Abstract  A single ip injection of perfluoro-n-decanoic acid (PFDA) to male Wistar rats resulted in an initially rapid, then gradual decrease in food consumption and a parallel loss of body weight. Body temperatures and resting heart rates were significantly depressed by PFDA treatment. As early as 12 h following a single dose of PFDA, serum thyroxine (T4) levels were significantly reduced and remained depressed throughout the 8 day study. Serum triiodothyronine (T3) was reduced by 35% 12 h following PFDA treatment and remained at that level throughout the study. These preliminary data suggest that an action on the thyroid axis may be an early primary response to PFDA and that some of the observed subsequent effects may in part be secondary to the change in thyroid hormone levels.

Abstract  Organic fluorochemicals are used in multiple commercial applications including surfactants, lubricants, paints, polishes, food packaging, and fire-retarding foams. Recent scientific findings suggest that several perfluorochemicals (PFCs), a group of organic fluorochemicals, are ubiquitous contaminants in humans and animals worldwide. Furthermore, concern has increased about the toxicity of these compounds. Therefore, monitoring human exposure to PFCs is important. We have developed a high-throughput method for measuring trace levels of 13 PFCs (2 per-fluorosulfonates, 8 perfluorocarboxylates, and 3 perfluorosulfonamides) in serum and milk using an automated solid-phase extraction (SPE) cleanup followed by high-performance liquid chromatography-tandem mass spectrometry. The method is sensitive, with limits of detection between 0.1 and 1 ng in 1 mL of serum or milk, is not labor intensive, involves minimal manual sample preparation, and uses a commercially available automated SPE system. Our method is suitable for large epidemiologic studies to assess exposure to PFCs. We measured the serum levels of these 13 PFCs in 20 adults nonoccupationally exposed to these compounds. Nine of the PFCs were detected in at least 75% of the subjects. Perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHxS), 2-(N-methylperfluorooctanesulfonamido)acetate (Me-PFOSA-AcOH), perfluorooctanoate (PFOA), and perfluorononanoate (PFNA) were found in all of the samples. The concentration order and measured levels of PFOS, PFOA, Me-PFOSA-AcOH, and PFHxS compared well with human serum levels previously reported. Although no human data are available for the perfluorocarboxylates (except PFOA), the high frequency of detection of PFNA and other carboxylates in our study suggests that human exposure to long-alkyl-chain perfluorocarboxylates may be widespread. We also found PFOS in the serum and milk of rats administered PFOS by gavage, but not in the milk of rats not dosed with PFOS. Furthermore, we did not detect most PFCs in two human milk samples. These findings suggest that PFCs may not be as prevalent in human milk as they are in serum. Additional studies are needed to determine whether environmental exposure to PFCs can result in PFCs partitioning into milk. Large epidemiological studies to determine the levels of PFCs among the U.S. general population are warranted.

Abstract  The main value in measuring environmental chemicals in biological specimens (i.e., biomonitoring) is the ability to minimize risk assessment uncertainties. The collection of biomonitoring data for risk assessment requires the analysis of a statistically significant number of samples from subjects with a significant prevalence of detectable internal dose levels. This paper addresses the practical laboratory challenges that arise from these statistical requirements: development of high throughput techniques that can handle, with high accuracy and precision, a large number of samples and can do a trace level analysis of multiple and diverse environmental chemicals (i.e., analytes). We review here examples of high throughput, automated solid-phase extraction methods developed in our laboratory for biomonitoring of analytes with representative hydrophobic properties and for typical biomonitoring matrices. We discuss key aspects of sample preparation, column, and solvent selection for off- and online extractions, and the so-called nuts-and-bolts of online column-switching systems necessary for developing-with minimal sample handling-rugged, automated methods.

