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DuPont-19567 Review II: Perfluorooctanoic Acid (PFOA) In The Environment John T. Gannon, Ph.D. Robert A. Hoke, Ph.D. Mary A. Kaiser, Ph.D. Timothy Mueller, Ph.D. DuPont Wilmington, DE Report Number: DuPont-19567 May 23, 2006 DuPont-19567 Author Signature Page ohn T. Gannon, Ph.D.1 Robert A. Hoke, Ph.D.2 "JMfy fl' ._ Mary A. Kaiser, Ph.D. r ZLIll SLZZ2.____ date o?3 /%ty200 date ih/iL 24} ^^A la te 7 /w 1: DuPont, Central Research & Development, Environmental Fate & Microbiological Sciences & Engineering 2: DuPont Haskell Laboratory for Health and Environmental Sciences 3: DuPont Central Research & Development, Corporate Center for Analytical Sciences 4: DuPont Central Research & Development, Information & Computing Technologies May 23, 2006 Page ii DuPont-19567 Table of Contents Author Signature page.......................................................................................... ii Table of Contents.................................................................................................. iii Executive Summary.............................................................................................. v Introduction / Purpose.......................................................................................... vii Purpose / Objective Literature Cited................................................................. viii Purpose / Objective Appendix:Table 1.................................................................. ix 1.0 Environmental Fate................................................................................... 1 1.1 Physical-Chemical Properties..................................................... 2 1.1.1 Physical-Chemical Properties Uncertainty............. 3 1.2 Persistence................................................................................... 3 1.2.1 Biodegradation......................................................... 3 1.2.2 Direct Photolysis / Indirect Photolysis.................. 5 1.2.3 Hydrolysis................................................................ 5 1.2.4 Persistence Uncertainty........................................... 6 1.3 Fate in the Environment............................................................. 6 1.3.1 Air................................................................................ 6 1.3.2 Water........................................................................... 7 1.3.3 Wastewater Treatment Plant.................................... 7 1.3.4 Soil............................................................................... 7 1.3.5 Sediments................................................................... 7 1.3.6 Fate in the Environment Uncertainty....................... 8 1.4 Environmental Fate Conclusion.................................................. 8 1.5 Environmental Fate Literature Cited.......................................... 10 1.6 Environmental Fate: Appendix A ............................................... 14 2.0 Bioaccumulation........................................................................................ 23 2.1 Bioconcentration/Bioaccumulation........................................... 24 2.1.1 Bioconcentration/Bioaccumulation Uncertainty...... 26 2.2 Bioaccumulation Conclusion...................................................... 26 2.3 Bioaccumulation Literature Cited................................................ 27 2.4 Bioaccumulation: Appendix A ..................................................... 29 3.0 Environmental Toxicity............................................................................... 31 3.1 Toxicity in the Aquatic Environment........................................... 32 3.1.1 Acute Toxicity............................................................. 32 3.1.1.1 Bacteria................................................... 32 3.1.1.2 Algae....................................................... 32 3.1.1.3 Invertebrates......................................... 33 3.1.1.4 Vertebrates............................................. 33 3.1.2 Chronic Toxicity.......................................................... 34 3.1.3 Environmental Toxicity Uncertainty......................... 34 3.2 Environmental Toxicity Conclusion............................................. 35 May 23, 2006 Page iii DuPont-19567 3.3 Environmental Toxicity Literature Cited..................................... 36 3.4 Environmental Toxicity: Appendix A-D....................................... 40 4.0 Environmental Concentrations................................................................ 46 4.1 Measured Levels of PFOA in Environmental Samples............. 47 4.1.1 Outdoor Air................................................................. 49 4.1.2 Soil............................................................................... 49 4.1.3 Sediment..................................................................... 49 4.1.4 Sewage Sludge and Effluent..................................... 50 4.1.5 Landfill Effluent.......................................................... 51 4.1.6 Ground Water.............................................................. 51 4.1.7 Fresh Water................................................................ 51 4.1.8 Salt Water.................................................................... 52 4.1.9 Plants........................................................................... 53 4.1.10 Invertebrates............................................................... 53 4.1.11 Freshwater Fish.......................................................... 53 4.1.12 Rain Water.................................................................... 54 4.1.13 Plankton and Shellfish............................................... 54 4.1.14 Saltwater Fish.............................................................. 55 4.1.15 Reptiles........................................................................ 56 4.1.16 Birds............................................................................ 57 4.1.17 Amphibians................................................................. 58 4.1.18 Mammals..................................................................... 58 4.1.18.1 Terrestrial Mammals............................. 58 4.1.18.2 Marine Mammals................................... 58 4.1.19 Environmental Concentrations: Uncertainty.............. 59 4.2 Environmental Concentrations: Conclusion.............................. 59 4.3 Environmental Concentrations Literature Cited......................... 60 4.4 Environmental Concentrations: Appendix A.............................. 65 5.0 Analytical: Approaches and Challenges in Environmental Matrices.... 107 5.1 Analytical Determination of Perfluorooctanoic Acid................. 108 5.1.1 From Total Fluorine to Low Level Speciation......... 108 5.1.2 Water........................................................................... 108 5.1.3 Air................................................................................ 110 5.1.4 Biota............................................................................ 111 5.1.5 Soil, Sludge, and Sediment....................................... 111 5.1.6 Other Media and Related Reports............................ 112 5.1.7 Analytical Determination of Perfluorinated Acid Uncertainty.................................................................... 112 5.1.8 Round Robin and ISO Standard Methods............... 113 5.2 Analytical: Literature Cited............................................................115 5.3 Analytical: Appendix A................................................................ 127 6.0 Summary of Conclusions............................................................................ 140 7.0 Acknowledgements...................................................................................... 143 May 23, 2006 Page iv DuPont-19567 Executive Summary This review of PFOA in the environment is based on findings from a literature search on perfluorooctanoic acid (C8F15O2H), perfluorooctanoate anion (C8F15O2), and ammonium perfluorooctanoate (NH4+, C8F15O2-). This review is limited to PFOA found in the environment and does not include any evaluation of potential PFOA precursors nor potential PFOA sources. The sources for review included public records, company records, journals, books, and meeting abstracts (e.g., SETAC, FLUOROS, and DIOXIN meetings). Considering international criteria (see page ix, Table 1) for persistence (P), PFOA meets the criteria for persistence based on expected half-lives of PFOA via biodegradation, hydrolysis, and photolysis under environmentally relevant conditions. It is anticipated that PFOA will exist predominantly in the water compartment. Partitioning to sludges, soils, and sediments will likely be very limited and any PFOA associated with these environmental matrices will likely be found in the water phase of sludges, soils, and sediments. However, there are still significant uncertainties concerning the environmental fate of PFOA including: 1) sources of PFOA in the environment; 2) potential for biotransformation in soil and sediments under varying environmental conditions and anaerobic sludges; 3) transport / distribution mechanisms; and 4) ultimate sinks. All available evidence indicates that PFOA is not bioaccumulative (i.e., B) considering the international criteria (see page ix, Table 1) for bioaccumulation. PFOA is not bioaccumulative based on both the reported bioaccumulation factor (BAF) and bioconcentration factor (BCF) values and it does not biomagnify in the food chain. Several groups of organisms and species were tested to assess the acute and chronic toxicity of PFOA including a soil nematode (Caenorhabditis elegans), and various aquatic organisms including a mixed bacterial community found in sewage sludge, the marine bacterium, Photobacterium phosphoreum (i.e., Microtox), the fathead minnow (Pimephales promelas), bluegill sunfish (Lepomis machrochirus), rainbow trout (Oncorhynchus mykiss), the invertebrate water flea (Daphnia magna), a chironomid (Chironomus tentans), aquatic vascular plants (Lemna sp.), and a green alga (Pseudokirchneriella subcapitata), as well as diatoms, snails, and the plant and zooplankton communities found in outdoor microcosms. Based on the Environment Canada definition of inherent toxicity (Ti) and the available data, PFOA is not inherently toxic. The available acute and chronic aquatic toxicity data for freshwater organisms indicate that PFOA is of low to medium concern for aquatic toxicity based on an evaluation scheme used by the U.S. Environmental Protection Agency. No data are available to assess the aquatic toxicity of PFOA to marine species (other than marine bacterium). There are also no PFOA toxicity test data available for either terrestrial wildlife or avian species. May 23, 2006 Page v DuPont-19567 This review also examined the literature for the levels of PFOA measured in environmental samples from around the world. Measurements were found for abiotic (outdoor air, soil, sediment, sewage sludge and effluent, landfill effluent, ground water, fresh water and salt water) and biotic (invertebrate, freshwater fish, plankton, shellfish, saltwater fish, reptile, bird and mammal) samples. The amount of PFOA found in the environment is relatively small. Current analytical methods make it possible to detect extremely low concentrations (i.e., parts-per-trillion to low parts-per billion range) in various environmental matrices. The first reports of PFOA in environmental samples in 1999 have been followed by reports using continuously improving analytical sensitivity, hence the number of non-detects is being replaced by measurable, but very small amounts being detected. Although the total number of environmental samples analyzed is growing, there currently are not enough data in any one matrix with significant samples to clearly define temporal or geographical trends among the various environmental media (including biota). Continuing studies, which incorporate more defined sampling strategies employing currently available analytical technology, should help define temporal / geographic trends. The data available to date do not seem to indicate that PFOA collects in any environmental media other than the aqueous phase of the aquatic environment, which appears to be the likely sink. Analytical methods for the determination of PFOA in various matrices continue to evolve. Improving sensitivity of analytical instrumentation allows for lower and lower instrumental detection limits. Sampling and sample preparation methodologies used with the improving instrumental methods often are not well characterized, leaving the overall method sensitivity, precision, and accuracy unknown. It is difficult to make comparisons between literature reports, especially over time, since details such as types of standards, methods for determining LOD and LOQ, spike recovery and blank types and results are not available or are defined inconsistently. Generally the reports at the higher levels are probably reliable. At lower levels, however, analytical issues concerning reporting limits, blanks, standards, and representativeness of sample need to be addressed. May 23, 2006 Page vi DuPont-19567 Introduction / Purpose This white paper is a six month follow-up to DuPont Report: DuPont-17709 "Review: Perfluorooctanoic Acid in the Environment" issued on June 30, 2005. The sources for review included public records, company records, journals, books, and meeting abstracts (e.g., SETAC, FLUOROS, and DIOXIN meetings) up to January 15, 2006. The objective of this white paper was to provide an updated literature review of information found on PFOA that covers: Environmental Fate Bioaccumulation Environmental Toxicity Environmental Concentrations Analytical Methodology As part of this review, the available information for PFOA was compared against international PBT criteria (see page ix, Table 1). This review of PFOA in the environment is based on findings from a literature search on perfluorooctanoic acid (C8F15O2H), perfluorooctanoate anion (C8F15O2-), and salts of perfluorooctanoic acid (C8F15O2H). This review is limited to PFOA found in the environment and does not include any evaluation of potential PFOA precursors nor potential PFOA sources. May 23, 2006 Page vii DuPont-19567 Purpose / Objective Literature Cited Environment Canada. 1999. Guidance Manual for the Risk Evaluation Framework for Sections 199 and 200 of CEPA 1999. CEPA Environmental Registry. http://www.ec.ac.ca/cepareaistrv/documents/regs/e2 guidance/sec2.cfm#221 Environment Canada. 2003. Guidance Manual for the Categorization of Organic and Inorganic Substances on Canada's Domestic Substances List: Determining Persistence, Bioaccumulation Potential, and Inherent Toxicity to Non-Human Organisms. Environment Canada. Gatineau, Quebec. June. EU-TGD. 2003. Technical Guidance Document in Support of Commission Directive 93/67/EEC on Risk Assessment for new notified substances, Commission Regulation (EC) No 1488/94 on Risk Assessment for existing substances and Directive 98/8/EC of the European Parliament and of the Council concerning the placing of biocidal products on the market: 2nd edition. EC. United Nations Environment Programme (UNEP). 2001. The Stockholm Convention on Persistent Organic Pollutants (POPs). Stockholm, Sweden. U.S. Environmental Protection Agency. 