Abstract  The interfacial tensions of the hexane solution of fluorooctanols (1,1,2,2-tetrahydrotridecafluorooctanol, TFC8OH, and 1,1-dihydropentadecafluorooctanol, DFC8OH) against water were measured as a function of temperature and molality under atmospheric pressure. By drawing the interfacial pressure a vs mean area per adsorbed molecule A curves, it was concluded that the adsorbed film of TFC8OH exhibits a first-order phase transition between the gaseous and expanded states and that of DFC8OH shows the two types of phase transitions from the gaseous to the expanded state and from the expanded to the condensed one at the hexane/water interface. The comparison of the pi vs A curve between TFC8OH and DFC8OH shows that the intermolecular interaction is enhanced by the substitution of fluorine for hydrogen on the beta -carbon of TFC8OH. Furthermore, the difference in the transition pressure between DFC8OH and TFC10-OH (1,1,2,2-tetrahydroheptadecafluorodecanol) is explained by the differences in London dispersion force between hydrophobic chains and the dipole moment of their hydroxyl group. The partial molar entropy (s) over bar (H)(s) - s(s)(O) and energy (u) over bar (H)(s) - u(s)(O) changes of adsorption were evaluated and compared to those of TFC10OH. The (s) over bar (H)(s) - s(s)(O) value is negative and therefore alcohol molecules have smaller entropy at the interface than in the solution, which is attributable to the orientation of the molecules at the interface. The phase transition from the expanded to the condensed state in the adsorbed TFC10OH film causes larger decrease in partial molar entropy than that in the DFC8OH one. This may arise from the larger partial molar entropy of TFC10OH molecules due to the larger entropy of mixing of longer fluorocarbon chain with hexane in the expanded state and the smaller entropy of TFC10OH due to the stronger attractive interaction in the condensed state than that of DFC8OH molecules. The (u) over bar (H)(s) - u(s)(O) value is less negative for DFC8OH than for TFC10OH and therefore the energetical stabilization of DFC8OH accompanied by the adsorption from the solution is less than that of TFC10OH. Furthermore, it was concluded that the DFC8OH molecules are stabilized by forming the condensed film at the interface because of the strong molecular interaction between them, and the TFC8OH molecules form mainly tetramers in the hexane solution to lower the energetical state of the system.

Abstract  Aerobic soil biodegradation of toluene-2,4-di(8:2 fluorotelomer urethane) (FTU) and hexamethylene-1,6-di(8:2 fluorotelomer urethane) (HMU) in a forest soil and FTU in an agricultural silty clay loam soil was monitored for up to 6 months. Fluorotelomer alcohols were measured in headspace and parent monomers and all metabolites in soil extracts. Negligible degradation of FTU biodegradation occurred in the agricultural soil with 94 ± 15% recovered at day 180. However, in the forest soil, both FTU and HMU degradation was evident with significant losses of 24% (117 d) and 27% (180 day), respectively, and concomitant increases in the terminal metabolite, perfluorooctanoic acid (PFOA) concentrations were well above what could result from residual 8:2 FTOH. Kinetic modeling estimated half-lives for FTU (aromatic backbone) and HMU (aliphatic backbone) in the forest soil to be 3-5 months and 15.9-22.2 months, respectively. The addition of a structurally similar non-fluorinated FTU analog, toluene-2,4-dicarbamic acid diethyl ester (TDAEE) enhanced production of terminal end products from 8:2 FTOH degradation. However, there was no clear evidence that TDAEE enhanced cleavage of the urethane bond, thus TDAEE appeared to just serve as an additional carbon source. TDAEE's half-life was ∼ one week. A second addition of TDAEE appeared to retard subsequent degradation of FTU exemplifying the microbial dynamics and diversity impacting degradation of polyfluoroalkyl substances. Enhanced degradation of HMU was observed upon re-aeration indicating oxygen may have been limiting during some periods although degradation of intermediate metabolites to terminal metabolites was still occurring, albeit at slower rates.

