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Biomedical subjects

Scott A Mabury

Publications and source records attributed to Scott A Mabury.

At least 19 recordsLinked to original sources

Poly and perfluorinated carboxylates in North American precipitation.

Although perfluorocarboxylates (PFCAs) have been detected in a number of environmental matrices, there are very few reports on concentrations in precipitation. In this study PFCAs, fluorotelomercarboxylates (FTCAs), and fluorotelomer-unsaturated carboxylates (FTUCAs), were determined in wet only precipitation samples from nine sites in North America. The analytical method involved derivatization of the carboxylates and measurement of the 2,4-difluoroanilide by GC-MS. Samples from three remote sites in Canada had low concentrations of perfluorooctanoate (PFOA) (<0.1-6.1 ng/L). Significantly higher concentrations of PFOA were found at 4 northeastern United States and 2 southern urban Canadian sites, with Delaware having the highest levels (85 ng/L PFOA, with a range of 0.6-89 ng/L) and a maximum flux of 13 000 ng/m2. 8:2- and 10:2 FTCAs and FTUCAs were detected at all 4 U.S. sites and 2 urban Canadian sites (<0.07-8.6 ng/L), most frequently at the Delaware site. Longer chained PFCAs (deca-, undeca-, and dodeca-perfluorocarboxylates) were detected (<0.07-5.2 ng/L) at 2 urban Ontario sites but not determined in other samples. Air mass back trajectory results for 3 U.S. sites indicate highly populated urban areas in the New York to Washington corridor as the main sources of PFOA, although low PFOA levels associated with air masses coming off the Atlantic Ocean imply multiple sources.

Air Movements↗

Analysis for perfluorocarboxylic acids/anions in surface waters and precipitation using GC--MS and analysis of PFOA from large-volume samples.

The presence of perfluorocarboxylates (PFCAs) in the environment is of increasing concern, following the discovery of perfluoroalkyl acids (PFAs) in wildlife and human samples. Here we report a method forthe determination of (C2-C9) PFCAs by preparing the 2,4-difluoroanilides of the acids and analyzing by using GC-MS. Detector response was linear over the range 0.1 -1000 pg of each perfluoroalkyl anilide. A complete suite of PFCAs can be analyzed in an individual sample with the PFCAs detected at levels similar to or lower than those determined by other methods. For a comparison between the present method and the more common LC-MS/MS method, 10 replicates of a sewage treatment plant discharge were analyzed for perfluoro-octanoic acid (PFOA) using both methods. Results were nearly identical with low standard deviation (GC-MS 30.9 +/- 1.88 ng/L; while the LC-MS/MS 34.7 +/- 3.05 ng/L). PFCA concentrations for water samples collected from depth profiles in mid-Lake Ontario were analyzed by GC-MS with most PFCAs (C2-C8) present above the detection limit (0.5 ng/L). Major PFCAs were trifluoroacetate (TFA) (100 ng/L) and perfluorobutanoate (PFBA) (> 5 ng/L). Results for PFOA (2.5 ng/L) were in good agreement with recent analyses by LC-MS/MS. PFCAs were also detected in the precipitation samples at concentrations lower than those of the samples from the lake profiles or sewage treatment plants (STPs) effluent. Since PFOA levels may be less than the lower detection limit (<0.5 ng/L) in 1 L samples, a method for large volumes using XAD-7 resin was developed that allows detection to 0.01 ng/L. This method was applied to Lake Superior samples which produced good agreement for C6-C9 PFCAs between regular analysis (GC-MS) and the XAD-7 followed by GC-MS analysis.

Anions↗

Isomer distribution of perfluorocarboxylates in human blood: potential correlation to source.