1999. Final TSCA New Chemicals Program Policy for PBT Chemical Substances. Federal Register 64(213): 60194-60204. November 4. May 23, 2006 Page viii DuPont-19567 Purpose / Objective Appendix (Table 1) May 23, 2006 Page ix DuPont-19567 Table 1: International PBT Criteria Criteria | Persistence (Half-life in:) | Bioaccum ulation | Toxicity [Reference Environm ent Canada Toxic Substances Management Program (TSMP) Criteria for the Selection of Substances fo r Virtual Elimination Air > 2 days; Water > 6 months; Sediment > 1 yr; Soil > 6 months BAF or BCF > 5000 or Log K ow > 6 A substance is considered toxic if it meets or is equivalent to the definition o f "to x ic " found in the Canadian Environmental Protection Act (CEPA), as determined through a systematic, risk-based assessment. CEPA states: "a substance is toxic if it is entering or may enter the environm ent in a quantity or concentration or under conditions that (a) have or may have an immediate or long-term harmful effect on the environm ent or its biological diversity; (b) constitute or may constitute a danger to the environm ent on which life depends; or (c) constitute or may constitute a danger in Canada to human life or health." E n viro n m e n t Canada 1999 Environm ent Canada Domestic Substances List (DSL) Air > 2 days; Water >182 days; Sediment > 1 yr; Soil > 182 days BAF or BCF > 5000 or Log K ow > 5 Inherent Toxicity - Acute / Chronic fo r algae, invertebrates, fish: LC60(EC60) < - I mg/L NOEC <= 0.1 mg/L Environment Canada 2003 EU PBT criteria EU vPvB criteria Stockholm Convention Marine Water > 60 days; Fresh Water > 60 days; Marine Sediment > 180 days; Freshwater sediment >180 days Marine Water > 60 days; Fresh Water > 40 days; Marine Sediment > 180 days; Freshwater sediment > 120 days Water > 2 months; Soil > 6 months; Sediment > 6 months BCF > 5000 BCF > 5000 BAF or BCF > 5000 or Log Kow > 6 US EPA TSCA New Chemicals Program Policy fo r PBTs: C o n tro ls1 US EPA TSC A New Chemicals Program Policy fo r PBTs: Ban pending2 > 2 months > 6 months >_1,000 + MW <1,000 and cross-sectional diameter < 20 x 10^ cm >_6,000 + MW <1,000 and cross-sectional diameter < 20 x 10** cm C hronic NOEC < 0.01 mg/L or CMR or endocrine disrupting effects Not Applicable Evidence of adverse effect on human health or the environment or toxicity characteristics indicating potential damage to human health or environment Toxicity data based upon level of risk concern Toxicity data based upon level of risk concern EU-TGD 2003 EU-TGD 2003 UNEP 2001 US EPA 1999 US EPA 1999 1: Testing and exposure/release controls required 2: Commercialization denied except if testing may justify removing chemical from "high risk concern*' May 23, 2006 Page x DuPont-19567 1.0 Environmental Fate May 23, 2006 Page 1 DuPont-19567 1.1 Physical-Chemical Properties Surfactants have a hydrophilic head group compatible with water and a hydrophobic tail, which repels water. The surfactant orients itself at the water-air interface with its hydrophilic part directed toward water and the hydrophobic tail pointed toward air. In water, surfactant molecules associate to form micelles or aggregates. The hydrophobic tails of the surfactant molecules form the interior of the micelle and the hydrophilic head groups are exposed to water (Kissa, 2001a). Perfluorinated surfactants are remarkably stable. Their outstanding thermal and chemical stability permits applications under conditions, which would be too severe for conventional hydrocarbon-based surfactants. The very strong C-F bond is stable to acids, alkali, oxidation, and reduction, even at relatively high temperatures. The unusual properties of fluorosurfactants arise from the unique properties of elemental fluorine: high oxidation potential; high ionization energy, high electron affinity, high electronegativity of covalently bonded fluorine, and fluorine is very difficult to polarize (Kissa, 2001b). A summary of the physical-chemical properties for perfluorooctanoic acid (PFOA) and ammonium perfluorooctanoate (APFO) can be found in Appendix A: Table 1. Considering properties such as the vapor pressure, water solubility, pKa, critical micelle concentration, and surface tension, p Fo a and APFO will likely most often be found in the environment in the dissociated form (essentially as an anionic surfactant: C8Fi 5O2-), will be non-volatile, and associated with water. In aqueous solutions, individual molecules of PFOA anion loosely associate on the water surface and partition between the air / water interface. Water solubility has been reported for PFOA but it is unclear whether these values are for a microdispersion of micelles rather than true solubility. Due to these same surface-active properties of PFOA, it is anticipated that PFOA will form multiple layers in octanol/water. Therefore, an n-octanol/water partition coefficient cannot be determined. (US EPA 2003). Fluorosurfactants lower the surface tension of aqueous systems below 20 mN/m, substantially lower than hydrocarbon surfactants. The concentration of fluorinated surfactant required to achieve these low surface tensions is 5-10 times less than would be required for hydrocarbon- or silicon-based surfactants if they could achieve this low surface tension. The "phobe" of fluorosurfactants is both hydrophobic and lipophobic (Taylor 1999). This characteristic also accounts for why a Log Kow measurement of perfluorosurfactants is difficult and more importantly not relevant for predicting how fluorosurfactants may partition in the environment. Three studies (Appendix A: Table 2) were found in the literature to address adsorption/desorption of APFO. These studies (3M Company 1978a; DuPont 2000; and Association of Plastic Manufacturers in Europe 2003) indicated low adsorption to soils and/or sludge, clay, sand, and sediments suggesting a potential for mobility in soils. May 23, 2006 Page 2 DuPont-19567 1.1.1 Physical-Chemical Properties Uncertainty To better understand potential mechanisms for transport or distribution of PFOA in the environment, it would be helpful to get an understanding of whether or not perfluorinated anionic surfactants such as PFOA (PFO anion): Have a tendency to accumulate in the water surface microlayer (i.e., surface films). Can be potentially sequestered in solid matrices (soil, sediments, sludge) via an "aging phenomenon". Are associated with just the water phase of solid matrices rather than adsorbed to solid matrices (i.e., soil, sediments, sludge). Have physical-chemical properties that enable presence in aerosols - (e.g., aerosols formed by wave and winds action on ocean surface microlayer films) or have pKa values that enable measurable sublimation from water surface microlayers. Furthermore, considering that PFOA is a mix of both linear and branched forms, there is a need to determine whether or not the linear and branched isomers have differences in physical-chemical properties, which may result in differences in environmental transport/distribution and ultimate fate in the environment. 1.2 Persistence The recalcitrant nature of perfluorinated compounds is attributed in part to the rigidity of the perfluorocarbon chain as well as the strength of the C-F bond (Moody and Field 1999; Smart 1986). In 1997, Key et al. reported that monofluorinated carboxylic acids can undergo hydrolytic defluorination, reductive defluorination, and decarboxylation, but they had no evidence of PFOA transformation. 1.2.1 Biodegradation Ten studies were found in the literature covering the biodegradation potential of PFOA (Appendix A: Table 3 a, b, c). There were four Biochemical Oxygen Demand / Chemical Oxygen Demand (BOD/COD) biodegradation studies reported by the 3M Company between 1977 and 1987. Three of the studies (3M Company 1977; 3M Company 1985; 3M Company 1987a) were inconclusive because they reported unexpectedly high BODs, which may be indicative of impurities or other quality issues with the studies. In another BOD/COD study (3M Company 1980a), BOD levels indicated no biodegradability in a 20-day study, however with inconsistent results with the COD data, it was not possible to determine a reliable BOD/COD value. The biodegradation determination based on BOD/COD ratios was difficult to interpret due to the COD methods apparently yielding incomplete oxidation resulting in two studies having BOD > COD values (3M Company, 1977 and 3M May 23, 2006 Page 3 DuPont-19567 Company, 1985). Typically, COD for raw domestic wastewater is about 2.5 times the 5-day BOD. 3M Company conducted an Alkylbenzenesulfonate / Linear (secondary) Alkylbenzenesulfonate (ABS/LAS) shake culture test (3M Company 1978b) that indicated no biodegradation of APFO after 78 days. A specific concern with this test was that the LAS positive control chemical, which typically completely degrades within 10 days, did not show appreciable biodegradation until day 37, thus indicating that biodegradation conditions may not have been optimal for the full duration of the study. In 1996, the biodegradation of APFO was studied using a biodegradability bottle assay test with aerobic bacteria previously shown to have a broad range of degradative capabilities (DuPont 1996). This study was inconclusive due to the PFOA analysis lacking sensitivity. DuPont conducted a Modified Sturm test (DuPont 1997) on APFO. The analysis was limited to CO2 evolution and on this basis, 13% biodegradation was observed. The conclusion was that the alkyl portion (COO-) may have been transformed, but in the absence of specific analysis of PFOA, this could not be confirmed. 3M Company conducted an Inherent Biodegradability test - Zahn-Wellens/EMPA test (3M Company 2001a) that indicated no measurable biodegradation of PFOA for the duration of the test. This test is typically conducted for 28 days, but the 3M study was limited to 18 days with measurements only taken at day 0 and day 18. Laboratory scale wastewater closed-loop bioreactors for aerobic and anaerobic treatment were used to assess the biodegradation potential of APFO (Schroder 2003; Meesters and Schroder 2004). The results indicated that under aerobic conditions PFOA was not biodegraded, whereas, under anaerobic conditions PFOA could no longer be detected after 25 days. However, elevated concentrations of fluoride ions were not observed, so degradation of the hydrophobic fluorine-containing moiety was not indicated. This study also indicated no adsorption onto glass walls of the reactor. The study concluded that the whereabouts of the fluorinated segment of the anionic perfluorinated surfactant (i.e., PFOA) remained unknown. Thus, it is possible that perhaps only the alkyl portion (COO-) of PFOA may have been transformed under anaerobic conditions, and the perfluorinated segment may have been adsorbed to the sludge and/or sequestered in the sludge matrix. An aquatic mesocosm study was conducted at the University of Guelph (Richards et al. 2001) and the initial results indicated that PFOA was persistent in the water column with no significant degradation observed 35 days post application. A second paper (Hanson et al. 2005) discussing a microcosm study at the University of Guelph Microcosm Facility indicated that there were no changes in the concentration of PFOA at the 0.3, 1, and 30 mg/L treatments over a 35-day field study. May 23, 2006 Page 4 DuPont-19567 Wang et al. 2005 noted that decarboxylation of 14C-PFOA by activated sludge was observed at a very slow rate (~0.5% over 63 days), suggesting that PFOA may potentially be biodegraded very slowly by microorganisms and such degradation may not be detected by conventional LC/MS/MS analysis. However, further study is needed to be conclusive. 1.2.2 Direct Photolysis / Indirect Photolysis Four studies were found in the literature that address the direct and/or indirect photolysis of ammonium perfluorooctonoate (Appendix A: Table 4). A direct photolysis study (3M Company 1979) showed that no photodegradation products were detected in a 30-day study using simulated sunlight (24 h/day), thus indicating that PFOA, ammonium salt does not undergo direct photolysis. In 2001, an Indirect Photolysis Screening test (US EPA OPPTS: 835.5270) and "Phototransformation of Chemicals in Water - Direct and Indirect Photolysis" tests were conducted to assess the potential for direct and indirect photolysis of perfluorooctanoic acid, ammonium salt (3M Company 2001b). Neither direct nor indirect photolytic decomposition of PFOA were observed based on the loss of starting material, nor were any of the hypothesized degradation products detected above their limit of quantitation (LOQ). Using an iron oxide (Fe2O3) photoinitiator matrix model, the PFOA half-life was estimated to be >349 days. There were two papers that reported photochemical approaches for decomposing PFOA but these studies were done under conditions that were not environmentally relevant. The studies were designed to develop techniques for decomposing stationary sources of PFOA. In a direct photolysis study, Hori et al. (2004) showed 89.5% loss of the initial PFOA after 72 hours of irradiation with a xenon mercury lamp in an aqueous solution of PFOA under 0.48 MPa of O2 at room temperature. They also demonstrated complete PFOA decomposition after 24 hours of irradiation using a tungstic heteropolyacid photocatalyst under similar conditions as the direct photolysis study. Hori et al. (2005) reported photochemical decomposition of PFOA in water by use of persulfate ion (S2O82-). In this study, PFOA was completely decomposed by a photochemical system with 50 mM S2O82- and 4 hours of irradiation from a 200-W xenon-mercury lamp. 1.2.3 Hydrolysis Only one study on the hydrolysis of PFOA was found in the literature (3M Company 2001c). In this study, hydrolysis was assessed over 109 days at pH 5, 7, and 9 at 50oC and the results were extrapolated to 25oC. Based on the results, the hydrolytic half-life of PFOA was estimated to be >97 years. Although, 6 pH levels were included in the study, pH levels of 3.0 and 11.0 failed to meet the data quality objective for matrix spike recovery and pH 1.5 was rejected because ion pairing led to artificially low May 23, 2006 Page 5 DuPont-19567 concentrations. However, pH levels of 5, 7, and 9 had results that indicated no clear dependence of the degradation rate of PFOA on pH. 1.2.4 Persistence Uncertainty A limited number of studies on the biodegradation potential of APFO have been reported, but most of the cited studies had high levels of uncertainty, so there is currently not a definitive answer on the biodegradation potential of APFO. These uncertainties include: BOD/COD testing of mixtures rather than discreet chemical; unexpectedly long adaptation of "readily biodegradable" controls before appreciable biodegradation observed; lack of PFOA-specific analysis; short duration of biodegradability studies. Furthermore, all of the biodegradation studies cited in this review have used an inoculum from activated sludge sources or cell cultures, whereas, there have been no reported studies in other relevant environmental matrices such as soils or sediments. It is noteworthy that two of the reviewed biodegradation studies have indicated a potential for primary biotransformation in anaerobic wastewater sludges. In addition to the direct and indirect photolysis studies reviewed in this white paper, research on the potential for photolysis of PFOA present in aerosols / vapor phase and/or associated with air particulates would be helpful for understanding the potential mechanisms of transport or distribution of PFOA in the environment. For hydrolysis, there was only one study found in the literature and hydrolysis was evaluated using only pH 5, 7, and 9. The potential hydrolysis at pH < 5 or > 9 has not been evaluated, so potential hydrolysis at extreme pH levels is still uncertain. 1.3 Fate in the Environment 1.3.1 Air As noted in the Physical-Chemical Properties section above, under most circumstances PFOA will exist in the dissociated form and will be non-volatile. The expectation is that PFOA found in air would be removed from air via a precipitation event (e.g., rain, snow, etc.). Based on the available literature, it appears that PFOA will meet the international criteria (see page ix, Table 1) for persistence in air. Berger et al., 2005 analyzed fluorinated alkyl compounds in air samples from England and they observed that PFOA exhibited the highest concentrations of all fluorinated analytes on aerosol samples. When air was bubbled through a water solution of PFOA, Waterland et al., 2005 observed that foams are significantly enriched in PFOA vs. solution. Based on this May 23, 2006 Page 6 DuPont-19567 data, the authors raised the following questions - Do sea foams and sea mists contain PFCAs and can PFCAs be found on marine aerosols? 1.3.2 Water (i.e., surface water and ground water) It is likely that water will be the predominant environmental compartment where PFOA is found. Based on the available literature, it appears that PFOA will meet international criteria (see page ix, Table 1) for persistence in water. 