Abstract  Hexaflumuron, one of the benzoylphenylurea insect growth regulators, can be leached into surface water and thus having a potential impact on aquatic organisms. In this study, the photodegradation processes of hexaflumuron under high-pressure mercury lamp irradiation were assessed. The photodegradation kinetics were studied, as were the effects of pH, different light sources, organic solvents and environmental substances, including nitrate ions (NO3 (-) ), nitrite ions (NO2 (-) ), ferrous ions (Fe(2+) ), ferric ions (Fe(3+) ), humic acid, sodium dodecyl sulfate (SDS) and hydrogen peroxide (H2 O2 ). Three photodegradation products in methanol were identified by gas chromatography-mass spectrometry (GC-MS). In general, the degradation of hexaflumuron followed first-order kinetics. In the four media studied, the photodegradation rate order was n-hexane > methanol > ultrapure water > acetone. Faster degradation was observed under high-pressure mercury lamp irradiation than under xenon lamp irradiation. The pH had a considerable effect, with the most rapid degradation occurring at pH 5.0. The photodegradation rate of hexaflumuron was promoted in the presence of NO3 (-) , NO2 (-) , Fe(2+) , humic acid, SDS and H2 O2 , but inhibited by Fe(3+) . Moreover, the presumed photodegradation pathway was proposed to be the cleavage of the urea linkage.

Abstract  Perfluoroalkyl substances (PFASs) are protein-binding blood-accumulating contaminants that may have detrimental toxicological effects on the early phases of mammalian development. To enable an evaluation of the potential health risks of PFAS exposure for polar bears (Ursus maritimus), an exposure assessment was made by examining plasma levels of PFASs in polar bear mothers in relation to their suckling cubs-of-the-year (~4 months old). Samples were collected at Svalbard in 1998 and 2008, and we investigated the between-year differences in levels of PFASs. Seven perfluorinated carboxylic acids (∑₇PFCAs: PFHpA, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, and PFTrDA) and two perfluorinated sulfonic acids (∑₂PFSAs: PFHxS and PFOS) were detected in the majority of the mothers and cubs from both years. In mothers and cubs, most PFCAs were detected in higher concentrations in 2008 than in 1998. On the contrary, levels of PFOS were lower in 2008 than in 1998, while levels of PFHxS did not differ between the two sampling years. PFOS was the dominating compound in mothers and cubs both in 1998 and in 2008. Concentration of PFHpA did not differ between mothers and cubs, while concentrations of PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTrDA, PFHxS, and PFOS were higher in mothers than in their cubs. Except from PFHpA, all compounds correlated significantly between mothers and their cubs. The mean cub to mother ratios ranged from 0.15 for PFNA to 1.69 for PFHpA. On average (mean±standard error of mean), the levels of ∑₇PFCAs and ∑₂PFSAs in cubs were 0.24±0.01 and 0.22±0.01 times the levels in their mothers, respectively. Although maternal transfer appears to be a substantial source of exposure for the cubs, the low cub to mother ratios indicate that maternal transfer of PFASs in polar bears is relatively low in comparison with hydrophobic contaminants (e.g. PCBs). Because the level of several PFASs in mothers and cubs from both sampling years exceeded the levels associated with health effects in humans, our findings raise concern on the potential health effects of PFASs in polar bears from Svalbard. Effort should be made to examine the potential health effects of PFASs in polar bears.

Abstract  The ivory gull is a high Arctic seabird species threatened by climate change and contaminant exposure. High levels of contaminants have been reported in ivory gull Pagophila eburnea eggs from Svalbard and the Russian Arctic. The present study investigated associations between high levels of contaminants (organochlorinated pesticides (OCPs), polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs), perfluorinated alkyl substances (PFASs) and mercury (Hg)) and three response variables: eggshell thickness, retinol (vitamin A) and α-tocopherol (vitamin E). Negative associations were found between levels of OCPs, PCBs and BFRs and eggshell thickness (p<0.021) and α-tocopherol (p<0.023), but not with retinol (p>0.1). There were no associations between PFASs and mercury and the three response variables. Furthermore, the eggshell thickness was 7-17% thinner in the present study than in archived ivory gull eggs (≤1930). In general, a thinning above 16 to 20% has been associated with a decline in bird populations, suggesting that contaminant-induced eggshell thinning may constitute a serious threat to ivory gull populations globally.