Detection of perfluorocarboxylate anions (PFCAs), such as perfluorooctanoate (C7F15COO-, PFOA), at ng/g levels in human tissues has engendered public scrutiny of industrial fluorochemicals. Routes of PFCA exposure for the general human population are likely diverse given direct (industrially produced) and indirect (production from precursor organofluorines) sources. Major industrial production of organofluorines, including PFCAs, stems from either electrochemical fluorination (ECF) or telomerization. ECF products are a mixture of structural isomers (linear and branched perfluoroalkyls) and telomerization products are assumed to have one perfluorocarbon arrangement, typically linear. The objective of this research was to investigate structural isomer patterns of PFCAs in human blood. Volatile derivatives of PFCAs in human blood were analyzed by GC-(NCI)-MS for quantitation and isomers. PFOA was the dominant PFCA (mean 4.4 ng/g). Blood serum isomer profiles consisted of predominantly (mean approximately 98%) the linear isomer for each PFCA (C8-C11). There were similarities in branched isomer patterns of an ECF PFOA standard with both PFOA and PFNA in blood. Direct exposure to ECF PFOA, which has a legacy of production for uses in fluoropolymer industries, is postulated to be a source of the observed branched isomer pattern. Predominance of linear PFCA isomers and the [even PFCA] > [odd PFCA] concentration trend in blood is suggestive of additional input from a strictly linear perfluoroalkyl source.

Anions↗

Atmospheric lifetime and global warming potential of a perfluoropolyether.

Perfluoropolyethers (PFPEs) are a family of perfluorinated fluids used mainly in industrial applications. Lower molecular weight commercial PFPE fractions have boiling points ranging between 55 and 270 degrees C, and have the potential to escape into the atmosphere. To improve our understanding of the atmospheric chemistry of PFPEs, a distilled fraction of a commercial mixture containing perfluoropolymethylisopropyl ethers (PFPMIEs) was introduced into an atmospheric chamber system. Relative rate techniques were used to determine upper limits for the rate constants for reactions of OH and Cl with PFPMIE in 700 Torr of air at 296 K. The reactivity of PFPMIE with Cl was less than 2 x 10(-17) cm3 molecule(-1) s(-1), while the reactivity with OH was less than 6.8 x 10(-16) cm3 molecule(-1) s(-1), indicating low reactivity in the troposphere. Consequently, the lifetime of PFPMIE should be limited bytransport to the mesosphere, where photolysis by Lyman-alpha radiation at 121.6 nm will be efficient. By analogy to perfluorinated alkanes, the lower limit for the total atmospheric lifetime is 800 years. PFPMIE was shown to have instantaneous radiative forcing of 0.65 W m(-2) ppb(-1), which corresponds to a global warming potential on a 100 year time scale of 9000 relative to CO2 and 1.95 relative to CFC-11.

Atmosphere↗

Atmospheric chemistry of N-methyl perfluorobutane sulfonamidoethanol, C4F9SO2N(CH3)CH2CH2OH: kinetics and mechanism of reaction with OH.

Relative rate methods were used to measure the gas-phase reaction of N-methyl perfluorobutane sulfonamidoethanol (NMeFBSE) with OH radicals, giving k(OH + NMeFBSE) = (5.8 +/- 0.8) x 10(-12) cm3 molecule(-1) s(-1) in 750 Torr of air diluent at 296 K. The atmospheric lifetime of NMeFBSE is determined by reaction with OH radicals and is approximately 2 days. Degradation products were identified by in situ FTIR spectroscopy and offline GC-MS and LC-MS/MS analysis. The primary carbonyl product C4F9SO2N(CH3)CH2CHO, N-methyl perfluorobutane sulfonamide (C4F9SO2NH(CH3)), perfluorobutanoic acid (C3F7C(O)OH), perfluoropropanoic acid (C2F5C(O)OH), trifluoroacetic acid (CF3C(O)OH), carbonyl fluoride (COF2), and perfluorobutane sulfonic acid (C4F9SO3H) were identified as products. A mechanism involving the addition of OH to the sulfone double bond was proposed to explain the production of perfluorobutane sulfonic acid and perfluorinated carboxylic acids in yields of 1 and 10%, respectively. The gas-phase N-dealkylation product, N-methyl perfluorobutane sulfonamide (NMeFBSA), has an atmospheric lifetime (>20 days) which is much longer than that of the parent compound, NMeFBSE. Accordingly,the production of NMeFBSA exposes a mechanism by which NMeFBSE may contribute to the burden of perfluorinated contamination in remote locations despite its relatively short atmospheric lifetime. Using the atmospheric fate of NMeFBSE as a guide, it appears that anthropogenic production of N-methyl perfluorooctane sulfonamidoethanol (NMeFOSE) contributes to the ubiquity of perfluoroalkyl sulfonate and carboxylate compounds in the environment.

