TP064 (HUS-1117-834435) Discovery of Semi-Volatile Fluoroalkyl Substances in Municipal Wastewater Treatment Plant Sludge.
Start time: 8:00 AM
Huset, C¹, Barofsky, D^{1, 2}, Field, J^{2, 3}, ¹ Department of Chemistry, Oregon State University, Corvallis, OR, USA² Environmental Health Sciences Center, Oregon State University, Coravllis, OR, USA³ Department of Environmental and Molecular Toxicology, Oregon State University, Corvallis, OR, USA
Fluoroalkyl substances are globally distributed and persistent in the environment. Semi-volatile fluoroalkyl substances are known to degrade to form anionic fluoroalkyl substances which have been measured in municpal wastewater treatment plant systems. The fate of semi-volatile fluoralkyl substances in municipal wastewater treatment systems is largely unknown. Given the ubiquitous presence of fluoroalkyl substances in the environment and the potential for wastewater treatment plants to act as environmental point sources for these substances, it is our objective to understand the role of the municipal wastewater treatment plants play in the fate and transport of fluoroalkyl substances in the environment. To this end, we have developed a method for the quantitative analysis of semi-volatile fluoroalkyl substances in anaerobially digested and activated sludge. Semi-volatile fluoralkyl substances detected in sludge include fluoroalkyl sulfonamides, acrylates, olefins and fluorotelomer alcohols. The results of solid-liquid extraction method experiments will be addressed with attention to the selection of extraction solvent, extraction efficiencies and recoveries of analytes.

TP065 (MAS-1117-859988) Environmental behavior and mass balance of perfluorinated surfactants in Tokyo Bay, Japan.
Start time: 8:00 AM
Masunaga, S¹, Odaka, R¹, ¹ Yokohama National University, Yokohama, Kanagawa, Japan
Perfluorinated surfactants; perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have been reported to be remaining in environment. Their environmental behavior, however, is still unknown. In this study, we measured their concentrations in the seawater and sediment from Tokyo Bay and in water of six major rivers that run into the bay. Then, their mass balances and behaviors in the bay were estimated. PFOS and PFOA existed mainly as dissolved-phase in water. Estimated annual input of PFOS from the rivers (120 - 260 kg/year) were about 6 to 13 times larger than the total amount of outflow to outer sea (20 kg/year) and sedimentation to the bottom (1.3 kg/year). On the other hand, estimated annual input of PFOA from rivers (38 - 85 kg/year) were about 1/4 to 2/3 times smaller than the outflow (140 kg/year). The amount of PFOA deposition to bottom sediment was negligible. These results suggested possibility of PFOS transformation in the bay and of unknown PFOA sources around the coast of the bay. The results also showed that bottom sediment was not their sink. Their environmental behaviors, therefore, were quite different from those of persistent organochlorine compounds. Furthermore, behaviors and location of sources were suggested to be different between PFOS and PFOA though they both belong to the same perfluorinated surfactant group.

TP066 (KOC-1117-823298) Environmental Exposure Assessment of Fluorotelomer-based Substances using a Multispecies Approach.
Start time: 8:00 AM
Koch, V¹, Russell, M², ¹ Clariant GmbH, Sulzbach, Germany² DuPont, Newark, DE, USA
Fluorotelomer-based substances like 2-Perfluorooctylethanol are speciality chemicals being used to synthesize e.g. high molecular weight Fluorotelomer-based acrylate polymers (FBAPs). FBAPs are used for coating of textiles, paper and carpet to achieve oil, stain and water repellency properties. Concerns that fluorotelomer-based polymers may be a source for low molecular Fluorotelomer-based substances which could be transformed to perfluorinated carboxylic acids like PFOA have triggered investigations on the fate and distribution of such chemicals in different environmental compartments. These data are pre-requisites for an environmental exposure assessment for Fluorotelomer-based substances which takes into account the releases across the whole life cycle. Single species exposure models cannot be used to estimate environmental concentrations for multiple kinetic transformations of the different species involved. Recently the approach of the environmental exposure assessment described in the European Union Technical Guidance Document on Risk Assessment of Substances, 2003 (http://ecb.jrc.it) was implemented in an EXCEL TM Spreadsheet allowing a transparent continental, regional and local assessment (van de Meent, D and Huijbregts M, University of Nijmegen, The Netherlands) for the 15 Member States of the EU as of 2003. This Spreadsheet model has provided an ideal starting point to incorporate the necessary multi-species component which addresses the mass loadings and degradation kinetics of each chemical species. In addition, the geographic parameter database for the spreadsheet model has been expanded to permit simulation of other continental settings in addition to Europe. The application of this globally scalable multispecies environmental exposure model will be shown for the fluorotelomer-based substances described above. In addition the applicability of the underlying scientific concepts and algorithms used in the model for the exposure assessment of fluorochemicals will be addressed as well.

