantwas detected in the benthic macroinvertebrate Diporeia, which occupies the lowest trophic level of all organisms analyzed. Perfluorinated acid concentrations in Diporeia were often 10-fold higher than in Mysis, a predominantly pelagic feeder, suggesting that a major source of perfluoroalkyl contaminants to this food web was the sediment, not the water. PFOS was the dominant acid in all samples, but long-chain PFCAs, ranging in length from 8 to 15 carbons, were also detected in most samples between <0.5 and 90 ng/ g. Among Mysis and the more pelagic fish species (e.g. excluding Diporeia and sculpin) there was evidence for biomagnification, but the influence of foraging on highly contaminated Diporeia and sculpin by these fish may have overestimated trophic magnification factors (TMFs), which ranged from 0.51 for FOSA to 5.88 for PFOS. By accounting for the known diet composition of lake trout, it was shown that bioaccumulation was indeed occurring at the top of the food web for all perfluoroalkyl compounds except PFOA. Future monitoring at other locations in Lake Ontario, and in other aquatic environments, is necessary to determine if these food web dynamics are widespread. Archived lake trout samples collected between 1980 and 2001 showed that mean whole body PFOS concentrations increased from 43 to 180 ng/g over this period, but not linearly, and may have been indirectly influenced by the invasion and proliferation of zebra mussels (Dreissena polymorpha) through effects on the population and ecology of forage fishes.

Alkanesulfonic Acids↗

Historical variations in the stable isotope composition of mercury in Arctic lake sediments.

The stable isotope composition of mercury (Hg) in a dated core from the anoxic zone of a saline, meromictic Arctic lake was found to vary as a complex function of the age and chemical composition of the sediment. Throughout the stratigraphic sequence, which spans the years 1899-1997, the ratios 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg, and 204Hg/202Hg expressed as delta-values (per mil deviations relative to a standard) reveal enrichment in 198Hg, 199Hg, 200Hg, and 201Hg, with depletion in 204Hg, the degree of enrichment varying inversely with atomic mass. A plot of delta198Hg, delta199Hg, delta200Hg, and delta201Hg against depth gave parallel profiles characterized by large, regular undulations superimposed on an overall trend toward increase with depth (i.e. age), and the delta204Hg profile is a mirror image of them. The delta198Hg, delta199Hg, delta200Hg, and delta201Hg values of the oldest (1899-1929) strata vary inversely with NH2OH.HCl/HNO3-extractable manganese concentration, but those of the youngest (1963-1997) strata give a positive correlation; intermediate (1936-1956) strata show no correlation and negligible variation in delta-values, possibly signifying a transition phase in which the two opposite trends offset each other. The delta-values show similar but weaker relationships with organic carbon. The results strongly suggest fractionation of Hg isotopes by microbial activities linked to oxidation-reduction reactions in the lake, although effects of isotopic signatures indicative of the sources of the Hg have not been ruled out. The radical change in the nature of the relationship between 6-values and sediment chemistry over time may reflect environmental and biotic changes that altered the isotope-fractionating processes. These findings imply that variations in the isotopic makeup of Hg, together with related physical, chemical, and biological data, could yield important new information about the biogeochemical cycle of Hg.

Arctic Regions↗

Altered thyroid status in lake trout (Salvelinus namaycush) exposed to co-planar 3,3',4,4',5-pentachlorobiphenyl.