1.3.3 Wastewater Treatment Plant The 3M Company reported four studies on activated sludge respiration inhibition (Appendix A: Table 6). These studies (3M Company 1980b; 3M Company 1987b; 3M Company 1990; 3M Company 1996) indicated that APFO is not expected to inhibit activity of activated sludge. The biodegradation studies described above generally indicate that aerobic biodegradation is unlikely under typical wastewater treatment conditions. To better understand the behaviour of fluorochemicals through a wastewater treatment, Schultz et al. 2005 conducted a field study at a full-scale municipal wastewater treatment plant to determine the mass flows in wastewater and sludge. They observed that perfluoroalkyl carboxylates were overall removed by the wastewater treatment plant, whereas perfluoroalkyl sulfonates were found to increase significantly(~ 200%) in the plant mass balance (30 days) and fluoroalkylsulfonamide acetic acids were also found to increase by at least 300% throughout the sludge treatment process within a residence time of a year. Section 4.1.4 of this report provides a summary of PFOA concentrations in sewage sludge and effluent. In summary, these studies indicate that PFOA tends to have higher concentrations in effluent versus PFOA concentrations found in sludge. It is likely that the PFOA concentrations observed in sludge are associated with the aqueous phase of sludge versus the sludge solids. 1.3.4 Soil Degradation potential is unknown. The extent of mobility in soil will depend on soil type. 1.3.5 Sediments Degradation potential is unknown. Section 4.1.3 of this report provides a summary of PFOA concentrations in sediment. In summary, these studies indicate that PFOA existed mainly in the dissolved-phase in water and that the amount of PFOA deposition to bottom sediment was negligible. Therefore, it is unlikely that sediment is a significant environmental compartment for PFOA. May 23, 2006 Page 7 DuPont-19567 1.3.6 Fate in the Environment Uncertainty It is unclear whether or not PFOA may be transported in air via aerosols. There is growing interest in the presence of surfactants in atmospheric aerosols (Ellison et al. 1999; Murphy et al. 1998; Latif and Brimblecombe 2004). A hypothesis is that PFOA may be present in the marine surface microlayer and enter the atmosphere after being aerosolized via wave action and winds. Furthermore, the observations of Berger et al., 2005 that PFOA was dominant in aerosol samples collected in England also raises questions about the role of aerosols in regards to the potential long-range transport of PFOA and/or widespread distribution of PFOA in the environment.. In water, there is still some uncertainty regarding the potential for long-term ultimate biodegradation or at least primary biotransformation under varying environmental conditions (e.g., anaerobic conditions in groundwater). In wastewater, no available biodegradation data were found to assess what may happen to PFOA under the conditions found in an anaerobic digester. It is not clear if PFOA found associated with sludge is actually part of the water phase in sludge or there is actual adsorption (i.e., perhaps by electrostatic interaction) or perhaps sequestration (aging) within the sludge matrix over time. In soils and sediments, no data was found to assess the biodegradation potential of PFOA under aerobic or varying anaerobic conditions in soil or sediments over time. Considering the physical-chemical properties of PFOA, the potential for sequestration ("aging") within the soil or sediment matrix needs to be evaluated to address bioavailability in soils or sediments as well as potential for PFOA to migrate through the soil vadose zone to groundwater. It is not clear if PFOA found associated with soils and sediments is actually part of the water phase in soil and sediment or if there is actual adsorption (i.e., perhaps by electrostatic interaction). Furthermore, considering that PFOA is a mix of both linear and branched forms, there is a need to determine whether or not the linear and branched isomers have differences in physical-chemical properties, which may result in differences in environmental transport/distribution and ultimate fate in the environment. 1.4 Environmental Fate Conclusions Based on studies in the available literature, PFOA will meet international criteria (see page ix, Table 1) for persistence based on expected half-lives of PFOA via biodegradation, hydrolysis, and photolysis under environmentally relevant conditions. It is anticipated that water will be the predominant environmental compartment in which PFOA resides. In regard to sludges, soils, and sediments, the expectation is that adsorption will be very limited and any PFOA associated with these environmental matrices will likely be found in the water phase of sludges, soils, and sediments and/or perhaps weakly adsorbed by electrostatic interactions. May 23, 2006 Page 8 DuPont-19567 However, there are still significant uncertainties concerning the environmental fate of PFOA including: 1) sources of PFOA in the environment; 2) potential for biotransformation in soil and sediments under varying environmental conditions and anaerobic sludges; 3) transport / distribution mechanisms; 4) potential for oceans to be predominant sinks; 5) role of aerosols in transport and distribution of PFOA in the environment. May 23, 2006 Page 9 DuPont-19567 1.5 Environmental Fate Literature Cited Additional Literature Cited for DuPont-19567 Berger, U., Barber, J.L., Jahnke, A., Temme, C., and Jones, K.C. 2005. Analysis of fluorinated alkyl compounds in air samples from England. FLUOROS meeting, Toronto. Hanson, M.L., Small, J., Sibley, P.K., Boudreau, T.M., Brain, R.A., and Mabury, S.A. 2005. Microcosm evaluation of the fate, toxicity, and risk to aquatic macrophytes from perfluorooctanoic acid (PFOA). Arch. Environ. Contam. Toxicol. 49: 307-316. Schultz, M.M., Luthy, R.G., Barofsky, D.F., and Field, J.A. 2005. Behavior of fluorochemicals during wastewater treatment. Society of Environmental Toxicology and Chemistry, North America 26th Annual Meeting. Baltimore, MD, USA. Wang, N., Szotek, B., Buck, R.C., Folsom, P.W., Sulecki, L.M., Powley, C.R., and Berti, W.R. 2005. Fluorotelomer alcohol microbial biotransformation pathways. Time for a pardigm shift ? FLUOROS meeting, Toronto. Waterland, R.L., Gannon, J., Kaiser, M., Botelho, M.A., Harding, T.W., Ellison, G.B., Vaida, V., Tuck, A.F., and Murphy, D.M. 2005. Global transport of biogenic and anthropogenic surfactants on marine aerosols. FLUOROS meeting, Toronto. Literature Cited for DuPont-17709 3M Company, Environmental Laboratory. 1977. Biodegradation (BOD/COD/TOC). St. Paul, MN. Lab Request number 3844. U.S. Environmental Protection Agency Administrative Record 226-0487. 3M Company, Environmental Laboratory. 1978a. Adsorption of FC95 and FC 143 on Soil. St. Paul, MN. Project 9970612633 Fate of Fluorochemicals, Report No. 1. U.S. Environmental Protection Agency Administrative Record 226-0488. 3M Company, Environmental Laboratory. 1978b. Biodegradation (ABS/LAS Shake Culture Test). St. Paul, MN. Project number 9970612613. U.S. Environmental Protection Agency Administrative Record 226-0489. 3M Company, Environmental Laboratory. 1979. FC-143 Photolysis Study Using Simulated Sunlight. St. Paul, MN. Report number 002. U.S. Environmental Protection Agency Administrative Record 226-0490. 3M Company, Environmental Laboratory. 1980a. Biodegradation (BOD/COD/TOC). St. Paul, m N. Lab Request number 5625S. U.S. Environmental Protection Agency Administrative Record 226-0492. 3M Company, Environmental Laboratory. 1980b. Activated Sludge Respiration May 23, 2006 Page 10 DuPont-19567 Inhibition. St. Paul, MN. Lab Request number 5625S. U.S. Environmental Protection Agency Administrative Record 226-0505. 3M Company. 1985. Biodegradation (BOD/COD/TOC). St. Paul, MN. Lab Request number C1006. Pace Analytical Services, Inc. Minneapolis, MN. U.S. Environmental Protection Agency Administrative Record 226-0494. 3M Company. 1987a. Biodegradation (BOD/COD/TOC). St. Paul, MN. Lab Request number E1282. Pace Analytical Services, Inc. Minneapolis, MN. U.S. Environmental Protection Agency Administrative Record 226-0495. 3M Company, Environmental Laboratory. 1987b. Activated Sludge Respiration Inhibition. St. Paul, MN. Lab Request number E1282. U.S. Environmental Protection Agency Administrative Record 226-0510. 3M Company, Environmental Laboratory. 1990. Activated Sludge Respiration Inhibition. St. Paul, MN. Lab Request number G2882. U.S. Environmental Protection Agency Administrative Record 226-0514. 3M Company, Environmental Laboratory. 1996. Activated Sludge Respiration Inhibition. St. Paul, MN. Lab Request number N2169. U.S. Environmental Protection Agency Administrative Record 226-0524. 3M Company. 2001a. The 18-day Aerobic Biodegradation Study of Perfluorooctanesulfonyl-Based Chemistries. Pace Analytical Services, Inc. Minneapolis, MN. 3M Company, Environmental Laboratory. 2001b. Screening Studies on the Aqueous Photolytic Degradation of Perfluorooctanoic acid (PFOA). St. Paul, MN. 3M Laboratory Report number E00-2192. 3M Company, Environmental Laboratory. 2001c. Hydrolysis Reactions of Perfluorooctanoic acid (PFOA). St. Paul, MN. 3M Laboratory Report number E00-1851. Association of Plastic Manufacturers in Europe. 2003. Adsorption/Desorption of Ammonium Perfluorooctanoate to Soil (OECD 106). DuPont Central Research & Development, Environmental & Microbiological Sciences & Engineering. Newark, DE. DuPont 1996. Aerobic Biodegradation Study of Trifluoroacetic Acid (TFA) and Ammonium Perfluoro-Octanoate (C8). Envirogen Inc., Lawrenceville, NJ. DuPont. 1997. Evaluation of the Biodegradability of C-8 Using the Modified Sturm Test (OECD 301 B). Newark, DE. AEM Laboratory Report No. 24-97. DuPont. 2000. Adsorption-Desorption Screening Studies of Ammonium Perfluorooctanoate. Newark, DE. Report No. EMSE-053-00. May 23, 2006 Page 11 DuPont-19567 Ellison, G.B., Tuck, A.F. and Vaida, V. 1999. Atmospheric processing of organic aerosols. J. Geophys. Res. 104(D9): 11,633-11,641. Environ International Corporation. 2004. Product-Specific Exposure Assessment and Risk-Characterization for Perfluorooctanoate in Select Consumer Articles. Environ, Emeryville, CA. Griffith, F.D. and Long, J.E. 1980. Animal toxicity studies with ammonium perfluorooctanoate. Am. Ind. Hyg. Assoc. J. 41(8): 576-583. Hekster, F.M., de Voogt, P., Pijnenburg, A.M.C.M., Lane, R.W.P.M. 2002. "Perfluoroalkylated Substances - Aquatic Environmental Assessment." Report RIKZ/2002.043. Directoraat-Generaal. Rijkswaterstaat. Hori, H., Hayakawa, E., Einaga, H., Kutsuna, S., Koike, K., Ibusuki, T., Kiatagawa, H., and Arakawa, R. 2004. Decomposition of environmentally persistent perfluorooctanoic acid in water by photochemical approaches. Environ. Sci. Technol. 38(22): 6118-6124. Hori, H., Yamamoto, A., Hayakawa, E., Taniyasu, S., Yamashita, N., and Kutsuna, S. 2005. Efficient decomposition of environmentally persistent perfluorocarboxylic acids by use of persulfate as a photochemical oxidant. Environ. Sci. Technol. 39(7): 2383-2388. Kaiser, M.A., Larsen, B.S., Kao, C.-P. C., and Buck, R.C. 2005. Vapor pressure of perfluoro- octanoic, nonanoic, decanoic, undecanoic, and dodecanoic acids. J. Chem. Eng. Data. 50: 1841-1843. Key, B.D., Howell, R.D., and Criddle, C.S. 1997. Critical Review: Fluorinated organics in the biosphere. Environ. Sci. Technol. 31(9): 2445-2454. Kirk-Othmer Encyclopedia of Chemical Technology. 1994. 4th ed. Volume 1: New York, NY. John Wiley and Sons. 1991-Present, p. V11 (1994) 551. Kissa, E. 2001a. Fluorinated Surfactants and Repellents. New York, Marcel Dekker. p. 202. Kissa, E. 2001b. Fluorinated Surfactants and Repellents. New York, Marcel Dekker. p. 80. Latif, M.T. and Brimblecombe, P. 2004. Surfactants in atmospheric aerosols. Environ. Sci. Technol. 38: 6501-6506. Meesters, J.W. and Schroder, H.F. 2004. Perfluorooctane sulfonate - a quite mobile anionic anthropogenic surfactant, ubiquitously found in the environment. Water Sci. Technol. 50(5): 235-242. May 23, 2006 Page 12 DuPont-19567 Moody, C.A. and Field, J.A. 1999. Determination of perfluorocarboxylates in groundwater impacted by fire-fighting activity. Environ. Sci. Technol. 33(16): 2800-2806. Moody, C.A. and Field, J.A. 2000. Critical Review: Perfluorinated surfactants and the environmental implications of their use in fire-fighting foams. Environ. Sci. Technol. 34(18): 3864-3870. Murphy, D.M., Thomson, D.S., and Mahoney, M.J. 1998. In situ measurements of organics, meteoritic material, mercury, and other elements in aerosols at 5 to 19 kilometers. Science 282 (November 27): 1664-1669. Richards, S., Boudreau, T., Sibley, P., Cheong, W.-J., Small, J, and Solomon, K. 2001. Perfluorooctanoic Acid and Perfluorooctane Sulfonic Acid I: Fate and Effects in Aquatic Mesocosms. Society of Environmental Toxicology and Chemistry Europe Annual Meeting, Madrid. Schroder, H.F. 2003. Determination of fluorinated surfactants and their metabolites in sewage sludge samples by liquid chromatography with mass spectrometry and tandem mass spectometry after pressurized liquid extraction and separation of fluorinemodified reversed-phase sorbents. J. Chromatogr. A 1020: 131-151. Smart, B.E. 1986. In Molecular Structures and Energetics. Liebman, J.F. and Greenberg, A. Eds. Vol. 3. VCH Publishers, Deerfield Beach, FL. Taylor, C. K. 1999. "Fluorinated surfactants in practice." Annual Surfactants Review 2 (Design and Selection of Performance Surfactants). p. 271-316. U.S. Environmental Protection Agency. 2005. Draft Risk Assessment of the Development Toxicity Associated with Exposure to Perfluorooctanoic Acid and its Salts. Office of Pollution Prevention and Toxics, Risk Assessment Division, January 4. May 23, 2006 Page 13 DuPont-19567 1.6 ENVIRONMENTAL FATE: APPENDIX A (Tables 1-6) May 23, 2006 Page 14 DuPont-19567 Table 1: Summary of Physical Chemical Properties of Perfluorooctanoic Acid (PFOA) _______ and Ammonium Perfluorooctanoate (APFO)____________________________ Chem ical Name P erfluorooctanoic acid (PFOA) A m m onium P erfluorooctanoate (APFO) Chem ical Formula c bh f 15o 21 c bh 4f 15n o 21 CAS R egistry No. 335-67-11 3825-26-11 M olecular W eight 414.1 g/m ole1 431.1 g /m o le 1 A p p e a ra n ce solid, white pungent o d o r1 solid, w hite1 Melting Point 54.3C 1; 52-54C 3 157 to 165C1 Sublim ation Point 40C (slight)1 130C1 B oiling P oint 188C (at 760 m m Hg)1; 189C3 D e c o m p o s e s 1; S ublim e s at 130C2 6 x 10'5 m m Hg (at 20C )1; 0.02 m m Hg (at 20C )1: 7 x 10`5 m m Hg (at 20C )2; Vapor pressure 128 Pa at (59C )5; 7.0 E1 Pa6 <1.3 E-3 / 9.2 E-3 Pa6 D e n s ity 1.8 g /c m 3 (at 20C)1 0.6 to 0.7 g/m L2 W ater Solubility 3.4 g/L (at 20C )1; 9.5 g /L 6 50% at ro om te m p e ra tu re 1; >5.00E2 g /L 6 A cid -D isso cia tio n C o n sta n t 1.5 to 2.8 (expressed as pK a)1 3.66 (expressed as K)1 pH H enry's Law C o n s ta n t (K H) (ca lcu late d) 2.6 (1 g/L at 20 C )1 4.6 E-66 a tm *m 3*m o l'1 4-7 (2% s o lu tio n )2 <1.1 E-11 / 7.8 E-11 a tm *m 3*m o l'1 O ctanol-W ater Partition C oefficient (Kow) C annot be determ ined (su rfacta nt)1 C annot be determ ined (su rfacta nt)1 P h o to d e g ra d a tio n Half-life > 349 days1 H y d ro lysis Half-life > 97 years (at 25C)1 Critical Micelle C oncentration 8.7 to 9.0 m m oles/L4 Surface Tension 15.2 dynes/cm 4 1: Environ International Corporation 2004 2: Griffith and Long 1980 3: Kirk-Othmer Enceyclopedia of Chemical Technology 1994 4: Moody and Field 2000 5: Kaiser et al. 2005 6: Heckster and de Voogt 2002 May 23, 2006 Page 15 DuPont-19567 Table 2: Summary of Soil Adsorption Studies ofAmmonium Perfluorooctanoate (APFO) Test Matrix/Texture Test method % adsorption Adsorption-desorption Kd Koc Conclusions Reference study using the approach recommended by US Low adsorption to soil EPA for pesticide and sludge; High Soil: Brill sandy loam registration Kaolin and US EPA OPPT method: Clays: 0-35%; Montmorlllonlte clays; Sediment and soil Sand: 0-7%; 14 mobility in soil 1 Company 1978a Low adsorption to clay, sand, soil and sediment; High mobility peatmoss; sand; 3 adsorptionldesorption Peat moss: 77-87%; Soils: 4.2 E-2 to 1.2 E-1; in soil; High adsorption soils; 2 sediments Isotherm Soils: 0-46% Sediments: 8.8 E-2 to 0 to peat moss DuPont 2888 4 soils; Sit clay loam, OECD IDS Adsorption sandy clay loam, sandy desorption using a Low adsorption to soil loam, loam; 1 sludge: Sandy loam May 23, 2006 batch equilibrium Soils: 27.S to 88,9%; Soils: 0.41 to 8.86 mL/g; Soils: 48.9 to 229 mLfg; method Sludge: 69.5-87.3% Sludge: 12.6to36.8mL!g Sludge: 20.5to59.6mL/g Page 16 and sludge; High mobility in soil APME2D03 DuPont-19567 Table 3a: Summary of BOD/COD Biodegradation Studies for PFOA Test Substance Test Method Study Duration Conditions Inoculum Conclusions Literature Cited Ammonium Perfluorooctanoate; FC-143 COD/BOD study; Method not noted 14 days Ammonium Perfluorooctanoate; FC-143 COD/BOD study; Method not noted 20 days Perfluorooctanoic acid; COD/BOD study; Method not PFOA; FX-1001 