Air Pollutants↗

Significant residual fluorinated alcohols present in various fluorinated materials.

Polyfluorinated telomer alcohols and sulfonamides are classes of compounds recently identified as precursor molecules to the perfluorinated acids detected in the environment. Despite the detection and quantification of these volatile compounds in the atmosphere, their sources remain unknown. Both classes of compounds are used in the synthesis of various fluorosurfactants and incorporated in polymeric materials used extensively in the carpet, textile, and paper industries. This study has identified the presence of residual unbound fluoro telomer alcohols (FTOHs) in varying chain lengths (C6-C14) in several commercially available and industrially applied polymeric and surfactant materials. NMeFOSE, a perfluoroalkyl sulfonamido alcohol, was also detected in a commercially available carpet protector product. A method was developed to remove these residual compounds from polymeric and surfactant materials by dispersion in water and stripping of the volatiles using a constant flow of air and trapping on XAD resin. Using gas chromatography mass spectrometry analysis, it was determined that the fluorinated materials examined consist of 0.04-3.8% residual alcohols on a fluoro alcohol to dry mass basis. These values indicate that residual alcohols, left unreacted and unbound from the manufacturing process of fluorinated polymers and surfactants, could be a significant source of the polyfluorinated telomer alcohols and sulfonamides released into the environment. This study suggests that elimination or reduction of these residual alcohols from all marketed fluorinated polymers and fluorosurfactants is key in reducing the prevalence of perfluorinated acids formed in the environment.

Fluorine Compounds↗

Temporal trends of perfluoroalkyl contaminants in polar bears (Ursus maritimus) from two locations in the North American Arctic, 1972-2002.

Perfluoroalkyl substances are globally distributed anthropogenic contaminants. Their production and use have increased dramatically from the early 1980s. While many recent publications have reported concentrations of perfluorooctane sulfonate (PFOS) and other perfluoroalkyl acids (PFAs) in biotic and abiotic samples, only limited work has addressed temporal trends. In this study we analyzed archived polar bear(Ursus maritimus) livertissue samples from two geographic locations in the North American Arctic, collected from 1972 to 2002. The eastern group, taken from the vicinity of northern Baffin Island, Canada, comprised 31 samples, and the western group, from the vicinity of Barrow, Alaska, comprised 27 samples. Samples were analyzed for perfluorocarboxylic acids (PFCAs) from carbon chain length C8 to C15, perfluorohexane sulfonate, PFOS, the neutral precursor perfluorooctane sulfonamide (PFOSA), as well as 8:2 and 10:2 fluorotelomer acids and their alpha,beta unsaturated acid counterparts. Concentrations of PFOS and PFCAs with carbon chain lengths from C9 to C11 showed an exponential increase between 1972 and 2002 at both locations. Doubling times ranged from 3.6 +/- 0.9 years for perfluorononanoic acid in the eastern group to 13.1 +/- 4.0 years for PFOS in the western group. PFOSA showed decreasing concentrations over time at both locations, while the remaining PFAs showed no significant trends or were not detected in any sample. The doubling time for PFOS was similar to the doubling time of production of perfluoroctylsulfonyl-fluoride-based products during the 1990s.

Alaska↗

Dissipation kinetics and mobility of chlortetracycline, tylosin, and monensin in an agricultural soil in Northumberland County, Ontario, Canada.