Abstract  Neutral, volatile polyfluorinated alkyl substances (PFAS) were determined in high-volume air samples collected onboard the German research vessel Polarstern during cruise ANTXXIII-1 between Bremerhaven, Germany (53 degrees N) and Capetown, Republic of South Africa (33 degrees S) in fall 2005. An optimized and validated analytical protocol was used for the determination of several fluorotelomer alcohols (FTOHs) as well as N-alkylated fluorooctane sulfonamides and sulfonamidoethanols (FOSAs/FOSEs). Quantitative analyses were done by gas chromatography-mass spectrometry. This study provides the first concentration data of airborne PFAS from the Southern Hemisphere. Results indicate a strongly decreasing concentration gradient from the European continent toward less industrialized regions. The study confirms that airborne PFAS are mainly restricted to the Northern Hemisphere with a maximum concentration of 190 pg/m3 (8:2 FTOH) in the first sample collected in the channel between the European mainland and the UK. However, south of the equator, trace amounts of several FTOHs and FOSAs with a maximum of 14 pg/m3 (8:2 FTOH) could still be detected. Furthermore, a selection of ionic PFAS including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) were determined in the particulate phase of high-volume air samples by liquid chromatography-mass spectrometry. Levels of ionic PFAS were almost 2 orders of magnitude lower than those of neutral PFAS, with maximum concentrations in the first sample of 2.5 pg/m3 (PFOS) and 2.0 pg/m3 (PFOA).

Abstract  The adsorption behavior of 1,1,2,2,-tetrahydroheptadecafluorodecanol (FC10OH), 1-eicosanol (C20OH), and their mixtures at the hexane solution/water interface is summarized briefly and examined from the viewpoints of interfacial tensions in the presence of domains, domain formation, and the correlation between the phase transition and the miscibility of film forming substances in the adsorbed films. The two-dimensional analogue of the Laplace equation showed that the interfacial tension is always higher in the presence of domains than that in the absence of them. The higher tendency of domain formation of FC10OH compared to C20OH is mainly ascribed to the excess Gibbs energy of mixing of fluorocarbon chains and hydrocarbon solvent being positive and to the interaction energy between domains being more stable against cohesion for FC10OH than for C20OH. The thermodynamic equations derived here suggested the heteroazeotropy in the phase diagram of adsorption and the temperature dependence of interfacial tension at the phase transition points, which are in accord with the experimental findings qualitatively.

Abstract  Waterborne cationic fluorinated polyurethane (WCFPU) was prepared by the reaction of isophorone isocyanate (IPDI), polyether polyol (PTMG1000), N-methyldiethanolamine (MDEA), trimethylol propane (TMP) and 2-(perfluorooctyl) ethyl alcohol (FEOH) and then the films of the WCFPU were prepared. Their structure, surface property, mechanical properties, thermal performance and chemical resistance of their membrane were characterized by fourier transform infared spectrometer (FT-IR), interfacial tension instrument (IT), contact angle (CA), thermogravimetry (TG) and spot test. The results revealed that WCFPU was endowed with good mechanical properties and low surface energy of its film. TG diagrams also revealed that the application range of product was enlarged. It was also found that the fluorinated polyurethane had outstanding chemical resistance.

Abstract  The interfacial tension gamma of a hexane solution of 1,1,2,2-tetrahydroheptadecafluorodecanol CF3(CF2)(7)(CH2)(2)-OH (FC10OH) against water was measured as a function of temperature T and molality m(1) under atmospheric pressure. By the calculation of the interfacial density Gamma(1)(H) and then drawing the interfacial pressure pi vs area per adsorbed molecule A curves, it was concluded that two types of first-order phase transitions take place from the gaseous to the expanded state and from the expanded to the condensed one in the adsorbed film of FC10OH. The partial molar entropy (s) over bar(1)(H) - s(1)(O) and energy changes (u) over bar(1)(H) - u(1)(O) associated with the adsorption were estimated and compared with those of 1,1,2,2-tetrahydrohenicosafluorododecanol CF3(CF2)(9)(CH2)(2)OH (FC12OH). It was found that these values of FC10OH are negative and larger than those of FC12OH. It was suggested that, although both (s) over bar(1)(H) and s(1)(O) values increase, the increment in s(1)(O) is larger than that in (s) over bar(1)(H) when the fluorocarbon chain is lengthened from FC10OH to FC12OH. Furthermore, it was realized that the energetical stabilization of the FC10OH molecule accompanied by adsorption is less than that of the FC12OH molecule. Furthermore, it was shown that the temperature and pressure dependencies of the pi vs A curve are related to the partial molar entropy and volume changes of adsorption, respectively. By estimation of the temperature and pressure coefficients of A at constant pi, it is found that a temperature increase of only 1 K is sufficient to keep pi and A constant upon a decrease of the pressure by 1 MPa.

Abstract  Purpose : The purpose of this study was to investigate the effects of change in daily physical activity during an exercise intervention oil health status and physical fitness.

Methods : Participants were 22 obese middle-aged men (BMI :29.1 +/- 2.8kg/m(2), 54.1 +/- 11.4% yr). They performed 90-min exercise sessions on a regular basis 3 days per week for 3 months. Physical activity (total energy expenditure, TEE activity energy expenditure, AEE : and step Counts) was measured using an accelerometer. Daily physical activity was defined as that which was pet-formed Outside of the exercise class. A 3-day food record was used to estimate energy intake.