Recent studies indicate that co-planar 3,3',4,4',5-pentachlorobiphenyl (PCB) congeners or their metabolites may disrupt thyroid function in fishes. Although co-planar PCB have been detected at microgram per kilogram levels in fish from contaminated areas, few studies have examined mechanisms whereby, co-planar PCBs may alter thyroid function in fish. We treated immature lake trout by intraperitoneal (i.p.)-injection or dietary gavage with vehicle containing 0, 0.7, 1.2, 25 or 40 microg 3,3',4,4',5-pentachlorobiphenyl (PCB 126) per kgBW. Blood and tissue samples were collected at various times up to 61 weeks following exposure. The treatments produced sustained dose-dependent elevations of tissue (PCB 126) concentrations. Thyroid epithelial cell height (TECH), plasma thyroxine (T4) and 3,3',5-triiodo-l-thyronine (T3) concentrations, hepatic 5'-monodeiodinase, hepatic glucuronidation of T4 and T3, as well as plasma T4 kinetics and fish growth were analyzed. Exposure to the highest doses of PCB 126 caused increased TECH, plasma T4 dynamics and T4-glucuronidation (T4-G). PCB 126 did not affect 5'-monodeiodinase and T3-glucuronidation (T3-G) and there were no effects on fish growth or condition. Because T3 status and growth were unaffected, the thyroid system was able to compensate for the alterations caused by the PCB 126 exposure. It is clear that concentrations of co-planar PCBs similar to those found in predatory fish from contaminated areas in the Great Lakes are capable of enhancing metabolism of T4. These changes may be of significance when T4 requirements are high for other reasons (e.g. periods of rapid growth, warm temperatures, metamorphosis, and parr-smolt transformation).

Analysis of Variance↗

Vapor pressures of the fluorinated telomer alcohols--limitations of estimation methods.

The influence of the unique, physical properties of poly- and perfluorinated chemicals on vapor pressure was investigated. Vapor pressures of a suite of fluorinated telomer alcohols (FTOHs) (CF3(CF2)nCH2CH2OH, where n = 3, 5, 7, or 9) were measured using the boiling point method and ranged from 144 to 992 Pa. Comparison of experimental and literature values indicate that perfluorocarbons (CF3(CF2)nCF3, where n = 0-6) and fluorinated telomer alcohols have vapor pressures equal to or greater than that of their hydrogen analogues. These chemically counterintuitive results can be explained by the unique geometry of poly- and perfluorinated chemicals--in particular the stiff, helical perfluorinated chain and the significant intramolecular hydrogen bonding of the FTOHs. The majority of models investigated for the estimation of vapor pressure did not compensate for this unique geometry and consistently underpredicted the vapor pressures of the FTOHs. Calculation of partitioning constants using both experimental and estimated vapor pressures indicate that both the Antoine and Modified Grain models, and to a lesser degree the Mackay model, are insufficiently accurate for estimating the vapor pressures of the FTOHs, particularly the longer chain FTOHs. Future models should consider parameters such as geometry, strength, and location of intramolecular hydrogen bonds and otherfunction groups in the molecule in order to improve vapor pressure estimation accuracy. It appears likely that the unique molecular geometry of the FTOHs influences not only their vapor pressure but also other physical properties and hence environmental fate and dissemination.

Alcohols↗

Polyfluorinated telomer alcohols and sulfonamides in the North American troposphere.

In 2001, a sampling campaign was conducted in six North American cities--Reno, NV; Griffin, GA; Cleves, OH; Winnipeg, MB; Long Point, ON; and Toronto, ON--to investigate the tropospheric distribution of a suite of polyfluorinated alcohols and amides. Analysis via gas chromatography-chemical ionization-mass spectrometry indicated that both polyfluorinated sulfonamides and fluorinated telomer alcohols (FTOHs) are widely distributed throughout the North American troposphere with mean concentrations ranging from 22 to 403 pg/m3 and from 11 to 165 pg/m3 respectively. The dominant polyfluorinated contaminant was dependent on sampling location. Large mean concentrations of N-methyl perfluorooctane sulfonamidoethanol (359 pg/m3) and N-ethyl perfluorooctane sulfonamidoethanol (199 pg/m3) identified in Griffin and Reno, respectively, may indicate the release of polyfluorinated sulfonamides to the environment through paper and carpet treatment processes. The nonuniform nature of the spatial distribution of both polyfluorinated sulfonamides and FTOHs is indicative of the importance of point sources for the dissemination of these contaminants in the North American troposphere.