noted Ammonium Perfluorooctanoate; FC-126 May 23, 2006 COD/BOD study; EPA Standard Method 507/508A Page 17 20 days 20 days aerobic aerobic aerobic aerobic No biodegradation at day 5; day 14 result inconclusive (BOD 2-3X > COD); Study procedures and raw data Not noted not found; Inconclusive 3M Company 1977 Based on BOD, no biodegradation observed; COD data questionable; Summary sheet noted duplicate results not Activated sludge collected from consistent; Weight of 3M Chemolite Facility, Cottage evidence no Grove, MN biodegradability 3M Company 1980a BOD results exceptionally high-purity questionable; Activated sludge collected from days 10 & 20 were more 3M Chemolite Facility, Cottage than 7X > COD; Raw data Grove, MN not found; Inconclusive 3M Company 1985 BOD results unexpectedly high likely due to mixture components (78-93% test Not noted substance); Inconclusive 3M Company 1987 DuPont-19567 Table 3b: Summary of Ready/lnherent Biodegradation Studies for PFOA Test Substance Test Method Study Duration Conditions Inoculum Conclusions Literature Cited Shake culture test modeled after the Soap and Detergent Ammonium Association's presumptive test for Perfluorooctanoate; determination of ABS/LAS FC-143 biodegradability 2,5 months PFOA Modified Sturm Test (OECD 301B) 28 days No biodegradation of FC- 143 observed; However, Linear Alkyl sulfonate (LAS) control, which is typically rapidly "readily biodegradable1' did not Activated sludge collected at 3M show appreciable Chemolite Facility, Cottage Grove, biodegradation until day MN; 3M Decatur facility, Decatur, 37, so there may be some AL; and Metro Wastewater concerns about the aerobic treatment Plant, St. Paul, MN robustness of the test. 3M Company 1978b Not "Readily Biodegradable", but 13% Activated sludge from biodegradability was aerobic Wilmington, DE POTW observed at day 28, DuPont 1997 Ammonium EPAOPPTS 835.3200: Zahn Perfluorooctanoate Wellens/EMPA Test 18 days Not measurably degraded after 18 days; This test is typically conducted for 28 days-18 days may be viewed as insufficient time Activated sludge collected at Metro Wastewater treatment Plant, aerobic St. Paul, MN to induce conditions needed for potential biodegradation, 3M Company 2001a May 23, 2006 Page 18 DuPont-19567 Table 3c: Summary of Other Biodegradation Studies for PFOA Test Substance Test Method Study Duration C onditions Inoculum C o n c lu s io n s Literature Cited Am m onium P e rflu o ro o c ta n o a te Biodegradability bottle assay tests with aerobic bacteria previously shown to have a broad range of degradative capabilities 12 hours aerobic 9 different strains o f bacteria Inconclusive; Analytical analysis lacked sensitivity DuPont 1996 Perfluorooctanoic acid Laboratory scale reactors for (PFOA); Fluorad FC-143 aerobic and anaerobic treatm ent Perfluorooctanoic acid (PFOA) Aquatic mesocosm studies at University of Guelph Microcosm Facility 25 days 35 days aerobic and anaerobic Aerobic: No biodegradation observed; Anaerobic: PFOA no longer detected after 25 days; increased concentrations of fluoride ions were not observed; no adsorption on glass walls Aerobic: STP effluent mixed with o f reactor; results indicate effluent from pre-settling tank of potential transform ation of Aachen-Soers m unicipal STP; COO- but whereabouts of Schroder 2003; Anaerobic: effluent from perfluorinated segm ent Meesters and stabilization tank o f same STP was not determined. Schroder 2004 aerobic none Persistent in water column; No significant degradation Richards e tal. 2001; after 35 days Hanson et, al., 2005 May 23, 2006 Page 19 DuPont-19567 Table 4: Summary of Photodegradation Studies for Ammonium Perfluorooctanoate (APFO) Test Substance A m m onium P erfluorooctanoate; FC-143 Test m ethod D ire ct p h o to ly s is p ro c e d u re d e s c rib e d in Federal R e g iste r (Voi. 43, No. 132M onday, J u ly 1 0 ,1 9 7 8 ) by US EPA Based on OPPTS: 835.5270 "In d ire ct E xposure period 30 days C onclusions R e fe re n ce No p ho todegradation was detected after 30 days. N either d ire c t n o r in d ire ct 3M C om pany 1979 P hotolysis S creening T e st" (1998) and photolytic deco m p o sition o f PFOA OECD Draft docu m e n t "P h o to tra n s fo rm a tio n o f C h e m ica ls in were obse rve d based on loss o f sta rtin g m aterial; E stim ated P e rflu o ro o cta n o ic acid, am m onium salt W a te r - D irect and In d ire ct P h o to lysis." (2000). 69.5-164 hrs m inim um in d ire ct p h o to lytic h alf life > 349 days. 3M C om pany 2001b D irect p h o to ly s is : 89.5% o f the initial PFOA deco m p o sed afte r 72 h o u rs w ith irrad ia tio n o f an aqueous solu tion o f PFOA under 0.48 m Pa o f 0 2 a t room tem perature; T ungstic Not e nviron m e n tally relevant; Tested d ir e c t p h o to ly s is , H20 2, h e te ro p o ly a c id heteropolyacid photocatalyst: U nder sim ilar co n d itio n s as the d ire c t p h o to ly s is s tu d y, led to P e rflu o ro o cta n o ic acid p h o to ca ta lyst u sin g a qu e o u s so lu tio n o f (P F O A ) PFOA u n d e r 0.48 m Pa 0 2 at RT. 24-72 hrs com plete PFOA deco m p o sition a fte r 24 h o u rs o f irradiation. H ori e t al. 2004 Not e nviron m e n tally relevant; Tested PFOA was com pletely decom posed by a p hotochem ical d ir e c t p h o to ly s is , H20 2, h e te ro p o ly a c id s y s te m w ith 50 mM S 20 82' a n d 4 P e rflu o ro o cta n o ic acid p h o to ca ta lyst u sin g a qu e o u s so lu tio n o f h o u rs o f irradiation fro m a 200-W (P F O A ) PFOA u n d e r 0.48 m Pa 0 2 at RT. 4 hrs xe n o n -m e rcu ry lam p. H ori e t al. 2005 May 23, 2006 Page 20 DuPont-19567 Table 5: Summary of Hydrolysis Study for Ammonium Perfluorooctanoate (APFO) Test Substance Test method pH levels Conclusions Reference Based on OPPTS: 835.2110: "Hydrolysis Perfluorooctanoic acid, as a function of pH": US EPA OPPTS ammonium salt publication no. 712-C-98-057. 5,7, and 9 Estimated Hydrolytic half-life of PFOA > 97 years 3M Company 2001c May 23, 2006 Page 21 DuPont-19567 Table 6: Summary of Activated Sludge Respiration Inhibition Studies for Ammonium Perfluorooctanoate (APFO) Test Substance Test method Exposure period Conclusions Reference Ammonium Acute toxicity of a compound to Perfluorooctanoate; activated sludge mixed liquor (3M Not expected to inhibit activity of FC-143 method) 7 minutes activated sludge 311 Company 1980b Ammonium Test material at 1,000 mg/L Perfluorooctanoate; induced 38% inhibition after 3 hrs. FC-126 OECD 209 30 min, and 3 hrs, of exposure 311 Company 1987b Ammonium 3-hr. EC50 for activated sludge Perfluorooctanoate; respiration inhibition was FX-1003 OECD 209 30 min, and 3 hrs, determined be >1,000 mg/L, 3111Company 1990 Ammonium 3-hr, EC50 for activated sludge Perfluorooctanoate; respiration inhibition was FC-1015-X May 23, 2006 OECD 209 Page 22 30 min, and 3 hrs, determined be >3,320 mg/L, 3111Company 1996 2.0 Bioaccumulation May 23, 2006 Page 23 2.1 Bioconcentration/Bioaccumulation Bioaccumulation is the process in which a substance accumulates in an organism via uptake from both food and water as a result of all processes that affect compound adsorption, distribution, metabolism, and elimination in the organism (Macek et al. 1979, Suedel et al. 1994). The cumulative effect of all these processes in an organism when the route of exposure is solely from water is known as bioconcentration (Macek et al. 1979, Seudel et al. 1994). Bioconcentration factors (BCF) represent the ratio of the exposure concentration in water to organism tissue residues while bioaccumulation factors (BAF) represent the ratio of the exposure concentrations in water and diet to tissue residues in the organism. Tissue residues in whole organisms are of concern in ecological risk assessments because predators typically consume entire organisms. Residue concentrations in edible tissues (e.g., fish fillets) are generally the focus of human health risk assessments. For many hydrophobic organic chemicals, bioconcentration and/or bioaccumulation factors may be estimated from the octanol-water partition coefficient (Kow) for the compound based on the assumption that hydrophobic organic chemicals preferentially accumulate in lipids. Since PFOA does not preferentially partition to lipids, the Kow for PFOA is not a suitable predictor for bioconcentration or bioaccumulation. The most appropriate method of determining bioaccumulation potential for such substances is via experimental approaches. Several studies have been completed in different laboratories to directly examine the bioconcentration and/or bioaccumulation potential of PFOA (Table 1). In a bioconcentration study conducted under static test conditions, the BCF for fathead minnows was determined to be 1.8 (3M Company, 1995). Using a flow-through test method (essentially OECD 305), the bioconcentration of PFOA in fish was tested using common carp (Cyprinus carpio) at two nominal exposure concentrations, 5 and 50 ug/L (Daikin 2000). Analyses were performed on water and fish extracts using liquid chromatography-mass spectrometry (LC-MS). No mortality or abnormalities in fish behavior or appearance were reported during the study. Mean measured concentrations of the test substance in water were used to calculate the bioconcentration factor (BCF). For the highest exposure concentration (nominal 50 ug/L), the average steady state BCF (based on study days 6-28) was reported to be 3.1. For the lowest exposure concentration (nominal 5 pg/L), the maximum BCF was determined to be 9.4 after day 16. The BCF fell to < 5.1 by day 28. However, tissue residue concentrations in fish in the 5 pg/L nominal exposure concentration were at or below the determination (i.e., quantitation) limit at day 28; therefore, the authors indicated that no steady state BCF could be determined for this exposure level (i.e. tissue concentration < LOQ). In a recent field investigation in Japan (Morikawa et al., in press), BCF values for two species of turtles, Trachemys scripta elegans and Chinemys reevesii, were reported to be less than 4 based on measured PFOA concentrations in the rivers from which the turtles were collected and in the turtle plasma. A total of 94 turtles were evaluated in May 23, 2006 Page 24 conjunction with ambient water samples; the authors also reported that the BCF values in turtles declined as the PFOA concentration increased in the ambient water samples. Additional peer reviewed data to support that PFOA neither bioaccumulates nor biomagnifies in the food chain can be found in laboratory studies by Martin et al. (2003a,b). In two separate laboratory experiments, juvenile rainbow trout (Oncorhynchus mykiss) were exposed either via water or diet containing PFOA as part of a mixture of a homologous series of perfluoroalkyl carboxylates and sulfonates. Trout were exposed to the test substances for 32 days followed by a 41-day depuration period (Martin et al. 2003a,b). The carcass bioconcentration factor (BCF) for PFOA was determined to be 4.0 0.6 (Martin et al. 2003a) while the blood and liver BCF values were 27 and 8, respectively. The carcass bioaccumulation factor (BAF) for PFOA was determined to be 0.038 0.006 (Martin et al. 2003b). In a recent study, Martin et al. (2004a) measured PFOA in various organisms from a food web of Lake Ontario. By accounting for the known diet composition of lake trout, it was shown that bioaccumulation did not occur for PFOA at the top of this food web nor did biomagnification occur through successive trophic levels of the food web. Similar observations were reported (Tomy et al. 2004) for an eastern Arctic marine food web where PFOA did appear to biomagnify between individual feeding relationships (BMF values of 0.04 - 2.7) but not through the entire food web. However, it is important to note that in their calculation of BMF values, the authors utilized one-half the limit of detection for analytical non-detect values. In a similar fashion, data from another Great Lakes food chain (Kannan et al. 2005) and Greenland and the Faroe Islands (Bossi et al. 2005a) provide support for the hypothesis that PFOA does not biomagnify through foodchains. Environmental monitoring studies indicate PFOA can occasionally be detected in wildlife, including polar bear and arctic foxes (Martin et al. 2004b; De Silva and Mabury 2004) and occasionally in birds (Giesy and Kannan 2001). Temporal trends have also been investigated in several studies. Tomy et al. (2005) reported an increase in tissue residues of PFOA in beluga whales from SE Baffin Island over the period from 1982 to 2002. However, evaluation of this data indicates no trend in the data from 1982 through 1995. No samples were analyzed for the period between 1995 and 2002 but the PFOA concentrations in the 2002 samples were greater than concentrations in the 1995 samples. While the data between 1995 and 2002 may be suggestive of a temporal trend, samples from additional time points will be necessary to confirm or refute any trend. In a study on temporal trends, the concentrations of PFOA in the Baltic Sea marine environment were measured using archived guillemot eggs, Uria aalga (Holmstrom et al. 2005). Egg samples collected from Stora Karlso (Sweden) between 1968 and 2003 were obtained from an environmental specimen bank and concentrations of PFOA were analyzed using high pressure liquid chromatography with electrospray ionization tandem mass spectrometry (HPLC ESI-MS/MS). PFOA was not detected in any of the samples at the LOD of 3 ng/g; consequently no trend existed in PFOA concentrations over the 35-year period represented by these egg samples. May 23, 2006 Page 25 Similarly, in an evaluation of ringed seal liver residues from western and eastern Greenland over the period from 1982 to 2003, Bossi et al. (2005b) reported that PFOA concentrations were below the minimum detection limit (MDL, 1.2 ng/g) for PFOA in all samples (n= 30 for western Greenland, n = 36 for eastern Greenland). The EU hazard classification and labelling scheme indicates that if the BCF for a compound is 100 or more the material may be classified as R53 (EEC 1967). The PFOA BCF is at least an order of magnitude lower than this limit. The Globally Harmonised System on Classification uses a BCF of 500 as the lower limit for classification (UNEP, 2003). Regulatory classification schemes such as the EU hazard classification and labelling scheme and the EU PBT-assessment approach indicate that PFOA is not bioaccumulative. In the EU PBT-assessment approach, environmental parameters are used as criteria for identification of a substance as persistent (P), bioaccumulative (B) and toxic (T). The limits for the bioaccumulation assessment are based on the BCF for a compound. If the BCF for a compound is 2000 or more the substance is categorized as bioaccumulative (B) (EU TGD 2003). If the BCF is more than 5000 the substance is categorized as very bioaccumulative (vB). The latter categorization scheme for B is also consistent with the terminology for B classification in CEPA 1999, i.e., bioaccumulative chemicals have a bioaccumulation factor greater than or equal to 5000. All available evidence indicates that PFOA is not B (bioaccumulative) based on relevant regulatory B criteria. 2.1.1 Bioconcentration/Bioaccumulation Uncertainty The existing laboratory bioconcentration/bioaccumulation data are for freshwater fish. There are no laboratory study data for freshwater invertebrates or marine invertebrates or fish. There are also no bioaccumulation data from laboratory studies with other vertebrate species (e.g., terrestrial mammals), birds or terrestrial plants. However, levels of PFOA in organisms sampled from the environment suggest that bioaccumulation and biomagnification of PFOA are unlikely to be significant issues for wildlife species. Considering that PFOA from ECF processes are a mix of linear and branched isomers, there is a need to learn if the isomers have differences in bioaccumulation potential. 2.2 Bioaccumulation Conclusion The available data indicate that BAF and BCF values for PFOA are below all regulatory levels that would trigger concern for bioconcentration and bioaccumulation. In addition, the available evidence indicates that PFOA does not biomagnify through the foodchain. Therefore, while PFOA appears to be environmentally persistent, PFOA is not bioaccumulative based on relevant data and regulatory B criteria. May 23, 2006 Page 26 2.3 Bioaccumulation Literature Cited Additional Literature Cited for DuPont-19567 Bossi, R., F.F. Riget, R. Dietz, C. Sonne, P. Fauser, M. Da, and K. Vorkamp. 