Results : Body weight decreased (-3.0 +/- 2.5kg, P<0.05). Vital age (VA), all index of comprehensive health status, and physical fitness age (PFA), an index of comprehensive physical fitness. significantly improved VA : -8.7 +/- 5.5 yr, PFA : -8.5 +/- 5.1 yr. P<0.05). Energy intake remained Unchanged during the intervention (+63.7 +/- 546.1 kcal/d). Daily physical activity increased (TEE : +83.0 +/- 130.1 kcal/d, AEE : +76.9 +/- 103.3 kcal/d, step counts : +1789 +/- 2819 steps/d, P < 0.05). Change in daily physical activity was correlated with change in VA (AEE : r = -0.52. step counts: r = -0.46, P < 0.05), while change in daily physical activity did not correlate with change in PFA.

Conclusion : These results suggest that changes in daily physical activity during an exercise intervention are associated with improved health status. (Jpn. J. Phys. Fitness Sports Med. 2008, 57 : 463 similar to 474)

Abstract  The interfacial tensions (gamma) of the hexane solutions of 1H,1H-perfluorononanol (FDFC9OH) and its omega-hydrogenated analogue 1H,1H,9H-perfluorononanol (HDFC9OH) against water were measured as a function of temperature and concentration under atmospheric pressure in order to know the effect of omega-dipoles on the adsorption behavior of fluorononanols. The interfacial pressure (pi) versus mean area per adsorbed molecule (A) curves consist of two discontinuous changes among three different states: the gaseous, expanded, and condensed states. The A values at given pi in the gaseous and expanded states are larger for HDFC9OH than for FDFC9OH. The changes in partial molar entropy (s1(H) - s1(O)) and energy (u1(H) - u1(O)) of adsorption were evaluated. Their values are negative, and therefore, the alcohols have a smaller entropy and energy at the interface than in the bulk solution. Furthermore, the u1(H) - u1(O) value is more negative for HDFC9OH than for FDFC9OH in the expanded state and also in the condensed film just above the expanded-condensed phase transition point. This seems to be due to the following: (1) HDFC9OH may tilt from interface normal for omega-dipoles to interact effectively with water molecules in the interfacial region and to reduce their own repulsive interaction between neighbors arranging parallel in the adsorbed film. This leads to a lower value for HDFC9OH than for FDFC9OH. (2) The contact of omega-dipoles with hexane molecules in the bulk solution is energetically unfavorable, and thus, the u1(O) value of HDFC9OH is expected to be larger than that of FDFC9OH.

Abstract  Polyfluoroalkyl phosphate surfactants (PAPS) are used on food contact paper to impart oil/grease resistance and have been shown to be able to migrate into food. The biotransformation of the congeners belonging to this class of compounds is considered to be a potential source of perfluorinated carboxylic acids (PFCAs). In this study, two methods were developed for the determination of seven perfluorinated compounds (PFCs) and eight polyfluorinated disubstituted phosphate surfactants (diPAPS) in human milk. PFCs were extracted from milk using an ion-pairing technique; while the diPAPs extraction involved a sample clean up using solid phase extraction. Analyses of all compounds in this study were performed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Of the seven PFCs analyzed in human milk, only perfluorooctanoic acid (PFOA) was detected in eleven out of thirteen (85%) individual human milk samples analyzed, with a concentration range of <0.072 to 0.52 ng mL(-1). Four diPAPS were detected and quantified in human milk samples. Eight out of thirteen samples contained 4:2 diPAP with a concentration range of <0.01-0.26 ng mL(-1); 6:2 diPAP was detected in five samples with a concentration range of <0.01-0.14 ng mL(-1); 8:2 diPAP was detected in only three samples with concentrations of 0.21, 0.27, and 0.30 ng mL(-1). The 10:2 diPAP was quantified in seven milk samples, with concentration range of <0.01-0.83 ng mL(-1). No correlation was established between PFCAs and PAPS levels in this small sample size. To the best of the authors' knowledge, this is the first study to report the presence of PAPS in human milk.