Abstract  BACKGROUND: Breast cancer (BC) is the most common cancer for women in the western world. From very few cases an extraordinary increase in BC was observed in the Inuit population of Greenland and Canada although still lower than in western populations. Previous data suggest that exposure to persistent organic pollutants (POPs) might contribute to the risk of BC. Rat studies showed that perfluorinated compounds (PFCs) cause significantly increase in mammary fibroadenomas. This study aimed at evaluating the association between serum levels of POPs/PFCs in Greenlandic Inuit BC cases and their controls, and whether the combined POP related effect on nuclear hormone receptors affect BC risk.

METHODS: Thirty-one BC cases and 115 controls were sampled during 2000-2003 from various Greenlandic districts. The serum levels of POPs, PFCs, some metals and the combined serum POP related effect on estrogen- (ER), androgen- (AR) and Ah-receptor (AhR) transactivity were determined. Independent student t-test was used to compare the differences and the odds ratios were estimated by unconditional logistic regression models.

RESULTS: We observed for the very first time a significant association between serum PFC levels and the risk of BC. The BC cases also showed a significantly higher concentration of polychlorinated biphenyls at the highest quartile. Also for the combined serum POP induced agonistic AR transactivity significant association to BC risk was found, and cases elicited a higher frequency of samples with significant POP related hormone-like agonistic ER transactivity. The AhR toxic equivalent was lowest in cases.

CONCLUSIONS: The level of serum POPs, particularly PFCs, might be risk factors in the development of BC in Inuit. Hormone disruption by the combined serum POP related xenoestrogenic and xenoandrogenic activities may contribute to the risk of developing breast cancer in Inuit. Further investigations are needed to document these study conclusions.

Abstract  The unique features of high porosity, shape selectivity, and multiple active sites make metal-organic frameworks (MOFs) promising as novel stationary phases for high-performance liquid chromatography (HPLC). However, the wide particle size distribution and irregular shape of conventional MOFs lead to lower column efficiency of such MOF-packed columns. Herein, the fabrication of monodisperse MOF@SiO2 core-shell microspheres as the stationary phase for HPLC to overcome the above-mentioned problems is reported. Zeolitic imidazolate framework8 (ZIF-8) was used as an example of MOFs due to its permanent porosity, uniform pore size, and exceptional chemical stability. Unique carboxyl-modified silica spheres were used as the support to grow the ZIF-8 shell. The fabricated monodisperse ZIF-8@SiO2 packed columns (5cm long x 4.6mm i.d.) show high column efficiency (23000platesm(-1) for bisphenolA) for the HPLC separation of endocrine-disrupting chemicals (bisphenolA, -estradiol, and p-(tert-octyl)phenol) and pesticides (thiamethoxam, hexaflumuron, chlorantraniliprole, and pymetrozine) within 7min with good relative standard deviations for 11replicate separations of the analytes (0.01-0.39, 0.65-1.7, 0.70-1.3, and 0.17-0.91% for retention time, peak area, peak height, and half peak width, respectively). The ZIF-8@SiO2 microspheres combine the advantages of the good column packing properties of the uniform monodisperse silica microspheres and the separation ability of the ZIF-8 crystals.