2005a. Preliminary screening of perfluorooctane sulfonate (PFOS) and other fluorochemicals in fish, birds and marine mammals from Greenland and the Faroe Islands. Environ. Pollut. 136:323-329. Bossi, R., F.F. Riget and R. Dietz. 2005b. Temporal and spatial trends of perfluorinated compounds in ringed seal (Phoca hispida) from Greenland. Environ. Sci. Technol. 39:7416-7422. Kannan, K. L. Tao, E. Sinclair, S.D. Pastva, D.J. Jude and J.P. Giesy. 2005. Perfluorinated compounds in aquatic organisms at various trophic levels in a Great Lakes food chain. Arch. Environ. Contam. Toxicol. 48:433-443. Morikawa, A., N Kamei, K. Harada, K. Inoue, T. Yoshinaga, N. Saito and A. Koizumi. In Press. The bioconcentration factor of perfluorooctanesulfonate is significantly larger than that of perfluorooctanoate in wild turtles (Trachemys scripta elegans and Chinemys reevesii): An Ai River ecological study in Japan. Ecotox. Environ. Safety http://dx.doi.org/10.1016/j.ecoenv.2005.03.007. Tomy, G., T. Halldorson and G. Stern. 2005. Time trend studies of perfluorinated compounds in beluga (Delphinapterus leucas) from SE Baffin Island. Organohalogen Compounds 67:1001-1004. Literature cited for DuPont-17709 3M Company. 1995. Assessment of Bioaccumulative Properties of Ammonium Perfluorooctanoic Acid: Static Fish Test. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0496. Daikin. 2000. Bioaccumulation Test of Perfluoroalkylcarboxylic Acid (C= 7-13) in Carp. Test No. 51519, p. 26. Kurume Laboratory, Chemicals Evaluation and Research Institute, Japan. De Silva, A.O., and S.A. Mabury. 2004. Isolating isomers of perfluorocarboxylates in polar bears (Ursus maritimus) from two geographical locations. Environ. Sci. Technol. 38(24): 6538-6545. EEC. 1967. Council Directive 67/548/EEC (as Amended for the Seventh Time by Directive 92/32/EEC) on the Approximation of Laws, Regulations and Administrative Provisions Relating to the Classification, Packaging and Labelling of Dangerous Substances. OJ L154, 1-98. May 23, 2006 Page 27 http://europa.eu.int/smartapi/cgi/sga_doc7smartapilcelexapilprodlCELEXnumdoc &lg=en&numdoc=31967L0548&model=guichett EU-TGD. 2003. Technical Guidance Document in Support of Commission Directive 93/67/EEC on Risk Assessment for New Notified Substances, Commission Regulation (EC) No. 1488/94 on Risk Assessment for Existing Substances and Directive 98/8/EC of the European Parliament and of the Council Concerning the Placing of Biocidal Products on the Market: 2nd edition. Giesy, J. P. and K. Kannan. 2001. Global distribution of perfluorooctane sulfonate in wildlife. Environ. Sci. Technol. 35:1339-1342. Holmstrom, K., U. Jaernberg and A. Bigner. 2005. Temporal trends of PFOS and PFOA in Guillemot eggs from the Baltic Sea, 1968-2003. Environ. Sci. Technol. 39(1): 80-84. Macek, K.J., S.R. Petrocelli and B.H. Sleight, III. 1979. Considerations in assessing the potential for, and significance of, biomagnification of chemical residues in aquatic food chains. IN: Marking, L.L. and R.A. Kimerle (eds), Aquatic Toxicology, ASTM STP 667. American Society for Testing and Materials, pp. 251-268. Martin, J. W., S.A. Mabury, K.R. Solomon, and D.C.G. Muir. 2003a. Bioconcentration and tissue distribution of perfluorinated acids in rainbow trout (Oncorhynchus mykiss). Environ. Toxicol. Chem. 22:196-204. Martin, J. W., S.A. Mabury, K.R. Solomon and D.C.G. Muir. 2003b. Dietary accumulation of perfluorinated acids in juvenile rainbow trout (Oncorhynchus mykiss). Environ. Toxicol. Chem. 22:189-195. Martin, J. W., Whittle, D. M., Muir, D. C. G., and Mabury, S. A. 2004a. Perfluoroalkyl contaminants in a food web from Lake Ontario. Environ. Sci. Technol. 38: 5379-5385. Martin, J. W., M.M. Smithwick, B.M. Braune, P.F. Hoekstra, D.C.G. Muir and S.A. Mabury. 2004b. Identification of long-chain perfluorinated acids in biota from the Canadian Arctic. Environ. Sci. Technol. 38:373-380. Suedel, B.C., J.A. Boraczek, R.K. Peddicord, P.A. Clifford and T.M. Dillon. 1994. Trophic transfer and biomagnification potential of contaminants in aquatic ecosystems. Reviews of Environmental Contamination and Toxicology, 136:21-89. Tomy, G.T., W. Budkowski, T. Halldorson, P.A. Helm, G.A. Stern, K. Friesen, K. Pepper, S.A. Tittlemier and A.T. Fisk. 2004. Fluorinated organic compounds in an eastern Arctic marine food web. Environ. Sci. Technol. 38:6475-6481. UNEP. 2003. Globally Harmonised Systems for the Classification and Labelling of Substances and Mixtures. United Nations, New York and Geneva. May 23, 2006 Page 28 2.4 Bioaccumulation: Appendix A May 23, 2006 Page 29 Table 1. Laboratory Bioconcentration, Bioaccumulation and Biomagnification Data for PFOA. Substance Species Bioconcentration Bioaccumulation PFOA (NH4+) Fathead minnow 1.8 a -- Rainbow trout 4 b 0.038b Biomagnification -- <1b Carp <9.4c -- -- Slimy Sculpin Lake Trout Various species _ -- TMF = 0.37 d _ TMF = 0.58 d -- BMF = 0.04 - 2.7 ef a - 3M 1995 b - Martin et al. 2003a, b c - Daikin 2000 d - Martin et al. 2004a e - Tomy et al. 2004 f - values may be based on 0.5 LOD substituted for analytical non-detect values May 23, 2006 Page 30 3.0 Environmental Toxicity May 23, 2006 Page 31 3.1 Toxicity in the Aquatic Environment 3.1.1 Acute Toxicity Most of the aquatic toxicology studies have been conducted with the ammonium salt of perfluorooctanoic acid (PFOA). PFOA is a completely fluorinated organic acid and the free acid is expected to be completely dissociated in water. The toxicity of PFOA to aquatic organisms has been investigated in numerous acute and chronic studies that are summarized in Appendices A, B, C and D. The algae species Selenastrum capricornutum was recently renamed Pseudokirchneriella subcapitata and the information in the Appendices reflects this name change although original report titles have been maintained in the reference section. Several groups of organisms and species were tested to assess the acute toxicity of PFOA including the mixed bacterial community found in sewage sludge, the marine bacterium, Photobacterium phosphoreum (i.e., Microtox), the fathead minnow (Pimephales promelas), bluegill sunfish (Lepomis machrochirus), rainbow trout (Oncorhynchus mykiss), the invertebrate water flea (Daphnia magna), an insect (Chironomus tentans), and a green alga, (Pseudokirchneriella subcapitata), as well as diatoms, snails, and the plant and zooplankton communities found in outdoor microcosms. The toxicity test endpoints in Appendices A, B, C and D are presented based on nominal test substance concentrations unless indicated otherwise. Information is also provided on the actual test substance purity in addition to citations to original source documents and the U.S. Environmental Protection Agency Administrative Record document number (e.g., U.S. EPA AR226-xxxx) if applicable. 3.1.1.1 Bacteria The 30-minute and 3-hour EC50 (effect concentration producing 50% inhibition) values for respiratory inhibition of sludge communities ranged from >1000 mg/L to > 3330 mg/L while 30-minute EC50 values from the Microtox assay with Photobacterium phosphoreum ranged from 870 to 3150 mg/L (see Appendix A). 3.1.1.2 Algae The lowest 96-hour EC50 and NOEC (no observed effect concentration) values reported from algal assays with Pseudokirchneriella subcapitata were 49 and 12.5 mg/L, respectively. Overall, 96-h EC50 values (based on growth rate, cell density, cell counts, and dry weights) ranged from 49 to > 3330 mg/L while NOEC values ranged from 12.5 to 430 mg/L (see Appendix A). Based on these values, U.S. EPA would classify PFOA as being of low to medium concern for acute aquatic toxicity to algae (Smrchek et al. 1995). May 23, 2006 Page 32 3.1.1.3 Invertebrates Protozoa An EC50 value of 424.1 124.0 pM PFOA and dose-dependent reductions in the backward swimming response were reported from a screening study evaluating the effects of PFOA on backward swimming ability of the protozoan, Paramecium caudatum (Matsubara et al. 2006). The authors hypothesized that the endpoint utilized in the study was related to the potential toxicity of PFOA on ion channels and that the alteration of backward swimming behavior in P. caudatum was due to changes in calcium conductance induced by PFOA. Aquatic Invertebrates Daphnid 48-h EC50 values (based on immobilization) ranged from 126 to >1200 mg/L. The 48-h LC50 for an unidentified species of snail was 820 mg/L while the 10-day NOEC for the sediment-dwelling chironomid species, Chironomus tentans, was > 100 mg/L (see Appendix B). Based on these values, U.S. EPA would classify PFOA as being of low concern for acute aquatic toxicity to invertebrates (Smrchek et al. 1995). Stevenson et al. (2005) reported on the effects of PFOA on the cellular p-glycoprotein (p-gp) transporter in gill tissue of the marine mussel, Mytilus californianus. The p-gp transporter has been identified in many aquatic organisms and has been suggested to function as the first line of defense against chemical exposure by binding and exporting moderately hydrophobic chemicals from the cell. The authors indicated that exposure to PFOA significantly inhibited the p-gp transporter, however, no specific data were presented in the abstract to support this statement. Terrestrial Invertebrates Effects of PFOA on the terrestrial nematode, Caenorhabditis elegans, were evaluated in a study by Tominaga et al. (2004). The authors reported that "generation-response and concentrations-response relationships were not observed in PFOA". A statistically significant reduction in adult nematodes relative to control was reported at the highest PFOA concentration tested (i.e., 10 nM) during the fourth generation. The PFOA 48-h EC50 for mobility of first generation organisms was reported to be 2.35 mM PFOA. There are questions concerning the study, however, since the authors reported that PFOA was "poorly soluble" in water (although PFOA water solubility exceeds 1 g/L) and 0.5% DMSO was used as a co-solvent to prepare test solutions. 3.1.1.4 Vertebrates PFOA was not observed to inhibit normal progesterone-induced germinal vesicle breakdown in vitro in oocytes of the African clawed frog, Xenopus laevis, although it was observed to inhibit normal androstedione-induced germinal vesicle breakdown (Fort et al. 2005). No specific EC50 values for PFOA were reported by the authors. May 23, 2006 Page 33 Fish 96-h LC50 (lethal concentration producing 50% mortality) values ranged from 280 to 2470 mg/L. Although most data are for the fathead minnow, data for bluegill and pumpkinseed sunfish and rainbow trout do not suggest any remarkable differences in species sensitivity to PFOA (see Appendix C). Based on these values, U.S. EPA would classify PFOA as being of low concern for acute aquatic toxicity to fish (Smrchek et al. 1995). 3.1.2 Chronic Toxicity The available chronic aquatic toxicity data (see Appendix D) include 14 day algal EC50 values of 43 and 73 mg/L (in addition to NOECs from the 96-hour studies), 35 day EC10, EC50, and NOEC values of > 5.7-8.4, > 31.8-35.8 and >23.9 mg/L, respectively, from aquatic plant microcosm studies, 21-day daphnid reproduction NOECs ranging from 20 - 22 mg/L, 35-day mixed zooplankton community LOECs from freshwater microcosm studies ranging from 10 - 70 mg/L, and chronic fish NOEC values ranging from 0.3 mg/L for steroid hormone levels in male fish from 39 day microcosm studies to 40 mg/L based on survival, length, and weight from an 85-day rainbow trout early life stage study. In a long-term study, rainbow trout fry were initiated to aflatoxin B1 and then exposed to PFOA at a concentration of 1800 mg/L in the diet (Tilton et al. 2005). At the end of 30 weeks of dosing, enhanced liver tumor incidence and multiplicity were observed in the fish. The authors reported that carcinogenesis appeared independent of peroxisome proliferation because of the lack of induction of peroxisomal b-oxidation and catalase. Plasma vitellogenin was elevated in the trout and the authors hypothesized that the data suggested the possibility of an alternative mechanism for tumor enhancement by PFOA in an organism that is relatively resistant to peroxisomal proliferation. However, this study is unlikely to be environmentally relevant given the high exposure concentration of PFOA used in the diet. Based on these values, U.S. EPA would classify PFOA as being of low concern for chronic aquatic toxicity to algae and low to medium concern for chronic aquatic toxicity to invertebrates and fish (Smrchek et al. 1995). 3.1.3 Environmental Toxicity Uncertainty A variety of different test substances with varying designations and lot numbers were tested in the reported studies. The ammonium salt was generally tested but the exact composition and identification of impurities, which may affect toxicity, was generally not reported. Purity of the test substance was not sufficiently characterized in some of the tests. In some tests, only nominal test chemical concentrations were used to determine test endpoints (although PFOA is stable in water). Tests may or may not have been conducted according to regulatory guidelines and Good Laboratory Practices (GLP) and a variety of testing laboratories conducted the PFOA toxicity studies over a period of time from approximately 1974-2004. May 23, 2006 Page 34 The acute and chronic studies performed by CIT (2003a,b,c; 2004a,b) were conducted following OECD and/or U.S. EPA test guidelines under GLP. These studies utilized a single, well-characterized batch of PFOA for aquatic acute base set testing as well as a chronic reproduction study with Daphnia magna and an early-life stage study with the rainbow trout, Oncorhynchus mykiss. In addition, although the acute trout and daphnid studies were conducted using nominal concentrations, the algal study and the chronic daphnid and trout studies were conducted with analytical confirmation of test substance concentrations. These studies, in conjunction with other recent studies reporting endpoints based on measured test concentrations (MacDonald et al. 2004, DuPont 1999, Oakes et al. 2004, Sanderson et al. 2003, 2004, Hanson et al. 2005) represent the most reliable evaluations of the acute and chronic aquatic hazard of Pf Oa to algae, invertebrates and fish. No data were available to assess the aquatic toxicity of PFOA to marine algal, invertebrate or fish species. Except for a single study with the nematode, Caenorhabditis elegans, there were also no PFOA toxicity test data available for terrestrial plant, wildlife, or avian species. Considering that PFOA from ECF processes are a mix of linear and branched isomers, there is a need to learn if the isomers have differences in acute or chronic toxicity. 3.2 Environmental Toxicity Conclusion Based on the Environment Canada criteria for Inherent Toxicity (Ti), which indicate that a substance is inherently toxic if its acute toxicity is < 1 mg/L or its chronic toxicity is < 0.1 mg/L, PFOA is not inherently toxic. The available acute and chronic aquatic toxicity data for PFOA also indicate that it is of low to medium concern for toxicity (i.e., hazard) to freshwater algae, invertebrates, and fish based on data from laboratory studies and the ranking scheme used by U.S. EPA. However, no data were available to assess the aquatic toxicity of PFOA to marine algal, invertebrate or fish species. There were also no PFOA toxicity test data available for either terrestrial plant and wildlife or avian species. May 23, 2006 Page 35 3.3 Environmental Toxicity Literature Cited Additional Literature Cited for DuPont-19567 Fort, D.J., R.L. Rogers, J.H. Thomas, P.D. Guiney and J.A. Weeks. 2005. Inhibition of oocyte maturation in Xenopus by polybrominated diphenyl ethers, perfluorooctane sulfonate, and perfluorooctanoic acid. Society of Environmental Toxicology and Chemistry, North America 26th Annual Meeting. Baltimore, MD, USA. Hanson, M.L., J. Small, P.K. Sibley, T.M. Boudreau, R.A. Brain, S.A. Mabury and K.R. Solomon. 2005. Microcosm evaluation of the fate, toxicity and risk to aquatic macrophytes from perfluorooctanoic acid (PFOA). Arch. Environ. Contam. Toxicol. 49:307-316. Matsubara, E., K. Harada, K. Inoue and A. Koizumi. 2006. Effects of perfluorinated amphiphiles on backward swimming in Paramecium caudatum. Biochem. Biophys. Res. Comm. 339:554-561. Stevenson, C., L. MacManus-Spencer, D. Epel and R. Luthy. 2005. Tissue concentrations of perfluorochemicals and their inhibitory effect on multi-drug transporters of the mussel, Mytilis californianus. FLUOROS meeting, Toronto. Tilton, S.C., G.A. Orner, A.D. Benninghoff, J.D. Hendricks and D.E. Williams. 