Abstract  Fluorotelomer alcohols (FTOHs) are the main precursors of environmentally ubiquitous perfluorinated acids, and determination of FTOHs at low concentrations presents significant challenges. In this study, a new liquid chromatography-electrospray mass spectrometry (LC-ESI-MS) method in conjunction with low-energy collision dissociation tandem mass spectrometry (CID-MS/MS) was developed by employing an optimized derivatization reaction with dansyl chloride (DNS) in acetonitrile under catalysis of 4-(dimethylamino)-pyridine (DMAP). The instrument detection limits (IDLs) of the newly developed method were 0.014, 0.015, 0.014, 0.0075 and 0.0093μg/L for 4:2 FTOH, 6:2 FTOH, 8:2 FTOH, 10:1 FTOH and 10:2 FTOH respectively, which were 7.5-241 times lower than those without derivatizaiton and 57-357 times lower than previous GC/MS method. The method was successfully applied to analyze FTOHs in sediments combined with WAX and silica cartridges cleanup. The overall method recoveries were from 67±6.0% to 83±9.4% with matrix effects of <15%. The limits of quantification for all FTOHs were 0.017-0.060ng/gdry weight (dw). The method was applied to analyze six marine sediment samples from Liaodong Bay, China. All FTOHs except for 10:1 FTOH were detected, and the total concentrations of FTOHs were 0.19-0.52ng/gdw. The developed method provides a new method to sensitively determine FTOHs in environmental matrices.

Abstract  The mixed adsorbed film of 1H,1H-perfluorooetanol (DFC8OH) and 1H,1H,2H,2H-perfluorodecanol (TFC10OH) at the hexane/water interface was studied on the basis of interfacial tension measurement and its thermodynamic data analysis. An adsorbed film at any composition of the mixed system as well as those of pure DFC8OH and TFC10OH systems exhibits three states: the gaseous, expanded, and condensed states. Construction of the phase diagram of adsorption clarified that DFC8OH and TFC10OH mix almost ideally in the gaseous and expanded states. On the contrary, the excess Gibbs energy of adsorption g(H,E) value evaluated in the condensed state was positive. These results are explained by considering the following two factors: (1) The mixing of binary alcohols is accompanied by the loss of dispersion interaction energy due to the difference in extent of fluorination of hydrophobic chains and in their chain length and increases the g(H,E) value. (2) Since the interchange energy concerning the interaction between dipoles with different dipole moments is negative, the mixing of these alcohols reduces the repulsive force between hydrophilic groups and thus leads to a decrease in the g(H,E) value. In the gaseous and expanded states, both of above two factors are not effective. On the other hand, the positive g(H,E) value in the condensed state is attributable to more effective dispersion interaction than the dipole-dipole interaction in short molecular distance, and so factor 1 becomes dominant. Comparison of the g(H,E) value of the present system with that of the homologous TFC10OH-TFC12OH mixture leads us to a conclusion that the hydrogenation on beta-carbons in hydrophobic chains affects appreciably the balance of interactions between hydrophilic and hydrophobic groups which governs the mixing of molecules in adsorbed films.

Abstract  A quantitative analytical method was developed to simultaneously detect fluorotelomer alcohols (6:2 FTOH, 8:2 FTOH and 10:2 FTOH) and polyfluorinated sulfonamides (perfluoro-1-octanesulfonamide (FOSA) and N-methylperfluoro-1-octanesulfonamide (NMeFOSA)) in biotic samples with liquid chromatography-atmospheric pressure photoionization mass spectrometry (LC-APPI-MS/MS). APPI mass spectra for FOSA and NMeFOSA showed that the major ionization mechanism was not photoionization, whereas for the FTOHs it was photoionization. For FTOHs, a [M+O(2)](-) ion was generated with a similar response as the deprotonated molecular ion [M-H](-). We demonstrated that FTOHs, FOSA and NMeFOSA can be measured in various biota samples using APPI with a minimized matrix effect. Using APPI, the linear response range for the FTOHs was 0-1,000 ng/mL (r(2)>0.9997), and for FOSA and NMeFOSA ranged from 0 to 250 ng/mL (r(2)>0.995). The instrument and method detect limits ranged from 0.16 to 0.63 pg and below 1 ng/g wet weight (w.w.), respectively. For the overall method applied to the test matrices, recovery efficiencies ranged from 73 to 102% for egg homogenate and 89-100% for liver tissue. The present study demonstrates for the first time that a far more response and sensitive approach for the detection and quantification of FTOHs and polyfluorinated sulfonamides is possible using APPI as opposed to electrospray ionization.