TP068 (LEH-1117-807053) Mixing of Perfluorooctanesulfonic Acid (PFOS) Potassium Salt.
Start time: 8:00 AM
Lehmler, H.¹, Bothun, G.^{2, 4}, Bummer, P.³, Knutson, B.², ¹ The University of Iowa, Department of Occupational and Environmental Health, Iowa City, Iowa, USA² University of Kentucky, Department of Chemical and Materials Engineering, Lexington, Kentucky, USA⁴ North Carolina A&T State University, NSF-STC Environmentally Responsible Solvents and Processes, Greensboro, North Carolina, USA³ University of Kentucky, College of Pharmacy, Lexington, Kentucky, USA
Perfluorooctane-1-sulfonic acid (PFOS) is emerging as an important persistent environmental pollutant, thus raising environmental and human health concerns. To gain insight into the interactions of PFOS with biological systems, the mixing behavior of dipalmitoylphosphatidylcholine (DPPC) with a commercial PFOS potassium salt was studied using differential scanning calorimetry (DSC) and fluorescence anisotropy measurements. Changes in the onset temperature of the DPPC pretransition (Tp) were investigated by DSC. The Tp decreased with increasing PFOS concentration, disappearing at X(DPPC) < 0.97. The main DPPC phase transition temperature showed a linear depression and peak broadening with increasing mole fraction of PFOS in both the DSC and the fluorescence anisotropy studies. From the melting point depression in the fluorescence anisotropy studies, which was observed at a concentration as low as 10 mg/L, an apparent partition coefficient of K = 5.3 x 10⁴ (mole fraction basis) was calculated. These results suggest that compared to other fluorinated surfactants, such as sodium perfluorooctanoate (K = 8.9 x 10³), PFOS has a high tendency to partition into phospholipid bilayers. This partition coefficient and the resulting changes in the phase behavior of lipid bilayers may be an important determinant of the disposition of PFOS and may represent one possible mechanism of PFOS mediated toxicity (Supported by ES 012475).