2005. Possible mechanism for hepatic tumor promotion by perfluorooctanoic acid in rainbow trout: a toxicogenomic approach. Society of Environmental Toxicology and Chemistry, North America 26th Annual Meeting. Baltimore, MD, USA. Tominaga, N., S. Kohra, T. Iguchi and K. Arizono. 2004. Effects of perfluoro organic compound toxicity on nematode Caenorhabditis elegans fecundity. J. Health Science 50:545-550. Literature Cited for DuPont-17709 3M Company. 1974. Acute toxicity to fish. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 225-0498. 3M Company. 1978a. 96-Hour Static Acute with Bluegill Sunfish. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0499. 3M Company. 1978b. 96-Hour Static Acute with Bluegill Sunfish. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0500. 3M Company. 1980a. Acute Toxicity of a Compound to Activated Sludge. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0505. May 23, 2006 Page 36 3M Company. 1980b. Acute Toxicity Testing: FC-143. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0504. 3M Company. 1981. Multi-phase Exposure/Recovery Algal Assay Test Method, St. Paul, m N. U.S. Environmental Protection Agency Administrative Record 226-0506. 3M Company. 1982. Acute Toxicity to Aquatic Invertebrates (Daphnia magna). St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0507. 3M Company. 1984. Chronic Toxicity to Freshwater Invertebrates. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0508. 3M Company. 1985. 96-Hour Acute Static Toxicity of FX-1001 to Fathead Minnow, (Pimephales promelas). St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0509. 3M Company. 1987a. Activated Sludge Respiration Inhibition Test. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0510 3M Company. 1987b. Microbics Microtox Test with FC-126. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0511. 3M Company.1987c. Acute Toxicity to Aquatic Invertebrates (Daphnia magna). St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0512. 3M Company. 1987d. 96-Hour Acute Static Toxicity of FC-126 to Fathead Minnow, (Pimephales promelas). St. Paul, MN. U.S. Environmental Protection Agency Administrative Record AR226-0513. 3M Company. 1990a. Activated Sludge Respiration Inhibition Test with FX-1003. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0514. 3M Company. 1990b. Microbics Microtox Toxicity Test with FX-1003. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0515. 3M Company. 1996a. Activated Sludge Respiration Inhibition Test with FC-1015-X. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226 0524. 3M Company. 1996b. Microbics Microtox Test with FC-143. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0521. 3M Company. 1996c. Microbics Microtox Test with FC-118. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0522. May 23, 2006 Page 37 3M Company. 1996d. Microbics Microtox Test with FC-1015-X. St. Paul, MN. U.S. Environmental Protection Agency Administrative Record 226-0523. CIT. 2003a. Acute Toxicity in Daphnia magna Under Static Conditions. Laboratory Study No. 22654 EAD, CIT, BP 563, 27005 Evreux, France. CIT. 2003b. Acute Toxicity in the Rainbow Trout Under Static Conditions. Laboratory Study No. 22655 EAP, CIT, BP 563, 27005 Evreux, France. CIT. 2003c. Daphnia magna Reproduction Test. Laboratory Study No. 22658 ECD, CIT, BP 563, 27005 Evreux, France. CIT. 2004a. Algal Inhibition Test. Laboratory Study No. 23685 EAA. CIT, BP 563, 27005 Evreux, France. CIT. 2004b. Early-life Stage Toxicity Test in Rainbow Trout Under Flow-Through Conditions. Laboratory Study No. 22659 ECP, CIT, BP 563, 27005 Evreux, France. DuPont. 1966. Bioassay Studies. Academy of Natural Sciences of Philadelphia. DuPont. 1994. Static, Acute 96-Hour LC50 of H-19704 to Bluegill Sunfish, Lepomis macrochirus. Haskell Laboratory Report No. HL-61-94. DuPont. 1999. H-24215: Static, Acute 96-Hour LC50 to Rainbow Trout, Oncorhynchus mykiss. Haskell Laboratory Report No. DuPont-3381. EG & G, Bionomics. 1978a. The Effects of Continuous Aqueous Exposure to 78.03 on Hatchability of Eggs and Growth and Survival of Fry of Fathead Minnow (Pimephales promelas). Report No. BW-78-6-175, EG & G, Bionomics, Wareham, MA. U.S. e Pa Administrative Record 226-0502. EG & G, Bionomics. 1978b. Summary of Histopathological Examination of Fathead Minnow (Pimephales promelas) Exposed to 78.03 for 30 Days. Report No. BW-789-301, EG & G, Bionomics, Wareham, MA. U.S. EPA AR226-0503. EnviroSystems, Inc. 1990a. Static Acute Toxicity of FX-1003 to the Daphnid, Daphnia magna. Study No. 9013-3, Hampton, N h . U.S. EPA AR226-0517. EnviroSystems, Inc. 1990b. Static Acute Toxicity of FX-1003 to the Fathead Minnow, Pimephales promelas. Study No. 9014-3, Hampton, NH. U.S. EPA AR226-0516. MacDonald, M.M., A.L. Warne, N.L. Stock, S.A. Mabury, K.R. Solomon and P.K. Sibley. 2004. Toxicity of perfluorooctane sulfonic acid and perfluorooctanoic acid to Chironomus tentans. Environ. Toxicol. Chem. 23:2116-2123. May 23, 2006 Page 38 Oakes, K.D., P.K. Sibley, K.R. Solomon, S.A. Mabury and G. J. Van der Kraak. 2004. Impact of perfluorooctanoic acid on Fathead Minnow (Pimephales promelas) fatty acyl-CoA oxidase activity, circulating steroids, and reproduction in outdoor microcosms. Environ. Toxicol. Chem. 23:1912-1919. Sanderson, H., T.M. Boudreau, S.A. Mabury and K.R. Solomon. 2003. Impact of perfluorooctanoic acid on the structure of the zooplankton community in indoor microcosms. Aquatic Toxicol. 62:227-234. Sanderson, H., T.M. Boudreau, S.A. Mabury and K.R. Solomon. 2004. Effects of perfluorooctane sulfonate and Perfluorooctanoic acid on the zooplankton community. Ecotox. Environ. Safety. 58:68-76. Smrchek, J., M. Zeeman and R. Clements. 1995. Ecotoxicology and the Assessment of Chemicals at the U.S. EPA's Office of Pollution Prevention and Toxics: Current Activities and Future Needs. pp. 127-158 In Making Environment Science. J.R. Pratt, N. Bowers and J.R. Stauffer (Eds.), Ecoprint, Portland, OR. 271 pp. T.R. Wilbury Laboratories. Inc. 1996a. Growth and Reproduction Toxicity Test with N2803-3 and the Freshwater Alga, Selenastrum capricornutum. T.R. Wilbury Study No. B93-TH, Marblehead, MA. U.S. EPA AR226-0518. T.R. Wilbury Laboratories, Inc. 1996b. Growth and Reproduction Toxicity Test with FC-1015 and the Freshwater Alga, Selenastrum capricornutum, T.R. Wilbury Study No. 1029-TH, Marblehead, MA. U.S. EPA AR226-0526. T.R. Wilbury Laboratories, Inc. 1996c. Acute Toxicity of FC-1015 to the Daphnid, Daphnia magna. T.R. Wilbury Study No. 1030-TH, Marblehead. MA. U.S. E p A AR226-0527. T.R. Wilbury Laboratories, Inc. 1996d. Acute Toxicity of N2803-3 to the Daphnid, Daphnia magna. T.R. Wilbury Study No. 892-TH, Marblehead, MA. U.S. EpA AR226-0520. T. R. Wilbury Laboratories, Inc. 1996e. Acute Toxicity of N2803-3 to the Fathead Minnow, Pimephales promelas. T.R. Wilbury Study No. 891-TH, Marblehead, MA. U. S. EPA AR226-0519. T.R. Wilbury Laboratories, Inc. 1996f. Acute Toxicity of FC-1015 to the Fathead Minnow, Pimephales promelas. T.R. Wilbury Study No. 1031-TH, Marblehead, MA. U.S. EPA AR226-0525. May 23, 2006 Page 39 3.4 Environmental Toxicity: Appendix A-D May 23, 2006 Page 40 Test Length 7 min 303mhin 303mhin 303mhin 30 min 30 min 30 min 30 min 30 min Effect Concentration mg/L * EC50 > 1000 EECC5500 >> 11000000 EECC5500 >> 11000000 EECC5500 >> 33332200 EECC2500 == 482700 EC50 > 1000 EC50=730 EC50 = 3150 EC50 = 1950 Appendix A. Acute Toxicity of PFOA to Bacteria and Freshwater Algae. Organism Comments Reference Sludge Sludge Sludge Sludge Photobacterium phosphoreum Photobacterium phosphoreum Photobacterium phosporeum Photobacterium phosphoreum Photobacterium phosphoreum PFOA, amFmCo-n1i4u3m, LsoalttN(pou.r3it7y >96.5%); PFOA, amFCm-o1n2i6u,mLosatlNt o(p.u3r9it0y > 78%); PFO50A%, awmatmero;nFiuXm-1s0a0l3t,(pLuortitNyo<. 4253%27) in 80P%FOwAat,ear;mFmCo-1n0iu1m5-Xsa,ltL(o2t0N%oF. CH-O14G3E) i2n05 PFOA, amFCm-o1n2i6u,mLosatlNt o(p.u3r9it0y > 78%); PFO50A%, awmatmero;nFiuXm-1s0a0l3t,(pLuortitNyo<. 4253%27) in PFOA, amFmCo-1n4iu3m, LsoatltN(pou. r4i2ty7> 96.5%); PFOA, am8m0o%niwumatesra;lFt (C2-01%18FC-143) in 80P%FOwAat,ear;mFmCo-1n0iu1m5-Xsa,ltL(o2t0N%oF. CH-O14G3E) i2n05 U3M.S.CEoPmApaAnRy212968-00a5;05 U3.SM. ECPoAmApaRn2y2169-08571a0 U3.SM. ECPoAmpAaRny22169-9005a1;4 U3.SM. ECPoAmpAaRny22169-9065a2;4 U3.SM. ECPoAmpAaRny22169-8075b1;1 U3.SM. ECPoAmpAaRny22169-9005b1;5 U3.SM. ECPoAmpAaRny22169-9065b2;1 U3.SM. ECPoAmpAaRny22169-9065c2;2 U3.SM. ECPoAmpAaRny22169-9065d2;3 * based on nominal test substance concentrations unless indicated otherwise DuPont-19567 May 23, 2006 Page 41 Appendix A. Acute Toxicity of PFOA to Bacteria and Freshwater Algae (continued) Test Length 96 h 72 h 96 h 96 h Effect Concentration EECC5500,,cmdelrgly/cLwou*tn=t =14499 EEEECCCC55550000,,,ggccrroeeollwwll tccthhooruuraannttttee====111188880000 ENCENO5CO0E5E,C0gC,,r,cogecwrleoltlwhlcoctrhouautnreantt=t=e=>=12934183300300 Organism Pseudokirchneriella subcapitata Pseudokirchneriella subcapitata Pseudokirchneriella subcapitata Comments PFOA, ammFCo-n1iu4m3, sLaoltt(Npou.ri3ty7> 96.5%) ; (TR WPiFFlbOCuA-r2y6(pS,uaLrmoitptylNe>oN9. 6o2..65N9%;2)8;03-3) PFOwAat,ear;mFmCo-1n0iu1m5-sXa,ltL(o2t0N%oF. CH-O14G3E) i2n0580% 96 h 168 h *******N*EENOCEC"OEsC55aCE005f,Ce,0ggg,,lrerbrboovoiiwwoewolmtmt"thhhaa==rsrsasas72tte2>4e=00>=41004210.0250.5 Pseudokirchneriella subcapitata Diatoms PFOA, ammobnaiutcmh #sa1l0t0(1094.6%) in water, PFOA, ammonium salt (unknownpurity) bbaasseedd oonn mnoemasiunareldtePsFt OsuAbsctaonncceenctornactieonntsrations unless indicated otherwise DuPont-19567 Reference U3.SM. ECPoAmApaRn2y2619-08510;6 UT.S.R. E. WPAilbAuRry22169-9065a1;8 UT.S.R. .EWPAilbAuRry22169-9065b2;6 CIT 2004a DuPont 1966 May 23, 2006 Page 42 Appendix B. Acute toxicity of PFOA to invertebrates. Test Length Effect Concentration, mg/L * Organism Comments Not reported 48 h Not reported 48 h 48 h 48 h 48 h 48 h 48 h 48 h 10 d EC50 = 183 (424 pM) EC50 = 1013 (2.35 mM) Not reported EEECCC555000>==1210220160 EC50 = 584 ENNECOOC5EE500CC====1773223600000 ** EC50 = 480 LC50 = 820 ** NOEC > 100 Paramecium caudatum Caenorhabditis elegans Mytilis californianus PFOA, ammonium salt (purity > 98%) PFOA PFOA Daphnia magna Daphnia magna Daphnia magna Daphnia magna Daphnia magna Daphnia magna Snails 80PPP%PFFFFOO5(OwTO0AAARa%At,,,e,WaaawrPamm;maFmiFFFFltmmmOCebCCmCroouoA---;o-1nn12ny1Fn2ii06i(4uuXuip6S1,u3mmmu,a-5Lm,r1mL-Loiss0Xstospaatyao0a,tlllNlt3ttet>lNLtN,o(((Noppo(29L.opuut.06o2.ouNrr.3.%6t5ii3r9ttN9ioN%7yyt0F;.y2o)><CH8;.>-049O21735634G8-%.2335%E7%))))i2i;)nn;05 PFOA, PFOA, aammmmoobnnaiiuutcmmh ss#aa1ll0tt0((u109n4.k6n%ow) innpwuaritteyr), Chironomus tentans PFOA (purity > 97%) Reference Matsubara et al. 2006 Tominaga et al. 2004 Stevenson et al. 2005 EnUUUv3.T..3SSSiMr.M...RoEEES.CCyPPPWosoAAAmtmielmAAApbpuaRRRasnr,ny222yyI222n11666c199---.990008816555729cc01197270a T.R. Wilbury 1996d CIT 2003a DuPont 1966 MacDonald et al. 2004 bbaasseedd oonn nmoemasinuareldtePsFt OsuAbsctaonncceenctornactieonntsrations unless indicated otherwise DuPont-19567 May 23, 2006 Page 43 Test Length Not reported Effect Concentration, mg/L * Not reported Appendix C. Acute Toxicity of PFOA to Vertebrates. Organism Comments Xenopus laevis PFOA Reference Fort et al. 2005 48 h LC50 = 1550 Pumpkinseed sunfish PFOA, ammonium salt (unknownpurity) DuPont 1966 Lepomis gibbosus 96 h LC50 = 440 Fathead minnow Pimephales prom elas PFFOCA-2(6p,uLriotyt N>o9.62.659%); U.3SM. ECPoAmApRan2y261-9074498 96 h LC50 > 420 Bluegill sunfish Lepomis macrochirus PFOA, amFmCo-n1i4u3m, LsaolttN(pou.ri8t3y > 96.5%); U3.SM. ECPoAmApaRn2y2169-07489a9 96 h LC50 = 569 Bluegill sunfish Lepomis macrochirus PFOA, ammonium salt (purity U3.SM. ECPoAmpAaRn2y2169-0785b00 96h LC50 = 766 Fathead minnow Pimephales prom elas PFOA, amFmCo-n1i4u3m, LsaolttN(pou.ri3t7y > 96.5%); U3.SM. ECPoAmpAaRn2y2169-0805b04 96h LC50 = 843 Fathead minnow Pimephales prom elas PFOAF(pXu-r1it0y01> 95%); U.3SM. ECPoAmApRan2y261-9085509 96h LC50 = 301 Fathead minnow Pimephales prom elas PFOA, amFCm-o1n2i6u,mLosatlNt o(p.u3r9it0y > 78%); U3.SM. ECPoAmpAaRn2y2169-08571d3 96h LC50 > 1000 Fathead minnow Pimephales prom elas PFO50A%, awmatmero;nFiuXm-1s0a0l3t,(pLuortitNyo<. 4253%27) in EnUv.iSro. SEyPsAtemAsR, 2In2c6.-,01591960b 96 h LC50 = 280 Fathead minnow Pimephales prom elas (TR WPiFFlbOCuA-r2y6(pS,uaLrmoitptylNe>oN9. 6o2..65N9%;2)8;03-3) U.TS..RE. PWAilAbuRry22169-9065e19 96h LC50 = 2470 Fathead minnow Pimephales prom elas 8P0F%OAw,ataemr;mFoCn-i1u0m15s,aLlto(t2N0%o. FHCO-G14E3)20in5 U.TS..RE. PWAilAbuRr2y2169-09562f5 96 h LC50 = 634 Bluegill sunfish PFOA, ammonium salt (purity > 99%) DuPont 1994 96 h ** LC50 = 800 LepRomaiinsbmoawcrtroocuhtirus FC-118, 20% PFOA solution DuPont 1999 96 h ****NLOCE50C==710275 OncRoarhinybnocwhutsromuvtkiss Oncorhynchus mykiss PFOA, ammobnaiutcmh s#a1l0t0(1094.6%) in water, CIT 2003b bbaasseedd oonnnmomeainsuarletedsPt FsuObAstacnocnecceonntcreantitorantsions unless indicated otherwise May 23, 2006 Page 44 DuPont-19567 Test Length Effect Concentration, mg/L * Appendix D. Chronic Toxicity of PFOA to Aquatic Organisms Organism Comment Reference 14 d 21 d 21 d 35 d 35 d 35 d 30 d 39 day 85 d 30 weeks ECE5C05,0c,edllrycowutn=t =7343 NOECEC, s5u0r,vrievparl,odre.p=ro4d3. = 22 ** NOEC = 20 Pseudokirchneriella subcapitata Daphnia magna Daphnia magna ** LOEC = 10 - 70 Miinxdeodozromoipclraonckotsomn - ** LOEC = 30 - 70 Moiuxteddoozromopiclarnokcotosnm- EC10 EC10 >>NN58OO..74EE,,CCEECC223355..0099 > > 31.8 35.8 Myoruitodpohoyrllmumicrsopciocasmtum M yoruiotdpohoyrllmu micrsoibciorsimcu m NgrOowECth,, hhaistctohpaabtihliotylo, gsyur>viv1a0l0, Fathead minnow Pimephales promelas PFOA, amFmCo-n1i4u3m, LsaolttN(pou.ri3t7y > 96.5%); PFOA amFmCo-n1i4u3m, LsaolttN(pou.r2it6y4> 96.5%); PFOA, ammobnaiutcmh s#a1l0t0(1094.6%) in water, PFOA, sodium salt, 18.7% in water PFOA, sodium salt, 18.7% in water PFOA, sodium salt, 18.7% in water PFOA, amFmCo-n1i4u3m, LsaolttN(pou.ri8t3y > 96.5%); ******1NtN1NoeO-sOvkOEtioeEpECtsoCotC,est,e,sirtmsoutitionromavneslieetv==eaptrol50ola.0n>f3seimr,1s0ta0 ** NOEC = 40 L18iv0e0r(teuxmpoorsuinrecicdoenncc.e) Fathead minnow Poimutedpohoarlmesipcrroocmoeslmas Rainbow trout Oncorhynchus mykiss Rainbow trout Oncorhynchus mykiss PFOA, 19.4% in water PFOA, ammobnaiutcmh s#a1l0t0(1094.6%) in water, PFOA U.3SM. ECPoAmApRan2y261-9085106 U.3SM. ECPoAmApRan2y261-9085408 CIT 2003c Sanderson et al. 2003 Sanderson et al. 2004 Hanson, et al. 2005 EGU&.S.GEBPAionAoRm2i2c6s-10957081a,b Oakes et al. 2004 CIT 2004b Tilton et al. 2005 bbaasseedd oonnnmomeainsuarletedsPt FsuObAstacnocnecceonntcreantitorantsions unless indicated otherwise May 23, 2006 Page 45 DuPont-19567 DuPont-19567 4.0 Environmental Concentrations May 23, 2006 Page 46 DuPont-19567 4.1 Measured Levels of PFOA in Environmental Samples This section presents the levels of PFOA as found in environmental samples, as reported in the literature through 1/15/2006. For the purpose of comparison, all reported measurements were standardized to parts per billion (i.e., ng/mL, ng/g). A summary table of these studies is included in Appendices A & B to this section. In keeping with the focus on ecological endpoints, data were collected for abiotic and biotic environmental media and not for the indoor or uniquely human environments. As a result drinking water, breast milk, human serum, indoor air, indoor dust, food, and consumer products were beyond the scope of the data collection effort. Also note that the data were collected solely for perfluorooctanoate (PFOA) and not for other compounds. May 23, 2006 Page 47 DuPont-19567 Recent advances in laboratory methodologies coupled to highly sensitive instrumentation are providing improved capabilities with increased sensitivity and significantly reduced limits of detection for PFOA. These advances make it possible to routinely detect and quantify PFOA in low concentrations (see table below) across a variety of environmental matrices. These new methods provide critical capabilities that are enabling scientists to determine at unprecedented levels: The concentrations of compounds that occur in the environment, The mechanisms by which these compounds enter the environment (source pathways), and The processes that affect the transport, persistence, and fate of the compounds in the environment. Before the widespread use of LC/MS/MS capabilities, the ability to detect PFOA was substantially hindered and sample contamination (primarily due to PTFE seals) was a common source of error. PFOA constitutes a small fraction of the total perfluorinated compound (PFC) burden found in the environment. Where studies were unable to quantify environmental PFOA levels, improved analytical sensitivity has resulted in greater detection frequencies albeit at lower concentrations. A table of the detection limits from more recent studies is as follows: Sam ple Type D e te c tio n Lim it O utdoor A ir Soil 0.4 pg/m 0.2 ng/g w w Ground W ater 0.010 ng/m L Fresh W ater Salt W ater 0.00006 ng/m L 0.0052 ng/m L Fish Liver 1 ng/g w w Bird Liver (C orm orant) 2.5 ng/g w w M am m al Liver (Seal) 0.3 ng/g w w D e te c tio n Frequency 20/20 11/22 85/87 11/11 20/20 4/44 12/12 8/8 Study Citation H arad a e t al. 2 005 DuPont 2003c DuPont 2003c K a lle n b o rn e t al. 2 00 4 Y a m a sh ita e t al. 200 4a K a lle n b o rn e t al. 2 00 4 C orsolini and Kannan 2004 K a lle n b o rn e t al. 2 00 4 The only study to examine PFOA levels in environmental samples over time (Holmstrom et al. 2005) did not detect PFOA in any of the 146 guillemot egg samples collected from 1968 to 2003 in the Baltic Sea, so no trend could be determined. Over this same period, however, perfluorooctane sulfonate (PFOS) levels increased (1968-1997) and then decreased (1997-2003). May 23, 2006 Page 48 DuPont-19567 4.1.1 Outdoor Air Published outdoor air measurements of PFOA are available from Japan and the USA. Japanese samples covered 2 areas, Oyamazaki and Morioka, both in the Kyoto prefecture (reporting limits in the pg/m3 range) covering the time frame of 4/23/2001 to 7/20/2003. The range of the 20 samples (combined from both cities) was 1.6 pg/m3to 920 pg/m3with no apparent temporal correlation (Harada et al. 2005). The geometric means for each of the two cities studied also varied widely: 2.0 pg/m3 (Morioka) and 263 pg/m3(Oyamazaki). In the USA, samples were collected at a manufacturing site in West Virginia (Barton et al. 2006) over the period 11/2003-1/2004. Of the 28 samples analyzed, 5 (18%) had levels above the quantitation limit (0.07 pg/m3) with the highest and average results being 0.9 pg/m3 and 0.45 pg/m3 respectively. 