Abstract  A bifunctional terminal organic-inorganic dendrimer with fluorocarbon and hydrocarbon units at its terminal groups was successfully prepared by a hydrosilylation reaction, and a combination of a ring-opening reaction and condensation reaction of octakis(propenylsuccinicanhydrido)polyhedraloctasilicate (OS-SA) with 1-decanol and 1H,1H,2H,2H-perfluoro-1-decanol. The structure of the OS-core dendrimer bearing the decyl and 1H,1H,2H,2H-heptadecafluorodecyl groups (OS-CF) was fully characterized by FT-IR, NMR spectra, and MALDI TOF MS spectrum. The crystallinity of the fluorinated domains in OS-CF decreased in comparison with that in I-CF and the fluorocarbon/hydrocarbon chains form no ordered structure due to suppression of the molecular motion of their branches resulting from the rigid inorganic core. The composite films of PMMA containing OS-CF were prepared through solution blending of PMMA with various concentrations of OS-CF (5, 10, and 20 wt %). The refractive index of the neat PMMA film is 1.49, and the refractive indices of the composite films containing OS-CF decrease linearly with increases in the OS-CF weight fraction. (c) 2017 Wiley Periodicals, Inc.

Abstract  8-2 Fluorotelomer alcohol (FTOH) and its metabolites, perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA), are developmental toxicants but metabolism and distribution during pregnancy are not known. To examine this, timed-pregnant mice received a single gavage dose (30 mg 8-2 FTOH/kg body weight) on gestational day (GD) 8. Maternal and neonatal serum and liver as well as fetal and neonatal homogenate extracts were analyzed using gas chromatography coupled with mass spectrometry. During gestation (GD9 to GD18), maternal serum and liver concentrations of PFOA decreased from 789 +/- 41 to 668 +/- 23 ng/ml and from 673 +/- 23 to 587 +/- 55 ng/g, respectively. PFOA was transferred to the developing fetuses as early as 24-h posttreatment with concentrations increasing from 45 +/- 9 ng/g (GD10) to 140 +/- 32 ng/g (GD18), while PFNA was quantifiable only at GD18 (31 +/- 4 ng/g). Post-partum, maternal serum PFOA concentrations decreased from 451 +/- 21 ng/ml postnatal day (PND) 1 to 52 +/- 19 ng/ml (PND15) and PFNA concentrations, although fivefold less, exhibited a similar trend. Immediately after birth, pups were cross-fostered with dams that had been treated during gestation with 8-2 FTOH (T) or vehicle (C) resulting in four treatment groups in which the first letter represents in utero (fetal) exposure and the second represents lactational (neonatal) exposure: C/C, T/C, C/T, T/T. On PND1, neonatal whole-body homogenate concentrations of PFOA from T/T and T/C groups averaged 200 +/- 26 ng/g, decreased to 149 +/- 19 ng/g at PND3 and this decreasing trend was seen in both neonatal liver and serum from PND3 to PND15. Based on detectible amounts of PFOA in neonatal serum in the C/T group on PND3 (57 +/- 11 ng/ml) and on PND15 (58 +/- 3 ng/ml), we suggest that the neonates were exposed through lactation. In conclusion, exposure of neonates to PFOA and PFNA occurs both pre- and postnatally following maternal 8-2 FTOH exposure on GD8.

Abstract  The contribution of direct (i.e., uptake of perfluorooctanoic acid (PFOA) itself) and indirect (i.e., uptake of 8:2 fluorotelomer alcohol (FTOH) and metabolism to PFOA) exposure to PFOA serum concentrations was investigated using a dynamic one-compartment pharmacokinetic (PK) model. The PK model was applied to six occupationally exposed ski waxers for whom direct and indirect exposures via inhalation were characterized using multiple measurements with personal air sampling devices. The model was able to predict the diverging individual temporal trends of PFOA in serum with correlation coefficients of 0.82-0.94. For the four technicians with high initial concentrations of PFOA in serum (250-1050 ng/mL), the ongoing occupational exposure (both direct and indirect) was of minor importance and net depuration of PFOA was observed throughout the ski season. An estimated average intrinsic elimination half-life of 2.4 years (1.8-3.1 years accounting for variation between technicians and model uncertainty) was derived for these technicians. The remaining two technicians, who had much lower initial serum concentrations (10-17 ng/mL), were strongly influenced by exposure during the ski season with indirect exposure contributing to 45% of PFOA serum concentrations. On the basis of these model simulations, an average metabolism yield of 0.003 (molar concentration basis; uncertainty range of 0.0006-0.01) was derived for transformation of 8:2 FTOH to PFOA. An uncertainty analysis was performed, and it was determined that the input parameters quantifying the intake of PFOA were mainly responsible for the uncertainty of the metabolism yield and the initial concentration of PFOA in serum was mainly contributing to the uncertainty of estimated serum half-lives.