TP070 (NAK-1117-883849) Measurement of perfluorooctane sulfonate and related perfluorinated compounds in human maternal and cord blood samples.
Start time: 8:00 AM
Nakazawa, Hiroyuki¹, Kawaguchi, Migaku¹, Nakata, Hisao¹, Okada, Fumio¹, Inoue, Koichi¹, Ito, Rie¹, Saito, Koichi¹, Saijo, Yasuaki², Sata, Fumihiro², Kishi, Reiko², ¹ Department of Analytical Chemistry, Faculty of Pharmaceutical Sciences, Hoshi University, Tokyo, Japan² Department of Public Health, Hokkaido University Graduate School of Medicine, Hokkaido, Japan
Perfluorochemicald(PFCs), such as perfluorooctane sulfonate (PFOS), perfluoro-octanoate (PFOA), and perfluorooctane sulfonylamide (PFOSA),which has their amphiphilic character and their thermal, biological, and chemical stability are widely used in the manufacture of plastic, electronics, textile, and construction material in the apparel, leather, and upholstery industries. On the other hand, evidence of toxic effects and environmental pollution was reported and discussed. Studies have indicated that PFCs may be detrimental to rodent development possibly affecting thyroid hormone levels. In the present study, the concentration of PFCs in maternal and cord blood samples was determined. For the measurement, pregnant women 17-37 years of age were enrolled as subjects. PFCs in 15 pairs of maternal and cord blood samples were analyzed by liquid chromatography-electrospray mass spectrometry coupled with online extraction. The limits of quantification of PFOS, PFOA, and PFOSA in human plasma or serum were 0.5, 0.5, and 1.0 ng/mL, respectively. The method enables the precise determination of PFCs and can be applied to the detection of PFCs in human blood samples for monitoring human exposure. PFOS concentrations in maternal samples ranged from 4.9 to 17.6 ng/mL, whereas those in fetal samples ranged from 1.6 to 5.3 ng/mL. In contrast, PFOSA was not detected in fetal or maternal samples, whereas PFOA was detected only in maternal samples (range, < 0.5 to 2.3 ng/mL, 4 of 15). Our results revealed a high correlation between PFOS concentrations in maternal and cord blood (r2 = 0.876). However, we did not find any significant correlations between PFOS concentration in maternal and cord blood samples and age bracket, birth weight, or levels of thyroid-stimulating hormone or free thyroxine. Our study revealed that human fetuses investigated in the present study may be exposed to relatively high levels of FOCs. For requirement of further investigation, we have studied the development of more highly sensitive and precise analytical method of PFCs by LC/MS/MS to estimate of the postnatal effects of fetal exposure to PFCs.

TP071 (YOO-1117-834205) Separation and characterization of structural isomers of perfluorinated compounds.
Start time: 8:00 AM
Yoo, H¹, Jones, P¹, Bradley, P¹, Gužviæ, M², Upham, B², Trosko, J², Newsted, J³, Giesy, J¹, ¹ National Food Safety and Toxicology Center, Zoology Department and Center for Integrative Toxicology, Michigan State University, East Lansing, MI, USA² Department of Pediatrics and Human Development, Michigan State University, East Lansing, MI, USA³ ENTRIX Inc., Okemos, MI, USA
The presence of complex mixtures of perfluorinated compounds (PFCs) with different physical-chemical and toxicological properties provides a challenge for risk assessment. In general, standards used for PFC quantification and toxicological studies have not been characterized for their isomer distribution. Using modifications of current PFC analytical methods we have separated a commercial PFOS mixture into three separate isomer peaks. The largest peak (peak III), presumed to be the straight chain isomer constitutes greater than 63 % of the materials mass while the earlier eluting peaks, peaks I and II constitute 2.5% and 34% of the mass respectively. The mixture also contained traces of PFOA and shorter chain sulfonates that were not quantified. Using a preparative HPLC column (150mm x 21.2mm) the straight chain peak was separated from the branched chain to greater than 99.5% purity. To assess the epigenetic toxicity of the purified isomers, a gap junction intercellular communication (GJIC) assay was used. GJIC plays a central role in maintaining tissue homeostasis, and chronic closure of gap junction channels has been associated with many human diseases including cancer. Previous in vitro and in vivo studies with this assay indicated that chain length, albeit mixtures of straight and branched chains, determined the toxic-potential of the PFC., The NOEL and EC50 values for a commercially available PFOS mixture were 3.1 g/ml and 14.98 g/ml, respectively.. In the current study the straight chain PFOS isomer was approximately equipotent, on a mass basis, at inhibiting GJIC compared to the commercial mixture. This indicates the different PFOS isomers have similar potency in the inhibition of GJIC. The potential for differences in compound potency in other assay systems due to isomer branching are currently being investigated. The ability to separate and quantify structural isomers of PFCs will be important for further risk assessment of PFCs.