4.1.2 Soil Three sets of soil measurements were found in the literature, none were considered to represent ambient conditions. Two sample sets (22 samples total) were collected near a manufacturing site in West Virginia and the results ranged from below the reporting limit (MDL = 1.70 ng/g dry weight) to 170 ng/g dry weight (DuPont 2003c, 2005). As expected, the concentration profile decreased with increasing bore depth (i.e., concmax at surface) with no sample above the LOQ (LOQ = 2 ng/g) below the water table. The third set of soil samples was collected in October 2003 (Tomakomai, Japan), two months after 40,000 liters (minimal) of fire fighting foam containing PFOS and a variety of perfluorinated carboxylic acids (unknown concentrations) had been used to put out a refinery fire. The mean (n=2) result was 0.00287 ng/mL [sic] (Yamashita et al. 2004b). 4.1.3 Sediment Measurements of PFOA in sediment samples have been reported for several Nordic countries, and the USA. Of the 5 Nordic counties sampled (Finland, Sweden, Norway, Faroe Islands, Iceland) only 2 samples from Norway (0.278 - 0.312 ng/g) were reported above the LOQ (LOQ = 0.20 ng/g) with 13 (non-Norway) samples being reported less than the LOQ (Kallenborn et al. 2004). In the USA, sediment results do not correlate with manufacturing as observed with other environmental matrices. Two studies have reported sediment values for a variety of urban sites, which appear to indicate that sediment is not a final sink for PFOA. Comparison of manufacturing cities (Decatur, AL; Mobile, AL; Columbus, GA; Pensacola, FL) to non-manufacturing (Cleveland, OH & Port St. Lucie, FL) (3M 2001), May 23, 2006 Page 49 DuPont-19567 generated 26 samples. Of the manufacturing related samples (14 total), 8 were below the LOD (LOD = 0.080 ng/g) and 6 were below the LOQ (LOQ = 0.200 ng/g). Of the remaining 2 cities, Port St. Lucie reported samples from 1999 were all below the LOD while 2000 and 2001 samplings reported PFOA concentrations ranging from 0.294 ng/g to 1.750 ng/g dry weight. Samples for Cleveland reported 2 samples below the LOD and 1 sample below the LOQ. Fifteen sites were sampled around the San Francisco Bay area (2004) with 3 samples reported below the LOQ of 0.011 ng/g with the remainder having a range of 0.136 to 0.625 ng/g. For comparison, two sites in Baltimore, MD were sampled with resultant concentrations of 0.186 and 0.390 ng/g (Higgins et. al., 2005) A single study was reported (Schrap et al. 2004) from the Netherlands in which a range of PFOA for the combination of suspended matter and sediments was reported at < 0.40 ng/g to 24 ng/g. 4.1.4 Sewage Sludge and Effluent Two studies measuring domestic sludge for PFOA have been reported. The first, generated from a survey of eight wastewater treatment plants (WWTP's) had PFOA concentrations (13 samples) ranging from non-detect (MDL = 1.00 ng/g) to a high of 29.4 ng/g (Higgins et. al. 2005). The second study had the highest reported concentration of PFOA in sewage sludge at 244 ng/g (dry weight) in a sample collected near a manufacturing site in the USA (3M 2001). Comparison with 5 other US cities show 2 cities below the reporting limit ( LOQ = 0.20 ng/g) and reported a range of 2.40 to 16.50 ng/g (dry weight). The highest concentration for a non-manufacturing site was in Cleveland with a reported result of 3.1 ng/g dry weight (3M 2001). Sewage sludge studies from Finland & Norway reported PFOA concentrations ranging from less than LOQ (LOQ = 0.20 ng/g) to a maximum of 0.391 ng/g and 0.779 ng/g (wet weight) for Norway and Finland respectively (Kallenborn et al. 2004). Similar to sewage sludge samples, sewage effluent measurements of PFOA were found to correlate to fluorochemical manufacturing locations. The highest value (as with sludge) was near a manufacturing site in Decatur with 2.42 ng/mL being reported for POTW effluent (3M 2001). Lower levels - ranging from 0.001 to 0.675 ng/mL - were detected elsewhere in the USA, Canada, Taiwan, and Nordic countries with the maximum value being reported in both the USA (Cleveland) and Denmark. All sewage effluent samples tested had detectable levels of PFOA. May 23, 2006 Page 50 DuPont-19567 4.1.5 Landfill Effluent The highest reported landfill effluent values were for manufacturing-related landfills and ranged from non-detect (3M 2001) to 3,200 ng/mL (DuPont 2003a). Comparison of public landfill leachates from cities with fluorochemical manufacturing (Decatur, AL; Mobile, AL; Columbus, GA; Pensacola, FL) to control cities (Port St. Lucie, FL) reported a range from (for control) 0.939 ng/mL to 1.03 ng/mL (Port St. Lucie) and for manufacturing sites ranged from non-detect (Pensacola & Mobile) and non quantifiable (Columbus) to a maximum of 48.1 ng/mL (Decatur). Outside the United States, 2 sets of landfill effluent studies have been reported (both from Nordic countries). The range of PFOA concentrations from Espoo, Finland (waste collection for Helsinki, Espoo, Vantaa, and other cities) was 0.300 - 0.399 ng/mL while five sites throughout Norway reported values ranging from ranged 0.091 to 0.516 ng/mL (Kallenborn et al. 2004). 4.1.6 Ground Water Ground water (well) tests are used to monitor PFOA concentrations at a number of manufacturing sites in the USA. Of the almost 800 tests reported, levels of PFOA ranged from not detected to a maximum of 322,000 ng/mL (DuPont. 2003a). Temporal trends (2001 - 2003) for industrial (i.e., Decatur, MN and Cottage Grove, AL) effluent and well water monitoring for PFOA concentration were varied with decreasing trends in effluent PFOA concentration and steady or increasing trends for well water PFOA concentrations being observed. (Santoro 2003). Previous fire-fighting activities that employed aqueous film-forming foams (AFFF's) containing a variety of perfluorinated compounds, including PFOA, have also been shown to impact ground water sources. Fire-fighting training areas have been sampled in both Nevada (NAS Fallon AFB) and Florida (Tyndall AFB, retired) with measurements ranging from below the reporting limit (which decreased from 36 ng/mL in 1999 to 3.0 ng/mL in 2003) to maximums of 116 ng/mL (Tyndall) and 6,570 ng/mL (NAS Fallon AFB) (Moody and Field 1999; Moody et al. 2003). As presented in the case of soil samples, ground water results cannot be considered typical environmental concentrations due to the impacts of manufacturing and fire fighting at these sites. 4.1.7 Fresh Water PFOA in fresh water samples (e.g., lakes, rivers, and streams) has been measured across a variety of geographic locations in Nordic countries, Germany, Japan, Canada and the USA. For moving fresh water sources (i.e., streams, rivers) PFOA concentrations vary greatly depending upon site specifications with the highest concentration being observed during April and May of 2003 near Osaka, Japan. Fifty-two sites were sampled in this area with May 23, 2006 Page 51 DuPont-19567 resultant PFOA concentrations ranging from 0.0045 ng/mL to 67 ng/mL (Saito et. al. 2004). The highest concentrations were observed slightly downstream of a waste disposal site and are not considered ambient concentrations. In North America, the highest stream or river PFOA concentration (11 ng/mL) was observed in the Etobicoke creek after a spill (approx. 22,000 L) of fire retardant foam. However, after a period of 21 days at the same sampling site, the PFOA concentration had dropped to 0.0022 ng/mL (Moody et al. 2002). In addition to the aforementioned incident-related concentrations, fluorochemical manufacturing site samples showed elevated PFOA concentrations for nearby rivers/streams. For instance, of 40 samples tested in November 2000 along the Tennessee River, twenty-two samples (approx 40 miles) upstream of a manufacturing site (located in Decatur, AL) reported PFOA concentration below the reporting limit (MDL = 0.025 ng/mL). Once past the manufacturing site, concentrations steadily increased reaching a maximum (0.598 ng/mL) in the lake formed by Wilson Dam, approx 36 miles downstream (Hansen et al. 2002). River sampling sites located in close proximity to industrial activities in Taiwan (Tseng, et. al. 2006) show elevated levels of PFOA. Two rivers, Tour-Chyan and Nan-Kan, in the northern (Taipei) region reported PFOA concentrations of 0.113 ng/mL and 0.181 ng/mL, respectively. Quiet water sources (i.e., lakes and ponds) exhibited a maximum PFOA concentration of 0.76 ng/mL (reported samples from 1999) being observed in Port St. Lucie, Florida, USA which was not reproducible the following year (0.097 ng/mL, sampling period 2000) (3M 2001). The maximum PFOA concentration for the Great Lakes region was 0.070 ng/mL (Lake Ontario, 2003; Boulanger et. al.,2004). In total, 26 samples from the Great Lakes area have been reported with a range of PFOA from < 0.0003 ng/mL (Simcik & Dorweiler, 2005) to 0.070 ng/mL (Boulanger, et. al. 2004). 4.1.8 Salt Water A variety of marine samples (e.g., oceans, seas, and coastal waters) have been analyzed for PFOA. The highest result (obtained from a sample collected off the Koshien Coast (Japan) was reported to be 0.447 ng/mL (Saito, et al. 2004). The majority of measurements (47/55, 86%) were below 0.010 ng/mL with the lowest result (0.00002 ng/mL) coming from the open Pacific Ocean (Yamashita et al. 2004a). Typical levels near the surface (< 5 m) of the central section of the open oceans reported the overall lowest range of P f O A concentration (0.000015 to 0.000056 ng/mL). As expected, there is a correlation of coastal manufacturing activity with the observed concentration for near-shore measurements. The highest near-shore (within 50 miles) PFOA concentrations were observed to correlate with large industrial cities, namely: Tokyo Bay, 0.154 - 0.192 ng/mL (Tokyo, Japan), Koshien Coast, 0.447 ng/mL (Kobe, Osaka, Sakai, Japan), and the western coast of Korea, 0.320 ng/mL (Seoul, Korea). May 23, 2006 Page 52 DuPont-19567 4.1.9 Plants No studies of PFOA in terrestrial wild plants were identified. Benthic algae from three areas around Lake Michigan were all reported to have PFOA concentrations below the reporting limit of 0.2 ng/g. (Kannan et al. 2005). 4.1.10 Invertebrates Three species of invertebrates were collected in the wild. Amphipods, from three Lake Michigan regions, all exhibited PFOA concentrations below the LOQ (LOQ = 5 ng/g) (Kannan et al, 2005). Mysis and Diporeia samples taken from Lake Ontario (2001) showed a large PFOA variation in reported averages - 2.5 ng/g (Mysis) and 90 ng/g (Diporeia) (Martin et al. 2004a). 4.1.11 Freshwater Fish Over 380 samples of freshwater fish from Nordic countries, Poland, Czech Republic, Canada and the USA have been analyzed for PFOA. Many of the reported results (> 81%) were below the respective reporting limits of these studies. N otropus cornutus E so x lucius S alvelinus alpinus Perca fluviatilis Lota loat C atostom us com m ersoni S alvelinus fontinalis C oregonus clupeaform is S alvelinus nam aycush Lepom is m achrochirus P im ephales prom elas Osm erus m ordax C ottus cognatus Alosa pseudoharengus C yprinus carpio M icropterus salm oides N eogobius m elanostom us M icropterus dolom ieui C arassius gibelio A n gu illa anguilla Salm o trutta C om m on S hiner Pike A rtic char Perch Burbot W hite S ucker Brook Trout Lake W hitefish Lake Trout B luegill Sunfish Fathead M innow R ainbow Sm elt S lim y Sculpin Alew ife C arp Largem outh Bass R ound G obies Sm allm outh Bass G iebel C arp Eel Brown Trout Table 1. Listing of Freshwater Species Covered in this Summary Report May 23, 2006 Page 53 DuPont-19567 The highest detected concentration, (91 ng/g wet weight; Moody et al. 2002), was from the liver of a common shiner downstream of a spill of fire retardant foam containing PFOA. PFOA concentrations were predictably distributed geographically along the spill zone ranging from a low of 6 ng/g upstream of the spill to the high previously mentioned. Of ambient measurements, samples from Lake Ontario (whole body homogenates: Lake Trout; 1.0 ng/g, Sculpin; 44 ng/g, Alewife; 1.6 ng/g, and Smelt; 2 ng/g) and Finland (liver: Pike 0.890 - 1.42 ng/g) reported PFOA concentrations above the lOq (Martin et al. 2004a). 4.1.12 Rain Water A single rain event in Winnipeg, Manitoba, Canada was captured and analyzed in July 2004 (Loewen et al, 2005). PFOA was not detected above the MDL of 0.0072 ng/mL. Rain samples were also collected in the Nordic region in the last quarter of 2003. All six samples tested showed PFOA concentrations above the l O q , ranging from 0.00823 ng/mL (Helsinki) to 0.0168 ng/mL (Rao) (Kallenborn, et. al., 2004). Temporal trends for three USA sites (Maryland, Delaware, New York) show a wide range of PFOA concentrations with a maximum being detected in a 1998 sample from Delaware (0.090 ng/mL) (Scott et al. 2003). Several samples from Maryland during the same time frame also exhibited similar spikes with several being in the 0.030 ng/mL 0.050 ng/mLrange. 