Air Pollutants↗

Hexachlorocyclohexanes in the North American atmosphere.

Annually integrated air concentrations of alpha- and gamma-hexachlorocyclohexane (HCH) were determined in 2000/2001 at 40 stations across North America using XAD-based passive air samplers to understand atmospheric distribution processes on a continental scale. Elevated levels of gamma-HCH in the atmosphere of the Canadian Prairies are consistent with the ongoing use of lindane as a seed treatment on canola and confirm the feasibility of detecting the agricultural use of a pesticide using long-term integrated passive air sampling. In contrast to gamma-HCH, the atmospheric concentrations of alpha-HCH show a rather uniform distribution across Canada and the United States, which is expected for a chemical with no current use on the continent. Higher levels in the atmosphere over Atlantic Canada can be explained by alpha-HCH evaporating from the waters of the Labrador Current, which is supported bythe chiral composition of alpha-HCH and the temperature dependence of its atmospheric concentrations along the east coast of Canada. Similarly, alpha-HCH is volatilizing from Lake Superior. Atmospheric HCH levels increase with elevation in the Canadian Rocky Mountains. The results suggest that evaporation, in particular from cold water bodies, is an important source of alpha-HCH to the North American atmosphere. Low levels of HCHs in Central America hint at efficient degradation under tropical conditions. Chiral analysis shows that (+)-alpha-HCH is often enriched in air over continental areas and at the Pacific Coast, which is opposite to the enantiomeric enrichment in the proximity to the Great Lakes and the Atlantic Ocean. Passive air sampling is a powerful tool to discern the large-scale variability of semivolatile and persistent organic chemicals in the atmosphere.

Agriculture↗

Identification of long-chain perfluorinated acids in biota from the Canadian Arctic.

Recently it was discovered that humans and animals from various urban and remote global locations contained a novel class of persistent fluorinated contaminants, the most pervasive of which was perfluorooctane sulfonate (PFOS). Lower concentrations of perfluorooctanoate, perfluorohexane sulfonate, and heptadecafluorooctane sulfonamide have also been detected in various samples. Although longer perfluoroalkyl carboxylates (PFCAs) are used in industry and have been detected in fish following a spill of aqueous film forming foam, no studies have been conducted to examine the widespread occurrence of long-chain PFCAs (e.g., CF3(CF2)xCOO-, where x > 6). To provide a preliminary assessment of fluorinated contaminants, including PFCAs, in the Canadian Arctic, polar bears, ringed seals, arctic fox, mink, common loons, northern fulmars, black guillemots, and fish were collected at various locations in the circumpolar region. PFOS was the major contaminant detected in most samples and in polar bear liver was the most prominent organohalogen (mean PFOS = 3.1 microg/g wet weight) compared to individual polychlorinated biphenyl congeners, chlordane, or hexachlorocyclohexane-related chemicals in fat. Using two independent mass spectral techniques, it was confirmed that all samples also contained ng/g concentrations of a homologous series of PFCAs, ranging in length from 9 to 15 carbons. Sum concentrations of PFCAs (sum(PFCAs)) were lower than total PFOS equivalents (sum(PFOS)) in all samples except for mink. In mink, perfluorononanoate (PFNA) concentrations exceeded PFOS concentrations, indicating that PFNA and other PFCAs should be considered in future risk assessments. Mammals feeding at higher trophic levels had greater concentrations of PFOS and PFCAs than mammals feeding at lower trophic positions. In general, odd-length PFCAs exceeded the concentration of even-length PFCAs, and concentrations decreased with increasing chain length in mammals. PFOS and PFCA concentrations were much lower for animals living in the Canadian Arctic than for the same species living in mid-latitude regions of the United States. Future studies should continue to monitor all fluorinated contaminants and examine the absolute and relative toxicities for this novel suite of PFCAs.