Abstract  Geological sequestration of CO2 in depleted oil reservoirs is a potentially useful strategy for greenhouse gas management and can be combined with enhanced oil recovery. Development of methods to estimate CO2 leakage rates is essential to assure that storage objectives are being met at sequestration facilities. Perfluorocarbon tracers (PFTs) were added as three 12 h slugs at about one week intervals during the injection of 2090 tons of CO2 into the West Pearl Queen (WPQ) depleted oil formation, sequestration pilot study site located in SE New Mexico. The CO2 was injected into the Permian Queen Formation. Leakage was monitored in soil–gas using a matrix of 40 capillary adsorbent tubes (CATs) left in the soil for periods ranging from days to months. The tracers, perfluoro-1,2-dimethylcyclohexane (PDCH), perfluorotrimethylcyclohexane (PTCH) and perfluorodimethylcyclobutane (PDCB), were analyzed using thermal desorption, and gas chromatography with electron capture detection. Monitoring was designed to look for immediate leakage, such as at the injection well bore and at nearby wells, and to develop the technology to estimate overall CO2 leak rates based on the use of PFTs. Tracers were detected in soil–gas at the monitoring sites 50 m from the injection well within days of injection. Tracers continued to escape over the following years. Leakage appears to have emanated from the vicinity of the injection well in a radial pattern to about 100 m and in directional patterns to 300 m. Leakage rates were estimated for the 3 tracers from each of the 4 sets of CATs in place following the start of CO2 injection. Leakage was fairly uniform during this period. As a first approximation, the CO2 leak rate was estimated at about 0.0085% of the total CO2 sequestered per annum.

Abstract  A simple gas chromatographic (GC) method has been developed to determine 2,4- and 2,6-diaminotoluenes in polyurethane foam. Diaminotoluenes were reacted with heptafluorobutyric anhydride in toluene, and the products, bis-heptafluorobutyrates, were determined by GC, using a 3% silicone OV-330 column. The 2,4- and 2,6-diaminotoluenes can be detected as heptafluorobutyryl derivatives by using an electron capture detector at levels of 5 and 2 pg, respectively. Finally, 2.7-3.0 micrograms/g of 2,4- and 1.3-1.9 micrograms/g of 2,6-diaminotoluene were detected in 3 commercial polyurethane foams.

Abstract  A well-defined subsample of 128 subadult (3-5 years) polar bears (Ursus maritimus) from 19 sampling years within the period 1984-2006 was investigated for perfluoroalkyl contaminants (PFCs), Linear regression analysis of logarithmic-transformed median concentrations showed significant annual increases for PFOS (4.7%), PFNA (6.1%), PFUnA (5.9%), PFDA (4.3%), PFTrA (8.5%), PFOA (2.3%), and PFDoA (5.2%). For four of the PFCs, a LOESS smoother model provided significantly better descriptions, revealing steeper linear annual increases for PFOSA of 9.2% after 1990 and between 18.6 and 27.4% for PFOS, PFDA, and PFTrA after 2000. Concentrations of Sigma PFCs, by 2006, exceeded the concentrations of all conventional OHCs (organohalogen compounds), of which several have been documented to correlate with a number of negative health effects. If the PFC concentrations in polar bears continue to increase with the steepest observed trends, then the lowest no-adverse-effect level (NOAEL) and lowest-adverse-effect level (LOAEL) detected for rats and monkeys will be exceeded in 2014-2024. In addition, the rapidly increasing concentrations of PFCs are likely to cause cumulative and combined effects on the polar bear, compounding the already detected threats from OHCs.

Abstract  We measured concentrations of selected organohalogens, fluorinated compounds and mercury in whole, ground silver (Hypophthalmichthys molitrix) and bighead (H. nobilis) carp from the Illinois River, Illinois, in 2010 and 2011 to characterize spatial and interspecific patterns of contaminant burdens. Silver carp, which had greater lipid content, tended to have greater concentrations of lipophilic compounds. Concentrations of organohalogens were generally greater in carp from the upper reaches of the river. The halogenated compounds were associated with length and lipid content in silver carp. Bighead carp had greater mercury concentrations than did silver carp; total mercury concentrations were negatively associated with lipid content of bighead carp. Perfluorinated compounds, comprised predominantly of perfluorooctane sulfonic acid, did not vary by species or river reach. Chlordanes and polychlorinated biphenyls were of potential concern with regard to the use of these carp as animal feed additives. Our results indicated that, even though they occupy a lower trophic level than many similarly-sized fish, these carp may accumulate measureable concentrations of organic contaminants.