Abstract  Pentadecafluorooctanoic acid is an established peroxisome proliferator. Little is known about effects of treatment with 1H,1H,2H,2H-heptadecafluorodecan-1-ol, which is metabolized to pentadecafluorooctanoic acid. We compared effects of various dosages (3, 10, or 25 mg/kg body wt) of each of these compounds on hepatic gene expression in rats with microarrays. Microarray data were validated by real-time RT-PCR. Expression data were also correlated with hepatic activities of selected enzymes and with hepatic levels of pentadecafluorooctanoic acid and 1H,1H,2H,2H-heptadecafluorodecan-1-ol. Pentadecafluorooctanoic acid caused the more powerful change in gene expression, in terms of both number of genes affected and extent of change in expression. Across the dosages used pentadecafluorooctanoic acid and 1H,1H,2H,2H-heptadecafluorodecan-1-ol caused significant (P < or = 0.05) changes in expression for 441 and 105 genes, respectively. With 1H,1H,2H,2H-heptadecafluorodecan-1-ol approximately 38% of the 105 genes exhibited decreased expression with a dose of 25 mg/kg body wt, these genes also appearing less responsive to treatment at the lower dosages. Bioinformatic analysis suggested that these genes are associated with regulatory functions. With pentadecafluorooctanoic acid, increasing dosage up to 10 mg/kg body wt brought about progressive increase in expression of affected genes. Pathways analysis suggested similar effects of the two compounds on lipid and amino acid metabolism. Marked differences were also found, particularly with respect to effects on genes related to oxidative phosphorylation, oxidative metabolism, free radical scavenging, xenobiotic metabolism, and complement and coagulation cascades.

Abstract  PFASs concentrations in dust samples collected from three microenvironments in Cairo ranged from 1.3 to 69 ng g(-1) with FTOHs being dominant. The 8:2 FTOH was detected in all samples. Among the FOSAs and FOSEs the MeFOSE was dominant while among ionic PFASs, PFOS and PFOA were most prominent. The concentrations of PFASs were among the lowest worldwide. Correlations between worldwide concentrations of PFOS + PFOA and country development indexes highlight higher usage and human exposure in more developed countries. Food packaging was analyzed for PFSAs, PFCAs and PAPs. The 6:2 and 8:2 monoPAPs were found to be above the MDL in 18% of the samples. PFOA was detected in 79% of the samples with median concentration of 2.40 ng g(-1). PFOS was detected in 58% of the samples with median concentration of 0.29 ng g(-1) while PFHxS and PFDS were below detection limit. Different human exposure scenarios were estimated.

Abstract  Twenty high-volume air samples were collected during a crossing of the North Atlantic and Canadian Archipelago in July 2005 to investigate air concentrations of fluorotelomer alcohols (FTOHs) and perfluoalkyl sulfonamido ethanols (PFASs). These commercial chemicals are widely used as surface treatments and are believed to be precursors for perfluorocarboxylic acids (PFCAs) and perfluorooctane sulfonate (PFOS) that accumulate in humans and biota, including those from remote arctic regions. The highest concentrations (sum of gas- and particle-phase) of FTOHs were for 8:2 FTOH (perfluoroctyl ethanol) (5.8-26 pg/m(3)), followed by 10:2 FTOH (perfluorodecyl ethanol) (1.9-17 pg/ m(3)) and 6:2 FTOH (perfluorohexyl ethanol) [BDL (below detection limit) to 6.0 pg/m(3)]. For the PFASs, MeFOSE (N-methyl perfluorooctane sulfonamido ethanol) was dominant and ranged from 2.6 to 31 pg/m(3); EtFOSE (N-ethyl perfluorooctane sulfonamido ethanol) ranged from BDL to 8.9 pg/m(3) and MeFOSEA (N-methyl perfluorooctane sulfonamide ethylacrylate) was BDL in all samples. Air parcel back-trajectories showed that the sampled air was largely representative of the arctic air mass. Air concentrations of target compounds were of the same order of magnitude as reported air concentrations in source regions. For instance, the mean 8:2 FTOH concentration was only a factor of about 3 lower than for three urban samples that were collected in Toronto for comparison. These findings confirm model results that predictthe efficient, long-range atmospheric transport and widespread distribution of FTOHs and related compounds in the arctic region. Mean particulate percentages for FTOHs and PFASs in the cruise samples (mean temperature, 5+/-4 degrees C) were BDL for 6:2 FTOH, 23% for 8:2 FTOH, 15% for 10:2 FTOH, 32% for MeFOSE, and 22% for EtFOSE. Further, the partitioning to particles for MeFOSE and EtFOSE was significantly correlated with inverse absolute temperature, whereas the FTOHs did not show this trend. The Toronto samples (mean temperature, -1+/-1 degree C) showed similar particulate percentages for MeFOSE and EtFOSE; however, the FTOHs were substantially less particle-bound. Although the mechanism for this partitioning is not understood, the results do indicate the need to better account for particle phase transport when modeling the atmospheric fate of these chemicals.