TP072 (SWA-1122-053658) The use of Isotopically Labeled Perfluorooctanoic Acid (PFOA) as a Quality Assurance Tool in Measuring the Effectiveness of Multi-Matrix Sampling and Analysis for Ammonium Perfluorooctanoic Acid (APFO).
Start time: 8:00 AM
Malotky, D¹, Swanson, W¹, Flaherty, J², ¹ Barr Engineering Company, USA² Exygen Research, USA
Many analytical challenges have surfaced during the development of sampling and analytical methodologies to accurately characterize soil, water and air samples for PFOA content. This has lead to questions about data accuracy and laboratory and sampling performance. In an attempt to determine the analytical accuracy in different sample matrices, isotopically labeled PFOA was added to over 390 field samples during collection procedures. This was performed as part of a large scale material balance project that took place in 2003 and 2004. All samples were analyzed using solid phase extraction followed by high-pressure liquid chromatography with a tandem mass spectrometric detector. Percent recoveries for the isotopically labeled standard from each analysis were evaluated to determine the data reliability for the individual sample results, the varied processes and for the overall analytical sampling and analysis for the project. The data indicated that the isotopically labeled PFOA was stable in multiple matrices in varied conditions and could be relied upon to adequately measure sampling and analytical data quality.

TP073 (ARS-1117-543015) Mass Spectral Studies of Native and Mass-labeled Perfluorooctanesulfonamides.
Start time: 8:00 AM
Arsenault, G¹, Chittim, B¹, McAlees, A¹, McCrindle, R², Potter, D¹, Tashiro, C¹, Yeo, B¹, ¹ Wellington Laboratories, Guelph, Ontario, Canada² University of Guelph, Guelph, Ontario, Canada
In recent years, concerns have been raised about the widespread distribution of fluorinated chemicals in the environment and their accumulation in humans. There have been numerous studies aimed at the analysis of perfluorooctanesulfonamide (FOSA) in the environment but very few involving NMeFOSA or NEtFOSA, or the perfluorooctanesulfonamidoethanol (FOSE) analogues. The results of an investigation of the mass spectral behaviour of FOSA and NEtFOSA have been previously published. In this earlier work, a number of fragmentation pathways were proposed, but some gaps still remain. No similar study appears to have been reported for NMeFOSA or the FOSE compounds. We have therefore synthesized samples of both native and mass-labeled NMeFOSA, NEtFOSA, NMeFOSE, NEtFOSE, and native NMe2FOSA, and studied them by GC/MS in an attempt to further our understanding of their modes of fragmentation. The objective of this work was to carefully examine the mass spectrum of these FOSA and FOSE compounds to elucidate the various possible fragmentation pathways accessible to these molecules under electron impact (EI) conditions. Some fragmentation pathways advanced in earlier work have been confirmed and additional pathways proposed to explain the identity of most of the fragments observed in the EI spectra.

TP074 (CRO-1117-840100) Temporal Study of Perfluorinated Alkyl Substances in Niagara River Suspended Sediments.
Start time: 8:00 AM
Lucaciu, C.¹, Furdui, V.², Crozier, P.¹, Marvin, C.³, Reiner, E.¹, Wania, F.², Mabury, S.², ¹ Ontario Ministry of the Environment, Etobicoke, Ontario, Canada² University of Toronto, Toronto, Ontario, Canada³ Environment Canada, Burlington, Ontario, Canada
Perfluorinated alkyl substances (PFAS) are toxic, bioaccumulative, persistent and undergo long range transport qualifying them as persistent organic pollutants under the United Nations Environmental Programme definition. Manufacturers have used these chemicals in a variety of applications including industrial polymers, stain-resistant coatings for fabrics, carpets and leather, and in grease and oil-repellent coatings for paper products. These chemicals bind to proteins in the blood influencing hormone feedback systems and causing a multitude of toxicological effects. The Great Lakes region is heavily industrialized. The Niagara River is the main discharger to Lake Ontario from Lake Erie, contributing over 80% of the total tributary flow and approximately 50% of fine-grained sediments entering the lake. Hazardous waste disposal sites (Hyde Park Dump that discharges into Niagara River through Bloody Run Creek and the Pettit Flume on Tonawanda Island) among other sources could potentially contribute to perfluorinated alkyl substances contamination of Niagara River suspended sediments. Suspended sediment samples collected annually at Niagara-on-the-Lake in the Niagara River over a 22-year (1980-2002) period were analyzed by LC-MS/MS for eleven targeted perfluorinated alkyl substances. Perfluorocarboxylate levels were between 10 and 300 pg/g with the highest values for perfluorooctanoic acid (PFOA). Perfluorosulfonate concentrations were between 5 and 1100 pg/g. In general, there was a trend towards increasing concentration for all perfluorinated organic compounds monitored over the study period. PFOS concentrations increased during the study period from less than 400 pg/g in the early 1980s to more than 1000 pg/g in 2002. The increase in the perfluorinated alkyl substance concentration in suspended sediment is very similar to the trends in polybrominated diphenyl ether (PBDE) data previously reported for the same location over the same time period.