Alkanesulfonates↗

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.

Animals↗

Is bone mineral composition disrupted by organochlorines in east Greenland polar bears (Ursus maritimus)?

We analyzed bone mineral density (BMD) in skulls of polar bears (Ursus maritimus) (n = 139) from East Greenland sampled during 1892-2002. Our primary goal was to detect possible changes in bone mineral content (osteopenia) due to elevated exposure to organochlorine [polychlorinated biphenyls (PCBs), dichlorodiphenyl trichloroethane (DDT) and its metabolites, chlordanes (CHLs), dieldrin, hexacyclohexanes, hexachlorobenzene] and polybrominated diphenyl ether (PBDE) compounds. To ensure that the BMD value in skull represented the mineral status of the skeletal system in general, we compared BMD values in femur and three lumbar vertebrae with skull in a subsample. We detected highly significant correlations between BMD in skull and femur (r = 0.99; p < 0.001; n = 13) and skull and vertebrae (r = 0.97; p < 0.001; n = 8). BMD in skulls sampled in the supposed pre-organochlorine/PBDE period (1892-1932) was significantly higher than that in skulls sampled in the supposed pollution period (1966-2002) for subadult females, subadult males, and adult males (all, p < 0.05) but not adult females (p = 0.94). We found a negative correlation between organochlorines and skull BMD for the sum of PCBs (SigmaPCB; p < 0.04) and SigmaCHL (p < 0.03) in subadults and for dieldrin (p < 0.002) and SigmaDDT (p < 0.02) in adult males; indications for SigmaPBDE in subadults were also found (p = 0.06). In conclusion, the strong correlative relationships suggest that disruption of the bone mineral composition in East Greenland polar bears may have been caused by organochlorine exposure.

Animals↗

Empirical and modeling evidence of regional atmospheric transport of current-use pesticides.

Water samples from 30 lakes in Canada and the northeastern United States were analyzed for the occurrence of 27 current-use pesticides (CUPs). Eleven CUPs were frequently detected in lakes receiving agricultural inputs as well as in remote lakes hundreds of kilometers from known application areas. These included the triazine herbicide atrazine and its desethylated degradation product; the herbicides alachlor, metolachlor, and dacthal; the organophosphate insecticides chlorpyrifos, diazinon, and disulfoton; the organochlorine insecticides alpha-endosulfan and lindane; and the fungicides chlorothalonil and flutriafol. For six of the pesticides, empirical half-distances on the order of 560 to 1,820 km were estimated from the water-concentration gradient with latitude. For most of the pesticides, a suite of assessment models failed to predict such atmospheric long-range transport behavior, unless the effect of periods of lower hydroxyl radical concentrations and dry weather were taken into account. Observations and model results suggest that under the conditions prevailing in south-central Canada (relatively high latitude, low precipitation rates), many CUPs will be able to undergo regional-scale atmospheric transport and reach lakes outside areas of agricultural application. When assessing the potential of fairly reactive and water-soluble substances to undergo long-range transport, it is imperative to account for periods of no precipitation, to assure that degradation rate constants are correct, and to apply oxidant concentrations that are valid for the region and time period of interest.

Agriculture↗

Biological and chemical factors of importance in the bioaccumulation and trophic transfer of persistent organochlorine contaminants in Arctic marine food webs.