Abstract  The aim of the Bavarian Monitoring of Breast Milk (BAMBI) project was to examine 10 organochlorine pesticides (OPs), 3 nitro musks, 6 indicator polychlorinated biphenyls (PCBs), 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), 12 dioxin-like PCBs (dl-PCBs) and several perfluorinated alkyl compounds in breast milk samples. A total of 516 breast milk samples were collected from seven regions in Bavaria and were analyzed by means of GC/ECD, GC/HRMS, and LC/MS-MS. Concerning the OPs, only hexachlorobenzene and a metabolite of DDT, 1,1-dichloro-2,2-bis(4-chlorophenyl) ethylene (p,p'-DDE), could be quantified in all samples (median: 16 ngg(-1) lipid and 63 ngg(-1) lipid, respectively). Median concentrations of 150 ngg(-1) lipid (range: 3-1900 ngg(-1) lipid) were found for the sum of the indicator PCBs. The concentrations of the PCDDs/PCDFs and the dl-PCBs ranged from 0.8 to 15.1 (median 5.7) pg WHO-TEQ1998g(-1) lipid and from 1.5 to 18.9 pg (median 6.4) WHO-TEQ1998 g(-1) lipid, respectively. The median perfluorooctane sulfonate concentration was 0.05 μgL(-1) (range: <0.02-0.26 μgL), while the other PFCs were observed only in a subset of samples. On the basis of the median and 95th percentile concentration, "medium" and "high" intake levels were estimated for a 3-month-old exclusively breastfed infant. In particular, "medium" and "high" intake levels were calculated of 69 and 133 pg WHO1998 TEQ kg(-1) b.w. for PCDDs/PCDFs, 8 and 21 ngkg(-1) b.w. for dl-PCBs, and 6 and 25 ngkg(-1) b.w. for perfluorooctane sulfonate, respectively. The calculated intake for perfluorinated substances is clearly below the tolerable daily intake (TDI), while the established TDI values are still clearly exceeded for PCDDs/PCDFs and dl-PCBs.

Abstract  Random bi-functional copolymers bearing fluorinated units and sol-gel forming units were prepared and used together with silica particles in a one-pot process for preparing superamphiphobic coatings. The copolymers P(FOEA-r-IPSMA) were prepared by atom transfer radical polymerization (ATRP) of 2-(perfluorooctyl) ethyl acrylate (FOEA) and 3-(triisopropyloxy)silylpropyl methacrylate (IPSMA). The uniform silica particles were prepared using a modified Stober process. Stirring P(FOEA-r-IPSMA), silica, water, and HCl together with substrates triggered the sol-gel reactions of the IPSMA units. These involved first the hydrolysis of IPSMA to yield silanol groups and then the condensation of the IPSMA silanol groups among themselves, and with silanol groups on silica or glass surfaces or with hydroxyl groups on cotton or filter paper. At optimized mass ratios of P(FOEA-r-IPSMA) to silica, the resultant coatings consisted of lightly covered silica particles that were embedded in a crosslinked P(FOEA-r-IPSMA) film. By optimizing the molar ratio between FOEA and IPSMA in P(FOEA-r-IPSMA), the rough particulate coatings on cotton, filter paper, and glass plates exhibited superamphiphobicity. More importantly, the particulate coatings were resistant to solvent extraction and NaOH etching.

Abstract  A method for determining isomers of diaminotoluene (25376458) was described. The method consisted of two procedures: procedure 1, which did not resolve the 2,4 and 2,5 isomers and procedure 2 which resolved all isomers. In procedure 1, 60 to 100 milligrams (mg) of sample were reacted with 1 milliliter (ml) trifluoroacetic-acid for 5 minutes, followed by reaction with 1ml trifluoroacetic-anhydride for 15 minutes. Ten microliters (microl) of sample was analyzed by a gas chromatograph (GC) using a column consisting of aluminum tubing packed with 2.0 percent neopentyl-glycol. In procedure 2, 60 to 100mg sample was shaken with chloroform, then reacted with trifluoroacetic-anhydride. The solution was then allowed to stand for 15 minutes. The solvent and excess reagent were evaporated in a stream of nitrogen. The sample was reconstituted by 1ml of acetone. A 5microl sample was injected into a GC equipped with a column consisting of aluminum tubing with 100 to 120 mesh Chromosorb. Repeated analyses of seven replicate samples of a synthetic sample according to procedure 1 produced a relative standard deviation of 0.7 to 8.4 percent. Analysis of 5 replicate samples of a crude product by procedure 2 had relative standard deviations of 0.6 to 7.7 percent for the 2,3, 3,4, 2,6, 2,4, and 2,5 isomers. The authors note that procedure 1 serves as an excellent method for quality control of factory grade material. Procedure 2 must be used when determining the 2,5 isomer is important.