Abstract  A new, fast and simple sampling method using commercially available Isolute ENV+ solid-phase extraction (SPE) cartridges for the enrichment of neutral, volatile polyfluorinated alkyl substances (PFAS) was developed and applied to selected air samples. The SPE cartridges showed good retention capacity for the target analytes, and most of the investigated compounds could be quantified in 20m(3) indoor air. Employing the developed method, it was shown that high levels of selected fluorotelomer alcohols (FTOHs) and N-alkyl fluorooctane sulfonamides/-ethanols (FOSAs/FOSEs) evaporated from a paraglider. Furthermore, the new method was compared to the 'classical' approach using glass-fibre filters (GFFs) and XAD-2 resin sandwiched between polyurethane foam plugs (PUF/XAD/PUF) to investigate environmental air concentrations in metropolitan Hamburg. Due to the high counter pressure of SPE cartridges, only low-volume air sampling was feasible. Therefore, the trace levels of FOSAs/FOSEs occurring in environmental air could only be quantified occasionally in the samples enriched on SPE cartridges. However, quantitative analysis of the higher concentrated 6:2 FTOH, 8:2 FTOH and 10:2 FTOH was possible in all low-volume environmental air samples. Finally, the determination of ionic PFAS, including perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA), bound to airborne particles in the air samples from Hamburg is described.

Abstract  The quantitative measurement of individual cells and their characteristics by means of flow cytometry is already for many years of great value for clinical studies. However, its potential as a tool in (eco)toxicology has only recently been discovered. Analysis of cell cycle kinetics with DNA-staining dyes can offer a valuable alternative to detect effects of chemicals on cell proliferation, an important endpoint in screening estrogen-like properties of chemicals. In the present study, flow cytometric cell cycle analysis in growth arrested MCF-7 cells exposed to five xenoestrogens correspond well with cell proliferation results of the conventionally used E-screen assay. Moreover, re-induction of proliferation in MCF-7 cells, indicated by the percentage of cells in S(ynthesis)-phase, is most pronounced after 24 h exposure, thus allowing a faster screening of xenoestrogens. This flow cytometric proliferation assay confirms that the estrogenic activity of structurally analogous parabens is mediated by the estrogen receptor pathway and is proportional to the alkyl chain length. Moreover, the ER-mediated mode of action of two fluorotelomer alcohols (6:2 FTOH and 8:2 FTOH), recently reported as xenoestrogenic, could be elucidated. These results support the potential of flow cytometric cell cycle kinetics as a screening assay for estrogen-like properties of chemicals.

Abstract  Perfluorochemicals (PFCs) are emerging persistent organic pollutants (POPs) and are widely present in the environment, wildlife and humans. Recently, reports have suggested that PFCs may have endocrine-disrupting activities. In the present study, we have developed a non-competitive enzyme-linked immunosorbent assay (ELISA) method to investigate estrogenic activities of selected PFCs using vitellogenin (VTG) induction in primary cultured hepatocytes of freshwater male tilapia (Oreochromis niloticus). Cultured hepatocytes were exposed to various concentrations of perfluorooctanyl sulfonate (PFOS), pentadecafluorooctanoic acid (PFOA), 1H, 1H, 2H, 2H-nonafluoro-1-hexanol (4:2 FTOH), 1H, 1H, 2H, 2H-perfluorooctanol (6:2 FTOH) and 1H, 1H, 2H, 2H-perfluoro-1-decanol (8:2 FTOH) for 48 h, while 17beta-estradiol (E2) and 4-nonylphenol (4-NP) were used as positive controls. A dose-dependent induction of VTG was observed in E2-, 4-NP-, PFOS-, PFOA- and 6:2 FTOH-treated cells, whereas VTG levels remained unchanged in the 4:2 FTOH and 8:2 FTOH exposure groups at the concentrations tested. The estimated 48-h EC(50) values for E2, 4-NP, PFOS, PFOA and 6:2 FTOH were 4.7 x 10(-7), 7.1 x 10(-6), 1.5 x 10(-5), 2.9 x 10(-5) and 2.8 x 10(-5)M, respectively. In the time-course study, significant VTG induction took place at 24 h (E2), 6 h (4-NP), 48 h (PFOS), 48 h (PFOA), 72 h (4:2 FTOH), 12 h (6:2 FTOH), 72 h (8:2 FTOH), and increased further after 96 h of exposure. Co-exposure to binary mixtures of individual PFCs and E2 for 48 h significantly inhibited E2-induced hepatocellular VTG production in a dose-dependent manner except for 4:2 FTOH. The estimated 48-h IC(50) (concentration of a compound that elicits 50% inhibition of maximally E2-induced VTG) values for PFOS, PFOA, 6:2 FTOH and 8:2 FTOH were 3.1 x 10(-7), 5.1 x 10(-7), 1.1 x 10(-6) and 7.5 x 10(-7)M, respectively. In order to further investigate the estrogenic mechanism of PFCs, the hepatocytes were co-exposed to binary mixtures of individual chemicals (E2, 4-NP, PFOS, PFOA and 6:2 FTOH) and the known estrogen receptor inhibitor tamoxifen for 48 h; tamoxifen significantly inhibited the ability of these chemicals to stimulate vitellogenesis. The overall results demonstrated that PFOS, PFOA and FTOHs have estrogenic activities and that exposure to a combination of E2 and PFCs produced anti-estrogenic effects. The results of the estrogen receptor inhibition assay further suggested that the estrogenic effect of PFCs may be mediated by the estrogen receptor pathway in primary cultured tilapia hepatocytes.