A robust high-throughput method was refined to extract three growth-promoting antibiotics, tylosin (TYL), chlortetracycline (CTC), and monensin (MON), from soil. Analysis was performed by electrospray liquid chromatography tandem mass spectrometry. Soil dissipation rate studies were performed in a farm field soil for antibiotics applied with and without manure. Tylosin, CTC, and MON followed first-order dissipation kinetics with half-lives of 4.5, 24, and 3.3 d, respectively, with the addition of manure and 6.1, 21, and 3.8 d, respectively, without manure. Manure application significantly increased TYL dissipation rate, perhaps because of the introduced microbial flora, but had no significant effect on CTC or MON. Monensin dissipation half-life was found to be much shorter in the field study than in a controlled laboratory study, perhaps because of differences in microbial communities. The antimicrobials were not highly mobile. Chlortetracycline was the only antibiotic detected at 25 to 35 cm depth and only up to 2% of the initial concentration in a sandy loam soil. These antibiotics are therefore expected to degrade primarily in agricultural soils before moving to greater depths or to groundwater in significant concentrations in most agricultural systems.

Animal Husbandry↗

Metabolic products and pathways of fluorotelomer alcohols in isolated rat hepatocytes.

Fluorotelomer alcohols (FTOHs; CF(3)(CF(2))(x)C(2)H(4)OH; where x=3, 5, 7, 9) are a novel class of polyfluorinated contaminants, recently detected in the North American atmosphere, that are possible precursors to the series of perfluoroalkyl carboxylates (PFCAs) in human blood. An in vivo rat study validated earlier independent work that poly- and per-fluoroalkyl carboxylates were metabolites of FTOHs, but our detection of several novel metabolites prompted us to examine their pathways in greater detail using isolated rat hepatocytes. Using 8:2 FTOH (i.e. where x=7) as a model compound, the metabolic products formed by isolated rat hepatocytes were identified, and three synthesized intermediates were incubated separately to elucidate the metabolic pathways. For 8:2 FTOH, a major fate was direct conjugation to form the O-glucuronide and O-sulfate. Using 2,4-dinitrophenylhydrazine (DNPH) trapping, the immediate oxidation product of 8:2 FTOH was identified as 8:2 fluorotelomer aldehyde (8:2 FTAL; CF(3)(CF(2))(7)CH(2)C(H)O). 8:2 FTAL was transient and eliminated HF non-enzymatically to yield 8:2 fluorotelomer alpha,beta-unsaturated aldehyde (8:2 FTUAL; CF(3)(CF(2))(6)CFCHC(H)O) which was also short-lived and reacted GSH and perhaps other endogenous nucleophiles. Four polyfluorinated acid intermediates were also detected, including 8:2 fluorotelomer carboxylate (8:2 FTCA; CF(3)(CF(2))(7)CH(2)C(O)O(-)), 8:2 fluorotelomer alpha,beta-unsaturated carboxylate (8:2 FTUCA; CF(3)(CF(2))(6)CFCHC(O)O(-)), tetrahydroperfluorodecanoate (CF(3)(CF(2))(6)(CH(2))(2)CO(2)(-)), and dihydroperfluorodecenoate (CF(3)(CF(2))(6)CHCHCO(2)(-)). The pathways leading to 8:2 FTCA and FTUCA involve oxidation of 8:2 FTAL, however, the pathways leading to the latter two polyfluorinated acids remain inconclusive. The fate of the unsaturated metabolites, 8:2 FTUAL and FTUCA, included conjugation with GSH and dehydrofluorination to yield alpha,beta-unsaturated GSH conjugates, and GS-8:2 FTUAL which was subsequently reduced to the corresponding alcohol. Perfluorooctanoate (PFOA) and minor amounts of perfluorononanoate (PFNA) were confirmed as metabolites of 8:2 FTOH, and the respective roles of beta- and alpha-oxidation mechanisms are discussed. The analogous acids, aldehydes, and conjugated metabolites of 4:2, 6:2, and 10:2 FTOH (i.e. where x=3, 5, and 9, respectively) were also detected, and metabolite profiles among FTOHs generally differed only in the length of their perfluoroalkyl chains. Preincubation with aminobenzotriazole, but not pyrazole, inhibited the formation of metabolites from all FTOHs, suggesting that their oxidation was catalyzed by P450, not alcohol dehydrogenase.