Abstract  A dicationic ion-pairing reagent, N,N'-dibutyl 1,1'-pentylenedipyrrolidinium, was used to form complexes with singly charged anions for their subsequent analysis by CE-ESI-MS in positive ion mode. This methodology offers the advantages of greater versatility and sensitivity relative to direct detection of the anions in negative ion mode, and it can be realized by a number of possible complexation strategies, including pre-column, on-column, and post-column modes. Four model anions, perfluorooctanoate, benzenesulfonate (BZSN), monochloroacetate (MCA), and trifluoromethanesulfonimide were amenable to complexation with the dicationic reagent, yielding singly charged cations with greater m/z. By optimizing various parameters, including the CE separation buffer composition and pH, the concentration of the dicationic reagent, the mode of complexation, the nebulizing gas pressure, and the sheath liquid composition, it was possible to develop a robust CE-ESI-MS method appropriate for the analysis of anions in a tap water sample. By this method, LODs were found to be 20.9 and 1.31 ng/mL for MCA and BZSN, respectively.

Abstract  Specific binding of [3H]naloxone to rat brain tissue in vitro was inhibited by the excitant organochlorinated insecticides (OCI), by ether (E) and octanol (OCT), and by the convulsant indoklon (IND) and its anesthetic isomer, isoindoklon (ISO). In the presence of 100 mM NaCl the inhibition of naloxone binding by E, OCT and ISO was greatly potentiated, whereas that by OCI and IND was attenuated. KCl (100 mM) was equally effective as NaCl on the action of anesthetics, but the effect of the excitant drugs was, in contrast to NaCl, unaffected by KCl. Specific binding of [3H]ouabain in the absence of Na, was depressed by anesthetics and enhanced by neuroexcitants. In the presence of NaCl, which by itself inhibits ouabain binding to brain, both anesthetics and excitants enhanced ouabain binding. DDE, a non-insecticidal analog of DDT, and the dimethyl derivative of the OCI, lindane, were inactive in the receptor assays. These observations point to a unique isolated system which responds consistently to anesthetic agents as a class and, in a different way, to neuroexcitant compounds.

Abstract  Activated persulfate oxidation technologies based on sulfate radicals were first evaluated for defluorination of aqueous perfluorooctanesulfonate (PFOS). The influences of catalytic method, time, pH and K2S2O8 amounts on PFOS defluorination were investigated. The intermediate products during PFOS defluorination were detected by using LC/MS/MS. The results showed that the S2O8 (2-) had weak effect on the defluorination of PFOS, while the PFOS was oxidatively defluorinated by sulfate radicals in water. The defluorination efficiency of PFOS under various treatment was followed the order: HT (hydrothermal)/K2S2O8 > UV (ultraviolet)/K2S2O8 > Fe(2+)/K2S2O8 > US (ultrasound)/K2S2O8. Low pH was favorable for the PFOS defluorination with sulfate radicals. Increase in the amount of S2O8 (2-) had positive effect on PFOS defluorination. However, further increase in amounts of S2O8 (2-) caused insignificant improvement in PFOS defluorination due to elimination of sulfate radicals under high concentration of S2O8 (2-). CF3(CF2)nCOOH (n = 0-6) were detected as intermediates during PFOS defluorination. Sulfate radicals oxidation and hydrolysis were the main mechanisms involved in defluorination process of PFOS.