TP075 (ELL-1118-339032) Determination of Perfluorinated Chemicals (PFCs) in Soils, Sediment and Other Matrices.
Start time: 8:00 AM
Ellington, J.¹, Washington, John¹, Strynar, Mark², Evans, John¹, Jenkins, Thomas¹, Henderson, W.¹, ¹ USEPA, National Exposure Research Laboratory, Ecosystems Research Division, Athens, Georgia, USA² USEPA, National Exposure Research Laboratory, Human Exposure and Atmospheric Sciences Division, Durham, North Carolina, USA
Perfluorinated chemicals (PFCs) serve either as the building-block monomers for commercial fluorotelomer-based polymers (FBPs) or the monomers may be applied directly to products to impart fire-protection or non-stick properties (e.g., carpets). Soils that receive land application of treated wastewater from carpet manufacturing plants were sampled for perfluorooctanoic acid (PFOA) and other PFCs that are potential degradation products of FBPs. Soils from other potentially impacted sites and soils remote from exposure to PFCs (except by atmospheric deposition) were analyzed to determine ambient levels of PFCs as well. Large hysteric effects in sorption can impact interpretation of spike-and-recovery quality-assurance practices. To determine the extent of soil-sorption hysteresis for PFOA, dried and sieved remote soil was fortified with PFOA, which is considered to be the stable degradant end-point for many PFCs, and the soil rehydrated to typical moisture conditions. Triplicate samples were extracted at 3-week intervals over three months. We report PFC concentrations measured in selected soils and recovery of PFOA spiked in soil through time.

TP076 (FLA-1117-827102) Quantitative determination of perfluorooctanoic acid in serum and plasma by liquid chromatography tandem mass spectrometry.
Start time: 8:00 AM
Flaherty, John¹, Connolly, Paul¹, Decker, Emily¹, Kennedy, S.², Ellefson, Mark³, Reagen, William³, Szostek, Bogdan², ¹ Exygen Research, Inc. (Exygen), State College, PA, USA² DuPont Haskell Laboratory for Health and Environmental Sciences, Newark, DE, USA³ 3M Environmental Laboratory, St. Paul, MN, USA
A selective and sensitive method for analysis of perfluorooctanioic acid (PFOA) in human serum and plasma, utilizing liquid chromatography tandem mass spectrometry (LC-MS/MS), has been developed and thoroughly validated to satisfy strict FDA guidelines for bioanalytical methods. A simple, automated sample preparation procedure, involving extraction of the target analyte with acetonitrile on protein precipitation media in a 96-well plate format was developed, allowing efficient handling of large numbers of samples. The proposed method uses the calibration standards prepared in a surrogate matrix (rabbit serum or plasma) and ¹³C-labeled PFOA as the internal standard to account for matrix effects, instrument drift, and extraction efficiency. Human serum and plasma could not be used for matrix matching of calibration standards as endogenous levels of PFOA observed in the control human serum and plasma significantly exceeded the targeted lower limit of quantitation (LLOQ) of the method. Precision and accuracy of the method were demonstrated by analysis of rabbit serum and plasma control samples fortified at 0.5, 5, and 40 ng/mL PFOA and human serum and plasma fortified at 1.0, 5.0, and 40 ng/mL PFOA. The LLOQ of 0.5 ng/mL PFOA was experimentally demonstrated for rabbit and human serum and plasma. Within-day precision and accuracy, short-term stability, freeze-thaw stability, equivalence of response between PFOA and APFO (the ammonium salt of PFOA), and dilution of concentrated samples were also investigated. The results of the validation experiments comply with the precision and accuracy limits defined by the FDA guidance document: Guidance for Industry, Bioanalytical Method Validation, May 2001.