Alcohols↗

Circumpolar study of perfluoroalkyl contaminants in polar bears (Ursus maritimus).

Perfluoroalkyl substances were determined in liver tissues and blood of polar bears (Ursus maritimus) from five locations in the North American Arctic and two locations in the European Arctic. Concentrations of perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate, heptadecafluorooctane sulfonamide, and perfluoroalkyl carboxylates with C(8)-C(15) perfluorinated carbon chains were determined using liquid chromatography tandem mass spectrometry. PFOS concentrations were significantly correlated with age at four of seven sampling locations, while gender was not correlated to concentration for any compound measured. Populations in South Hudson Bay (2000-2730 ng/g wet wt), East Greenland (911-2140 ng/g wet wt), and Svalbard (756-1290 ng/g wet wt) had significantly (P < 0.05) higher PFOS concentrations than western populations such as the Chukchi Sea (435-729 ng/g wet wt). Concentrations of perfluorocarboxylic acids (PFCAs) with adjacent chain lengths (i.e., C9:C10 and C10:C11) were significantly correlated (P < 0.05), suggesting PFCAs have a common source within a location, but there were differences in proportions of PFCAs between eastern and western location sources. Concentrations of PFOS in liver tissue at five locations were correlated with concentrations of four polychlorinated biphenyl congeners (180, 153, 138, and 99) in adipose tissue of bears in the same populations, suggesting similar transport pathways and source regions of PFOS or precursors.

Adipose Tissue↗

Microcosm evaluation of the fate, toxicity, and risk to aquatic macrophytes from perfluorooctanoic acid (PFOA).

Perfluorooctanoic acid (PFOA) is an anthropogenic contaminant detected in various environmental and biological matrices. This compound is a fluorinated surfactant, belonging to a class of molecules known for persistence and their global distribution, but for which little ecotoxicological data are currently available, especially under field conditions. The environmental fate and toxicity of PFOA to the aquatic macrophytes Myriophyllum sibiricum and M. spicatum were investigated using 12,000 L outdoor microcosms. Replicate microcosms (n = 3) were treated with 0.3, 1, 30, and 100 mg/L PFOA as the sodium salt, plus controls, and assessed at regular intervals over 35 days. PFOA showed no significant dissipation from the water column, except at the greatest concentration, where partitioning from the water column into other compartments is suspected. The two species of Myriophyllum were similar in their sensitivity to PFOA under these simulated field conditions. Toxicity after 14 to 35 days of exposure in the evaluated endpoints for M. spicatum was > or = 5.7 mg/L PFOA for EC10s and > or = 31.8 mg/L PFOA for EC50s and in M. sibiricum was > or = 8.4 mg/L PFOA for EC10s and > or = 35.8 mg/L PFOA for EC50s. The no observed effects concentrations (NOECs) for Myriophyllum spp. were consistently > or = 23.9 mg/L PFOA. A risk assessment for these plant species estimated a negligible probability of toxicity being observed from PFOA exposure at current environmental concentrations.

Caprylates↗

Aqueous photochemical reaction kinetics and transformations of fluoxetine.