Abstract  Short-chain perfluoroalkyl acids (PFAAs), which have less than seven fluorinated carbons, have been introduced as substitutes for eight-carbon homologue products. In this study, water, sediment, and biological samples (fish and plant) were collected from Tangxun Lake, which is located near a production base of the fluorochemical industry in Wuhan, China. Perfluorobutane sulfonate (PFBS) and perfluorobutanoic acid (PFBA) were the predominant PFAAs in surface water, with average concentrations of 3660 ng/L and 4770 ng/L, respectively. However, perfluorooctane sulfonate (PFOS) was the most abundant PFAA in sediments, with an average concentration of 74.4 ng/g dw. The organic carbon normalized distribution coefficients (KOC) indicated that short-chain PFAAs (CF2 < 7) tended to have lower adsorption potentials than PFOS, perfluorooctanoic acid (PFOA), and longer perfluoroalkyl chain compounds. PFBS and PFBA could transport to a farther distance in the horizontal direction along the water flow and infiltrate into deeper depths in the vertical direction. However, levels of PFOS and PFOA in water dropped exponentially along the current, and their proportions were decreased gradually with the increasing depth in sediment cores. Furthermore, values of log bioconcentration factor (BCF) of the short-chain PFAAs were all relatively low (<1), indicating no bioaccumulation potentials for short-chain PFAAs in aquatic species. [PUBLICATION ABSTRACT]

Abstract  Perfluoroalkyl acids (PFAAs) are globally found in various media, including food and especially fishery products. In the present study, the dietary exposure to 15 perfluoroalkyl acids was assessed for 3 French adult populations, namely high seafood consumers, high freshwater fish consumers, and pregnant women. Purified food extracts were analysed by LC-MS/MS and PFBA, PFPA, PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFTrDA, PFTeDA, PFBS, PFHxS, PFHpS, PFOS and PFDS were monitored and quantified according to the isotope dilution principle. Under lower bound (LB) hypothesis (i.e. contamination values<LOD considered as 0), high freshwater fish consumers appear as the most exposed to PFOS (7.5ng.kg(-1) bw.d(-1)), PFUnA (1.3ng.kg(-1) bw.d(-1)), PFDA (0.4ng.kg(-1) bw.d(-1)) and PFHpS (0.03ng.kg(-1) bw.d(-1)) while high seafood consumers appear as the most exposed to PFOA (1.2ng.kg(-1) bw.d(-1)), PFNA (0.2ng.kg(-1) bw.d(-1)) and PFHxS (0.06ng.kg(-1) bw.d(-1)). For all considered populations, the major exposure contributors are fish, seafood and water under LB hypothesis, while dairy products, bread and crispbread are the main contributors under upper bound (UB) hypothesis. Besides this food exposure assessment, further studies are needed to assess the more global PFAA exposure, taking into account indoor and outdoor air, dust and cutaneous contact, which could be other important contributors for this particular class of chemicals.

Abstract  The distribution in water and sediment, the sources/sinks and the risk of perfluorinated compounds (PFCs) in Lake Taihu, China were investigated. The total PFCs concentration was 164 to 299ngL(-1) in water and 5.8 to 35ngg(-1) (dw) in sediment. The highest concentrations of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) in water were 29.2ngL(-1) and 136ngL(-1). PFOS was largely associated with sediment, whereas short chain PFCs predominated in water. The partition coefficient (Kd) was positively correlated with the organic carbon fraction (ƒoc) for PFOS but not for the other PFCs. The organic carbon normalized partition coefficient (Koc) increased by 0.51 log units for each additional CF2 moiety from perfluoro-butanesulfonate (PFBS) to PFOS. For the same chain length but different functional groups, the log Koc of PFOS was 1.35 units higher than PFOA. PFOS exhibited the highest affinity for sediment through the partition mechanism, and ƒoc affected the sediment as a sink of PFOS. Although there was no immediate health impact by the intake of the water alone, the consumption of aquatic products may cause potential health risks for animals/humans on the time scale of months to years. The relationship between the concentration, water-sediment distribution, bioaccumulation and toxicity should be considered in determining the water standards of PFCs.