Recent studies of arctic marine food webs have provided detailed insights regarding the biological and chemical factors that influence the bioaccumulation and trophic transfer of persistent organochlorine (OC) contaminants in aquatic systems. The present paper summarizes the recent literature with an emphasis on identifying important ecological factors for explaining variability of OC concentrations among organisms. The Arctic ecosystem has a number of unique attributes, including long food chains, reduced diversity of species, similar food webs across the entire region, and limited influence from pollution point sources. Lipid content, body size, age, gender, reproduction, habitat use, migration, biotransformation, seasonal changes in habitat conditions, feeding ecology, and trophic position have all been demonstrated to influence OC concentrations and bioaccumulation in arctic marine biota. The relative importance of each factor varies among OCs and organisms. Diet or trophic level is the dominant factor influencing OC concentrations and dynamics in seabirds and marine mammals, although biotransformation can significantly influence nonrecalcitrant OCs, such as hexachlorocyclohexane isomers. Dietary accumulation of OCs is also an important route of exposure for arctic fish and zooplankton, and biomagnification of OCs may also occur among these organisms. To date, only limited attempts have been made to model trophic transfer of OCs in the arctic marine food web. Although models developed to assess OC dynamics in aquatic food webs have included some biological variables (e.g., lipid content, feeding rate, diet composition, and growth rate), selection of processes included in these models as well as their mathematical solutions and parameterization all introduce simplification. This reduces biological validity of the models and may be particularly problematic in a highly seasonal environment, such as the Arctic Ocean.

Age Factors↗

Levels and temporal trends of toxaphene congeners in beluga whales (Delphinapterus leucas) from the St. Lawrence Estuary, Canada.

Environmentally relevant toxaphene congeners were determined in blubber samples of stranded beluga whales (Delphinapterus leucas) from the St. Lawrence Estuary (SLE), Canada. The purpose of this study was to evaluate the levels and the temporal trends (1988-1999) of a suite of six chlorobornanes (P26, P40/41, P44, P50, and P62) in the SLE belugas. P26 and P50 mean concentrations were in the same range as those reported for animals living in the Arctic environment suggesting that the atmospheric transport represents the main input of toxaphene to the SLE. A general exponential decline of chlorobornane concentrations in belugas was observed, except for P26 and P50 in males. On average, concentrations decreased by a factor of two in 8.5 years during the 1988-1999 time period. This rate of decline is similar to the reduction of toxaphene emission from agricultural soils in the southern United States reported over the same time period. Some differences in decline rates were observed among the studied CHB congeners. For instance, P62 decreased more rapidly than P26 and P50 in both male and female belugas. Several hypotheses were advanced to explain these differences such as selective metabolism of specific chlorobornanes by SLE belugas or their prey. However, a most likely explanation is the selective degradation of the technical product in soils and atmosphere in the source region.

Adipose Tissue↗

Airborne haloacetic acids.

Haloacetic acid (HAA) concentrations were measured in air samples from a semi-rural and a highly urbanized site in southern Ontario throughout 2000 to investigate their sources and gas-particle partitioning behavior. Denuders were efficient for collection of gaseous HAAs, and the particle phase was collected on a downstream quartz filter with negligible breakthrough. Total HAA concentrations (i.e., gas + particles) ranged between <0.025 and 19 ng m(-3) for individual HAAs at both sites. The dominant airborne HAA was monochloroacetic acid (MCA), followed in decreasing order by dichloroacetic acid (DCA), trifluoroacetic acid (TFA), and trichloroacetic acid (TCA). Difluoroacetic acid (DFA), monofluoroacetic acid (MFA), and chlorodifluoroacetic acid (CDFA) were also frequently detected at lower concentrations. Between sites, TFA, DFA, MFA, and TCA concentrations were significantly higher in Toronto, while CDFA concentrations were higher in Guelph. HAAs were primarily in the gas phase all year; however, during colder months, particle-phase HAA concentrations increased relative to the gas phase. Trichloroacetic acid had the highest particle fraction (phi) for all detected HAAs, with a mean phi of 0.51 and 0.56 for Guelph and Toronto, respectively, and both vapor pressure and acid strength appeared to influence gas-particle partitioning. Temporal trends at both sites were partially explained by temperature, short-wave radiation, and particle mass (PM10), leading to indications of the respective sources. A simple deposition model indicated that dry deposition of TFA and TCA should not be neglected in temperate mid-latitude environments and that precipitation concentrations can be successfully predicted by the Henry's law constant.

Acetates↗