Fluoxetine (FLX) was shown to be photoreactive in sunlit surface waters. FLX degraded in deionized water when exposed to simulated sunlight with a half-life of 55.2+/-3.6 h(-1). Photodegradation products were identified using high performance liquid chromatography-UV (HPLC-UV) and liquid chromatography tandem mass spectrometry (LC-MS-MS) using electrospray (ES) ionization. Defluorination of the trifluoromethyl group in FLX and in fluometuron and flutalanil,two other compounds containing this functional group, is suggested to be a common direct photolysis pathway for trifluoromethylated compounds. Products resulting from O-dealkylation of FLX were also observed. The rate of degradation was faster in synthetic field water where .OH was the likely dominant oxidant in the system. The bimolecular rate constant for the reaction between FLX and .OH was measured as (8.4+/-0.5) x 10(9) and (9.6 +/-0.8) x 10(9) M(-1) s(-1) using two different methods of competition kinetics. Indirect photodegradation reactions could lead to the production of hydroxylated and O-dealkylated compounds. Although direct photolysis could potentially limitthe persistence of FLX in surface waters, its degradation by indirect photolysis would proceed faster. Thus, this latter process could be important in the elimination of FLX in surface waters.

Fluoxetine↗

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↗

Short-term exposures of fish to perfluorooctane sulfonate: acute effects on fatty acyl-coa oxidase activity, oxidative stress, and circulating sex steroids.

This study investigated the effects of exposure to waterborne perfluorooctane sulfonate (PFOS) on oxidative stress and reproductive endpoints in fish. Exposures utilized species commonly used in toxicological testing, including the fathead minnow (Pimephales promelas) and rainbow trout (Oncorhynchus mykiss), as well as relatively insensitive taxa such as creek chub (Semotilus atromaculatus), spottail shiner (Notropis hudsonius), and white sucker (Catostomus commersoni). In all fish species, short-term (14-28 d) exposure to PFOS produced only modest mortality at concentrations consistent with environmental spill scenarios. However, PFOS consistently increased hepatic fatty acyl-CoA oxidase activity and increased oxidative damage, as quantified using the 2-thiobarbituric acid-reactive substances assay. Plasma testosterone, 11-ketotestosterone, and 17beta-estradiol titers were often elevated with PFOS exposure. Vitellogenin, the egg yolk precursor protein, was occasionally altered in the plasma with PFOS exposure, but responses varied with maturity. Oviposition frequency and egg deposition in fathead minnow were not significantly impaired with PFOS exposure, despite a trend toward progressive impairment with increasing exposure concentrations. Although short-term PFOS exposure produced significant impacts on biochemical and reproductive endpoints in fish at concentrations consistent with environmental spills, the impact of long-term exposure to environmentally relevant concentrations of PFOS is unclear.

Acyl-CoA Oxidase↗

Aqueous photolysis of 8:2 fluorotelomer alcohol.

The 8:2 fluorotelomer alcohol (8:2 FTOH) was photodegraded in aqueous hydrogen peroxide solutions, synthetic field water (SFW) systems, and Lake Ontario (Canada) water samples. It was found to undergo indirect photolysis, with the data suggesting that the hydroxyl radical was the main degradation agent and that nitrate promoted photolysis whereas dissolved organic carbon inhibited it. The half-lives of 8:2 FTOH were 0.83 +/- 0.20 h (10 mM H2O2), 38.0 +/- 6.0 h (100 microM H2O2), 30.5 +/- 8.0 to 163.1 +/- 3.0 h (SFW systems), and 93.2 +/- 10.0 h (Lake Ontario). No significant loss of the parent compound by direct photolysis could be observed. The major monitored products were the 8:2 fluorotelomer aldehyde, the 8:2 fluorotelomer acid (8:2 FTCA), and perfluorooctanoate (PFOA); the minor monitored products were the 8:2 fluorotelomer unsaturated acid (8:2 FTUCA) and perfluorononanoate (PFNA). The intermediates, 8:2 FTCA and 8:2 FTUCA, were photodegraded to verify the degradation pathway, and a mechanism for the photolysis was proposed whereby the end products of the photolysis pathway were PFOA (major) and PFNA (minor).

Alcohols↗

Isolating isomers of perfluorocarboxylates in polar bears (Ursus maritimus) from two geographical locations.