Abstract  A perfluorooctane sulfonic acid (PFOS) assessment was conducted on gibel carp (Carassius auratus gibelio), carp (Cyprinus carpio), and eel (Anguilla anguilla) in Flanders (Belgium). The liver PFOS concentrations in fish from the Ieperlee canal (Boezinge, 250-9031 ng/g wet weight, respectively) and the Blokkersdijk pond (Antwerp, 633-1822 ng/g wet weight) were higher than at the Zuun basin (Sint-Pieters-Leeuw, 11.2-162 ng/g wet weight) and among the highest in feral fish worldwide. Eel from the Oude Maas pond (Dilsen-Stokkem) and Watersportbaan basin (Ghent) had PFOS concentrations ranging between 212 and 857 ng/g wet weight. The hepatic PFOS concentration was significantly and positively related with the serum alanine aminotransferase activity, and negatively with the serum protein content in eel and carp. The hepatic PFOS concentration in carp correlated significantly and negatively with the serum electrolyte concentrations whereas a significant positive relation was found with the hematocrit in eel. Although 13 organochlorine pesticides, 22 polychlorinated biphenyl (PCB) congeners and 7 polybrominated diphenyl ethers (PBDEs) were also measured in the liver tissue, only PCB 28, PCB 74, gamma-hexachlorocyclohexane (gamma-HCH) and hexachlorobenzene (HCB) were suggested to contribute to the observed serological alterations in eel.

Abstract  BIOSIS COPYRIGHT: BIOL ABS. A procedure for the simultaneous identification of seventy-three primary and secondary aromatic amines (including alkyl-, chloro- and nitro-substituted anilines, benzidines, aminonaphthalenes and aminobiphenyls) is described. The amines were derivatized by reaction with heptafluorobutyric anhydride to form the corresponding heptafluorobutyramides. The electrophoric derivatives were analyzed by gas chromatography combined with electron-capture negative-ion chemical ionization mass spectrometry. Linearity was satisfactory for all the compounds examined. Detection limits were in the range 0.3-66.3 pg injected in the full-scan acquisition mode and 0.01-0.57 pg injected in the selected ion monitoring acquisition mode. Application of the procedure to contaminated groundwater samples was also attempted.

Abstract  The perfluoroalkyl compounds (PFCs), perfluoroalkyl sulfonates (PFXS) and perfluoroalkyl carboxylates (PFXA) are environmentally persistent and recalcitrant towards most conventional water treatment technologies. Here, we complete an in depth examination of the UV-254 nm production of aquated electrons during iodide photolysis for the reductive defluorination of six aquated perfluoroalkyl compounds (PFCs) of various headgroup and perfluorocarbon tail length. Cyclic voltammograms (CV) show that a potential of +2.0 V (vs. NHE) is required to induce PFC oxidation and -1.0 V is required to induce PFC reduction indicating that PFC reduction is the thermodynamically preferred process. However, PFCs are observed to degrade faster during UV(254 nm)/persulfate (S(2)O(8)(2-)) photolysis yielding sulfate radicals (E° = +2.4 V) as compared to UV(254 nm)/iodide (I(-)) photolysis yielding aquated electrons (E° = -2.9 V). Aquated electron scavenging by photoproduced triiodide (I(3)(-)), which achieved a steady-state concentration proportional to [PFOS](0), reduces the efficacy of the UV/iodide system towards PFC degradation. PFC photoreduction kinetics are observed to be dependent on PFC headgroup, perfluorocarbon chain length, initial PFC concentration, and iodide concentration. From 2 to 12, pH had no observable effect on PFC photoreduction kinetics, suggesting that the aquated electron was the predominant reductant with negligible contribution from the H-atom. A large number of gaseous fluorocarbon intermediates were semi-quantitatively identified and determined to account for ∼25% of the initial PFOS carbon and fluorine. Reaction mechanisms that are consistent with kinetic observations are discussed.