Abstract  Levels of perfluorinated carboxylates (PFCAs) in different environmental and biological compartments have been known for some time, but the routes of exposure still remain unclear. The opinions are divergent whether the exposure to general populations occurs mainly indirect through precursor compounds or direct via PFCAs. Previous results showed elevated blood levels of PFCAs in ski wax technicians compared to a general population. The objective of this follow-up study was to determine concentrations of PFCAs, perfluorosulfonates (PFSAs), and fluorotelomer alcohols (FTOHs), precursor compounds that are known to degrade to PFCAs, in air collected in the breathing zone of ski wax technicians during work. We collected air samples by using ISOLUTE ENV+ cartridges connected to portable air pumps with an air flow of 2.0 L min(-1). PFCAs C5-C11 and PFSAs C4, C6, C8, and C10 were analyzed using LC-MS/MS and FTOHs 6:2, 8:2, and 10:2 with GC-MS/MS. The results show daily inhalation exposure of 8:2 FTOH in μg/m(3) air which is up to 800 times higher than levels of PFOA with individual levels ranging between 830-255000 ng/m(3) air. This suggests internal exposure of PFOA through biotransformation of 8:2 FTOH to PFOA and PFNA in humans.

Abstract  A laboratory investigation on the biotransformation of 8:2 fluorotelomer stearate monoester (8:2 FTS) in aerobic soils was conducted by monitoring the loss of 8:2 FTS, production of 8:2 fluorotelomer alcohol (8:2 FTOH) and stearic acid, which would be released by cleavage of the ester linkage, and subsequent degradation products from FTOH for 80 d. Soil microcosms were extracted with ethyl acetate followed by two heated 90/10 v/v acetonitrile/200 mM NaOH extractions. 8:2 FTS was degraded with an observed half-life (t(1/2)) of 10.3 d. The rate of 8:2 FTS biotransformation substantially decreased after 20 d with 22% of 8:2 FTS still remaining on day 80. No biotransformation of 8:2 FTS occurred in autoclaved soil controls, which remained sterile with 102 ± 6% recovery, through day 20. 8:2 FTOH was generated with cleavage of the ester linkage of 8:2 FTS followed by a rapid decline (t(1/2) ~ 2 d) due to subsequent biodegradation. All the expected 8:2 FTOH degradation products were detected including 8:2 fluorotelomer unsaturated and saturated carboxylic acids, 7:2s FTOH, 7:3 acid, and three perfluoroalkyl carboxylic acids with the most prominent being perfluorooctanoic acid (PFOA). PFOA consistently increased over time reaching 1.7 ± 0.07 mol % by day 80. Although cleavage of the ester linkage was evidenced by 8:2 FTOH production, an associated trend in stearic acid concentrations was not clear because of complex fatty acid metabolism dynamics in soil. Further analysis of mass spectrometry fragmentation patterns and chromatography supported the conclusion that hydrolysis of the ester linkage is predominantly the first step in the degradation of 8:2 FTS with the ultimate formation of terminal products such as PFOA.

Abstract  Smog chamber/FTIR techniques were used to measure a 92 +/- 7% yield of C8F17CH2CHO in the chlorine atom initiated oxidation of C8F17CH2CH2OH ( 8: 2 FTOH) in 700 Torr of air. Relative rate techniques were used to measure k(Cl + C8F17CH2CHO) = (1.9 +/- 0.4) x 10 (11) and k(OH + C8F17CH2CHO) = (2.0 +/- 0.4) x 10 (12) cm(3) molecule (1) s (1) in 700 Torr of N-2 or air diluent at 296 K. The results are discussed with respect to the atmospheric chemistry of fluorotelomer alcohols. (C) 2008 Elsevier B.V. All rights reserved.