The source of involatile, anthropogenic perfluorocarboxylate anions (PFCAs) in biota from remote regions is of heightened interest due to the persistence, toxicity, and bioaccumulation of these materials. Large-scale production of fluorinated compounds is carried out primarily by one of two methods: electrochemical fluorination (ECF) and telomerization. Products of the two processes may be distinguished based on constitutional isomer pattern as ECF products are characteristically comprised of a variety of constitutional isomers. The objective of this research was to develop a method for identifying the constitutional isomer profile of PFCAs in environmental samples and to apply the method to polar bear livers from two different locations. Resolution of constitutional isomers of derivatized PFCAs (8-13 carbons) was accomplished via GC-MS. Seven isomers of an authentic ECF perfluorooctanoate (PFOA) standard were separated. The linear isomer comprised 78% of this standard. Isomer profiles of PFCAs in liver samples of 15 polar bears (Ursus maritimus) from the Canadian Arctic and eastern Greenland were determined by GC-MS. The PFOA isomer pattern in Greenland polar bear samples showed a variety of branched isomers while only the linear PFOA isomer was determined in Canadian samples. Samples of both locations had primarily (>99%) linear isomers of perfluorononanoate and perfluorotridecanoate. Branched isomers of perfluorodecanoate, perfluoroundecanoate, and perfluorododecanoate were determined in the polar bear samples. Unlike the PFOA isomer signature, only a single branched isomer peak on the chromatograms was observed for these longer chain PFCAs. The presence of branched isomers suggests some contribution from ECF sources. However, in comparison to the amount of branched isomers in the ECF PFOA standard, such minor percentages of branched PFCAs may suggest additional input from an exclusively linear isomer source.

Animals↗

Microcosm evaluation of the effects of an eight pharmaceutical mixture to the aquatic macrophytes Lemna gibba and Myriophyllum sibiricum.

Pharmaceuticals have been detected in surface waters of the US and Europe, originating largely from two sources, sewage effluent and agricultural runoff. These compounds often occur as mixtures leading to potential combined effects. In order to investigate the effects of a realistic pharmaceutical mixture on an ecosystem, a study utilizing 15 of 12,000 L aquatic microcosms treated with eight common pharmaceuticals (atorvastatin, acetaminophen, caffeine, sulfamethoxazole, carbamazepine, levofloxacin, sertraline, and trimethoprim) at total (summed) molar concentrations of 0, 0.044, 0.608, 2.664, and 24.538 micromol/L (n = 3) was conducted. Phytotoxicity was assessed on a variety of somatic and pigment endpoints in rooted (Myriophyllum sibiricum) and floating (Lemna gibba) macrophytes over a 35-day period. EC10, EC25 and EC50 values were calculated for each endpoint exhibiting a concentration-dependent response. Generally, M. sibiricum and L. gibba displayed similar sensitivity to the pharmaceutical mixture, with phytotoxic injury evident in both species, which was concentration dependent. Through single compound 7-day daily static renewal toxicity tests with L. gibba, the sulfonamide antibiotic sulfamethoxazole, the fluoroquinolone antibiotic levofloxacin and the blood lipid regulator atorvastatin were found to be the only compounds to elicit phytotoxic effects in the concentration range utilized (0-1000 microg/L). Atorvastatin concentration was highly correlated to decreased pigment content in L. gibba, likely inhibiting the known target enzyme HMGR, the rate-limiting enzyme in isoprenoid biosynthesis. Hazard quotients were calculated for both microcosm and laboratory studies; the highest HQ values were 0.235 (L. gibba) and 0.051 (L. gibba), which are below the threshold value of 1 for chronic risks. The microcosm data suggest that at an ecological effect size of >20%, biologically significant risks are low for L. gibba and M. sibiricum exposed to similar mixtures of pharmaceutical compounds. For M. sibiricum and L. gibba, respective minimum differences of 5 and 1%, were detectable, however, these effect sizes are not considered ecologically significant.

Acetaminophen↗

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↗