TP077 (ARS-1117-544387) Separation and Fluorine Nuclear Magnetic Resonance Spectroscopy Analysis of the Individual Branched Isomers Present in Technical PFOS.
Start time: 8:00 AM
Arsenault, G¹, Chittim, B¹, McAlees, A¹, McCrindle, R², ¹ Wellington Laboratories, Guelph, Ontario, Canada² University of Guelph, Guelph, Ontario, Canada
The production of perfluoroalkylsulfonate derivatives via electrochemical fluorination is not a clean process but rather gives a complex mixture. The presence of C₈ isomers in commercial perfluorooctanesulfonate (PFOS) is evidenced by their partial separation by liquid chromatography (LC), resulting into two broad peaks. In other studies, PFOS appears as a broad signal. Indeed, commercial perfluorooctanesulfonyl fluoride (PFOF), and derived products, were found to be mixtures of 70% linear and 30% branched isomers as determined by ¹⁹F NMR spectroscopy. This study allowed quantification of the individual normal chain, isopropyl branched, alpha branched, t-butyl branched and internal gem-dimethyl branched isomers. Apparently, in this study, it was not possible to quantify the individual internal CF₃ branched isomers, presumably due to overlap of their NMR spectra. The objective of this work was to isolate individual isomers present in a mixture prepared from technical PFOF and characterize their structures by ¹⁹F NMR. A commercial sample of PFOF was converted to secondary sulfonamides (PFOSamide) using benzylamine and the resulting mixture separated by a combination of crystallisation and semi-preparative-scale HPLC. A set of six fractions was obtained, each containing a different isomer as the major component accompanied by smaller amounts of up to four further isomers. The normal chain sulphonamide was purified to better than 99%. The ¹⁹F-NMR spectra of these PFOSamide isomers were run on a 400 MHz Bruker instrument using d₄-methanol as solvent and hexafluorobenzene as an internal standard (set at -169.00 ppm). As a result, the quantification of the individual internal CF₃ branched isomers present in technical PFOS proved possible.

TP078 (HEL-1117-832486) Occurrence of Perfluorochemicals in the Nearshore waters of the Laurentian Great Lakes.
Start time: 8:00 AM
Helm, P.¹, Furdui, V.^{1, 2}, Crozier, P.¹, Reiner, E.¹, ¹ Ontario Ministry of the Environment, Toronto, Ontario, Canada² Univeristy of Toronto, Toronto, Ontario, Canada
Environmental contamination by perfluorinated surfactants, particularly perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), have received considerable attention in recent years. They have been reported in environmental matrices worldwide, and recently in water from the Great Lakes and in the Lake Ontario food web. In this study, lake water was collected from the nearshore areas of locations in Lake Ontario, Lake Erie, and Lake Superior to examine possible influences on concentrations of these compounds in nearshore waters due to inputs of these compounds from tributaries and sewage treatment works. Samples were analyzed by LC/MS/MS using a previously reported method involving standard additions, internal standards, and direct injection of water into the instrument. Analytes included PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA, PFHxS, PFOS and PFOSA. The compounds with the greatest concentrations were PFOS, ranging 2-9 ng/L, and PFOA, ranging from 2-6 ng/L, which are considerably lower than reported for open lake samples from Lake Ontario and Lake Erie.