4.1.13 Plankton and Shellfish Concentrations of PFOA in homogenate samples of zooplankton, northern shrimp and blunt gaper clams were reported from the Canadian eastern Arctic in 2002 (clams & zooplankton) and 2000-2001 (shrimp). Zooplankton concentrations (5 samples) ranged from 1.75 ng/g to 3.42 ng/g with an average of 2.58 ng/g. In comparison, only 1 of the 7 shrimp samples (14%) was above the MDL of 0.200 ng/g with a value of 0.520 ng/g. All 5 clam samples collected in the same region as the zooplankton were below the MDL. Similarly, 77 oysters sampled from the Gulf of Mexico and the Chesapeake Bay, had PFOA levels below the limit of quantification of <19 ng/g (Giesy and Kannan 2001 as summarized in APME 2002). Recent analysis of oysters from Taiwan (Tseng et. al, 2006), showed significantly higher levels of PFOA with concentrations ranging from 130 ng/g (muscle) to 180 ng/g (homogenate). Crayfish and zebra mussel samples from 3 Lake Michigan regions were reported to have PFOA levels below the MDL of 0.200 ng/g, crayfish and the LOQ of 5 ng/g, zebra mussels (Kannan et. al. 2005). May 23, 2006 Page 54 DuPont-19567 4.1.14 Saltwater Fish Over 33 species of saltwater fish have been sampled for PFOA and are included in this paper. The geographic distribution of samples is quite diverse and ranges from the Baltic and Mediterranean Seas, North Pacific Ocean, to the coasts of the Canadian Arctic, Belgium, Colombia and Antarctica. Historically, most results were below the limits of quantification. However, recent advances in both instrumental and laboratory methodologies provide a greater ability to quantify PFOA levels in fish samples. The highest level of PFOA was detected in a liver samples with all other biological matrices (muscle, plasma) reported below the LOQ or MDL. Less than 9 percent of the samples reported were above the LOQ and, of those, the highest concentrations were sampled near Denmark (Herring, 5.4 ng/g wet weight; Kallenborn et al. 2004), and the eastern Canadian Arctic (Redfish, 5.3 ng/g wet weight; Tomy et al. 2004). Platichthys flesus F lo u n d e r Zoarces viviparous E e lp o u t C lupea harengus H erring M yoxocephalus scorpius Shorthorn Sculpin Lim anda lim anda Dab H ippoglossoides platessoides Long-rough Dab G adus m orhua A tlantic Cod Thunnus thynnus Bluefin Tuna X iphias gladius Sw ordfish Salm o salar A tla ntic Salm on M yoxocephalus scorpioides A rctic Sculpin S ebastes m entella D eepw ater R edfish B oreogadus saida A rtic Cod O ncorhynchus tshaw ytscha C hinook Salm on Thunnus albacares Y ellow -fin Tuna Lateolabrax japonicus Seabass C onger m yriaster Conger Eel P leuronectiform es pleuronectidae F la tfis h Sebastiscus m arm oratus Japanese S tingfish S ebastes inerm is R o c k fis h A canthopgrus schlegeli B lack Seabream Trachurus japonicus Japanese Scad Argyrosom us argentatus W hite C roaker Tham naconus m odestus Black Scraper S tephanolepis cirrhifer F ile fis h Konosirus punctatus G izzard Shad Liza haem atocheila R edlip M ullet Pagrus m ajor Red Seabream A canthopagrus schlegeli Y ellow fin S eabream P aralichtys olivaceus Lefteye Flounder C aran x ignobilis G iant Trevally T ropidinius am oenus O rnate Jobfish N em atalosa com e Perth H erring Table 2. Listing of Saltwater Species Covered in this Summary Report May 23, 2006 Page 55 DuPont-19567 4.1.15 Reptiles Plasm a sam ples from loggerhead and Kem p's ridley sea turtles along the southeastern coast of the U SA w ere sam pled during 2003 and analyzed for PFO A (Keller et al. 2004). The mean result for the 73 loggerhead turtles was 3.2 ng/mL and 3.57 ng/mL for the 6 K em p's ridley turtles. W hile m ean results differed by only 10% , the variability in the range of the 2 species was significantly greater being 0.493 - 8.14 ng/mL and 2.77 4.25 ng/mL for loggerhead and Kem p's ridley respectively. In com parison, snapping turtles ( 5 sam ples, plasm a) & yellow-blotched m ap turtles (6 sam ples, liver)] w ere sam pled in the 199 0 's (G iesy e t a l 2 0 0 1 ) in M ichigan and Mississippi (respectively). The PFO A concentration for both sample groups was found to be below the LOQ (l O q range 2.5 ng/g to 180 ng/g). Lepidochelys kem pii K em p's ridley sea Turtle C aretta caretta Loggerhead Turtle C helydra serpentina Snapping Turtle G raptem ys flavim aculata Y ellow -blotched M ap Turtle Table 3. Listing of Reptiles Species Covered in this Summary Report May 23, 2006 Page 56 DuPont-19567 4.1.16 Birds Sample information has been compiled on 32 species of birds (see table 4). F ulm arus glacialis Uria aalge Larus crassirostris A nas poecilorhyncha Larus ridibundus M ilvus lineatus A rdea cinerea Phalacrocorax carbo C epphus grylle H aliaeetus albicilla G avia im m er Larus hyperboreus Rissa tridactyla Lim osa lapponica Larus canus P odiceps nigricollis S terna hirundo C alidris tenuirostris Tringa nebularia Larus argentatus C rocethia alba Egretta garzetta P halacrocorax auritus S tercorarius m accorm icki Larus delaw arensis P hoebastria nigripes Pelecanus occidentalis H aliaeetus leucocephalus Corvus corone A nas platyrhynchos A nas acuta A nas platyrhynchos var. dom estica Fulm ar G uillem ot Black-tailed G ull Spot-billed D uck B lack-headed G ull Black-eared Kite G ray Heron Com m on Corm orant Black G uillem ot W hite-Tailed Eagle Common Loon G laucous G ulls B lack legged Kittiw ake B ar-tailed G odw it C om m on G ull Black-necked G rebe Com m on Tern G reat Knot G re e n sh a n k H erring G ull S a n d e rlin g Little E gret D ouble-C rested C orm orant Polar Skua R ing-billed G ull Black-footed Albatross Brow n Pelican Bald Eagle C arrion C orw M allard D uck Pintail D uck D om estic D uck Table 4. Listing of Bird Species Covered in this Summary Report Of the 32 species of birds (over 1700 samples), the highest concentration of PFOA was reported in cormorant samples taken in 1997 along the Mediterranean (450 ng/g, Kannan et al. 2002b) and was likely related to the close proximity of the sampling sites to a fluoro-based manufacturing site. Overall, the highest (100-450 ng/g) concentrations were found in liver samples with the remainder of reports (encompassing a broad set of biological matrices including: eggs, muscle, plasma, ovaries, and testes) all below the LOQ. May 23, 2006 Page 57 DuPont-19567 It is important to note that the majority of bird samples (> 89%) were below the LOQ of the individual study and the aforementioned value of 450 ng/g sample was treated as an outlier. 4.1.17 Amphibians Only a single report of amphibian studies was found (Giesy et al 2001). Green frog liver was analyzed for PFOA and found to be below the LOQ (2.5 to 180 ng/g). 4.1.18 Mammals Sampling of mammalian tissue can be classified by type (i.e., terrestrial or marine) and by tissue. 4.1.18.1 Terrestrial Mammals A study of Black Cattle from Japan (Guruge et. al. 2004) reported only 12% (2 of 16) of samples at or above the concentration observed in solvent blanks (0.090 ng/mL). In addition, there was no correlation between PFOA concentration and age of the cattle over the range of 9 - 27 months. The highest result for liver samples from mink was reported to be 27 ng/g dry weight (sample source Massachusetts; Giesy and Kannan 2001), whereas the average of 31 samples was 8 ng/g. Similar studies from Illinois, South Carolina, and Louisiana (81 samples) reported only 6% of samples above LOQ with a maximum of 24 ng/g. Similar studies for liver samples from river otters (Giesy and Kannan) reported a maximum concentration of 19 ng/g wet weight (LOQ = 35 ng/g). A manufacturing related study was performed (Hoff et al. 2004) in which wood mice were captured in Blokkersdijk (manufacturing site) and Galgenweel (3 km distance) in Belgium. All of the 42 samples (21 from each location) reported PFOA levels below the MDL of 11 ng/g. 4.1.18.2 Marine Mammals Polar bear samples (liver tissue) have been extensively studied in a variety of locations. A recent circumpolar study (Smithwick et. al. 2005a) of liver samples covering 7 sites reported PFOA concentrations ranging from < LOD of 2.3 ng/g to a high of 57.1 ng/g (wet wt.; South Baffin Island) with the majority (> 85%) of the samples having a level of PFOA above the LOD. Seal samples have been broadly studied across a variety of locations for 7 seal species. Liver tissue samples were the only tissue matrix that were reported to have PFOA concentration(s) above the LOQ. The highest PFOA value for the entire sample population (PFOA concentrations above LOQ) was reported for a harbor seal in Denmark with a value of 5.6 ng/g. May 23, 2006 Page 58 DuPont-19567 Walrus samples from the Eastern Arctic reported a range of PFOA concentrations ranging from < MDL of 0.2 ng/g wet weight) to a high of 0.69 ng/g. (Tomy et. al., 2003) Six species of whales have been studied using liver tissue as the primary sampling medium (2 muscle samples also reported, both < LOD). The highest concentration of PFOA in this group was from a Beluga whale sampled in 1996 with a reported concentration of 2.76 ng/g (wet weight) (Tomy et. al., 2004). Free ranging dolphins present a widely studied group of mammals with tissue samplings from liver, kidney, muscle, and blood. The majority of the samplings were reported below the LOQ. Two study areas have reported concentrations of PFOA > 100 ng/g in blood (Houde et. al., 2005). The first, east of Charleston, South Carolina, had a PFOA range of 4.6 ng/g to 163 ng/g (average of 47 samples equals 44 ng/g). The second area, Delaware Bay, has a reported range of 20 ng/g to 115 ng/g (average for 5 samples equals 72 ng/g). Blood samples taken from the Bermuda region showed significantly smaller concentrations of PFOA, ranging from 0.6 ng/g to 0.9 ng/g. Two porpoise samples from liver were reported (van De Vijver, 2003) below the MDL of 110 ng/g, wet weight. 4.1.19 Environmental Concentrations Uncertainty Current analytical methods make it possible to detect PFOA at low concentrations in a variety of environmental matrices. The first reports of PFOA in environmental samples in 1999 have been followed by reports with continuously improving analytical sensitivity, hence the number of non-detects is being replaced by measurable, but small amounts being detected. Although the total number of environmental samples analyzed is growing, there currently is not enough data in any one matrix with significant sample density to clearly define temporal or geographical trends among the various environmental media (including biota). Continuing studies, which incorporate more defined sampling strategies employing currently available analytical technology, should help define temporal / geographic trends. Considering that PFOA from ECF processes are a mix of linear and branched isomers, it is not clear whether or not the isomers would behave differently in regards to where they are found in the environment. 4.2 Environmental Concentrations Conclusion The data available to date do not seem to indicate that PFOA collects in any environmental media other than the aquatic environment, which appears to be the likely sink. May 23, 2006 Page 59 DuPont-19567 4.3 Environmental Concentrations Literature Cited Additional Literature Cited DuPont-19567 Barton, D.A., Butler, L.E., Zarzecki, C.J., Flaherty, J.M., and Kaiser, M.A. 2006. Characterizing Perfluorooctanoate in Ambient Air Near the Fence Line of a Manufacturing Facility: Comparing Modeled and Monitored Values. J. Air Waste Manage. Assoc. 56:48-55 . Houde, M., Wells, R., Fair, P., Bossart, G., Hohn, A., Rowles, T., Sweeney, J., Solomon, K., Muir, D. 2005. Polyfluoroalkyl Compounds in Free-Ranging Bottlenose Dolphins (Tursiops truncates) from the Gulf of Mexico and the Atlantic Ocean. Environ. Sci. Technol. 39(17): 6591-6598. Loewen, M., Halldorson, T., Wang, F., Tomy, G., Fluorotelomer Carboxylic Acids and PFOS in Rainwater from Urban Center in Canada Environ. Sci. Technol. 39(9): 2944 2951. Olivero-Verbel, J., Tao, L., Johnson-Restrepo, B., Guette-Fernadez, G., Baldiris-Avila, R., O'byrne-Hoyos, I., Kannan, K. 2006. Perfluorooctanesulfonate and related fluorochemicals in biological samples from the north coast of Columbia. Environmental Pollution xx (2005) 1-6 [In Press] Simcik, M., Dorweiler, K. 2005. Ratio of Perfluorochemical Concentrations as a Tracer of Atmospheric Deposition to Surface Waters, Environ. Sci. Technol. 39(22): 8678 8683. Tseng, C., Liu, L., Chen, C., Ding, W., 2006. Analysis of perfluorooctanesulfonate and related fluorochemicals in water and biological tissue samples by liquid chromatography-ion trap mass spectrometry, J. Chromatogr. A 1105(2006) 119-126. Literature Cited fo r DuPont-17709 3M. 2001. Environmental Monitoring - Multi-City Study: Water, Sludge, Sediment, POTW Effluent and Landfill Leachate Samples. Executive Summary. U.S. Environmental Protection Agency Administrative Record 226-1030a111. June 25. Association of Plastic Manufacturers in Europe. 2002. The Occurrence of Perfluorooctanoate in Environmental, Dietary and Human Samples. U.S. Environmental Protection Agency Administrative Record 226-1055. January 11. Berger, U., Jarnberg, U., and Kallenborn, R. 2004. Perfluorinated alkylated substances (PFAS) in the European Nordic environment. Organohalogen Compounds 66:4046 4052. May 23, 2006 Page 60 DuPont-19567 Bossi, R., Riget, F.F., Dietz, R., Sonne, C., Fauser, P., Dam, M., and Vorkamp, K. 2005. Preliminary screening of perfluorooctane sulfonate (PFOS) and other fluorochemicals in fish, birds and marine mammals from Greenland and the Faroe Islands. Environ. Pollut. 136(2): 323-329. Boulanger, B., Vargo, J., Schnoor, J.L., and Hornbuckle, K.C. 2004. Detection of perfluorooctane surfactants in Great Lakes water. Environ. Sci. Technol. 38(15): 4064 4070. Caliebe, C., Gerwinski, W., Huhnerfuss, H., and Theobald, N. 2004. Occurrence of perfluorinated organic acids in the water of the North Sea. Organohalogen Compounds 66: 4074-4078. Corsolini, S. and Kannan, K. 2004. Perfluorooctanesulfonate and related fluorochemicals in several organisms including humans from Italy. Organohalogen Compounds 66: 4079-4085. De Silva, A.O. and Mabury, S.A. 2004. Isolating isomers of perfluorocarboxylates in polar bears (Ursus maritimus) from two geographical locations. Environ. Sci. Technol. 38(24): 6538-6545. DuPont. 2002. Two-mile Radius Survey and C-8 Sampling Report. U.S. Environmental Protection Agency Administrative Record 226-1235. December. DuPont. 2003a. February 2003; Surface Water Monitoring Report for Washington Works Facility and Local, Letart and Dry Run Landfills; Washington, WV. U.S. Environmental Protection Agency Administrative Record 226-1508. April. DuPont. 2003b. DuPont Telomer Manufacturing Sites: Environmental Assessment of PFOA Levels in Air and Water. U.S. Environmental Protection Agency Administrative Record 226-1534. September. DuPont. 2003c. Sampling Investigation Results Little Hocking Water Association Well Field Washington County, Ohio. U.S. Environmental Protection Agency Administrative Record 226-1509. April. DuPont. 2005. Personal communication from Andrew S. Hartten, Project Director, DuPont Corporate Remediation Group. Giesy, J.P. and Kannan, K. 2001. Global distribution of perfluorooctane sulfonate in wildlife. Environ. Sci. Technol. 35(7): 1339-1342. Guruge, K.S., Taniyasu, S., Miyazaki, S., Yamanaka, N., and Yamashita, N. 2004. Age dependent accumulation of perfluorinated chemicals in beef cattles. Organohalogen Compounds 66: 4029-4034. May 23, 2006 Page 61 DuPont-19567 Hansen, K.J., Johnson, H.O., Eldridge, J.S., Butenhoff, J.L., and Dick, L.A. 2002. Quantitative characterization of trace levels of PFOS and PFOA in the Tennessee River. Environ. Sci. Technol. 36(8): 1681-1685. Harada, K., Nakanishi, S., Saito, N., Tsutsui, T., and Koizumi, A. 2005. Airborne perfluorooctanoate may be a substantial source contamination in Kyoto area, Japan. Bull. Environ. Contam. Toxicol. 74(1): 64-69. Higgins, C.P., Field, J.A., Criddle, C.S., and Luthy, R.G. 2005. Quantitative determination of perfluorochemicals in sediments and domestic sludge. Environ. Sci. Technol. 39(11): 3946-3956. Hoff, P.T., Scheirs, J., Van de Vijver, K., Van Dongen, W., Esmans, E.L., Blust, R., and De Coen, W. 2004. Biochemical effect evaluation of perfluorooctane sulfonic acidcontaminated wood mice (Apodemus sylvaticus). Environ. Health. Perspect. 112(6)681-686. Holmstrom, K.E., Jarnberg, U., and Bignert, A. 2005. Temporal trends of PFOS and PFOA in Guillemot eggs from the Baltic Sea, 1968--2003. Environ. Sci. Technol. 39(1): 80-84. Johnson, B., Olivero, J., and Kannan, K. 2004. Perfluorinated Compounds in Fish, Birds and Humans from Colombia. Society of Environmental Toxicology and Chemistry North America Annual Meeting. Abstract PW177. Kallenborn, R., Berger, U., and Jarnberg, U. 2004. Perfluorinated Alkylated Substances (PFAS) in the Nordic Environment. Nordic Council of Ministers, Tromso, Norway. Kannan, K., Choi, J.W., Iseki, N., Senthilkumar, K., Kim, D.H., Masunaga, S., and Giesy, J.P. 2002a. Concentrations of perfluorinated acids in livers of birds from Japan and Korea. Chemosphere 49: 225-231. Kannan, K., Corsolini, S., Falandysz, J., Oehme, G., Focardi, S., and Giesy, J.P. 2002b. Perfluorooctanesulfonate and related fluorinated hydrocarbons in marine mammals, fishes, and birds from casts of the Baltic and the Mediterranean Seas. Environ. Sci. Technol. 36(15): 3210-3216. Kannan, K., Tao, L., Sinclair E., Pastva S., Jude, D., Giesy, P. 2005. Perfluorinated Compounds in Aquatic Organisms at Various Trophic Levels in a Great Lakes Food Chain. Arch. Environ. Contam. Toxicol. 48: 559-566 (2005) Kannan, K., Newsted, J., Halbrook, R.S., and Giesy, J.P. 2002c. Perfluorooctanesulfonate and related fluorinated hydrocarbons in mink and river otters from the United States. Environ. Sci. Technol. 36(12): 2566-2571. May 23, 2006 Page 62 DuPont-19567 Keller, J.M., Kannan, K., Taniyasu, S., Yamashita, N., Day, R., Arendt, M.D., Maier, P.P., Segars, A.L., Whitaker, J.D., and Kucklick, J.R. 2004. Perfluorinated organic compounds in the plasma of juvenile loggerhead and Kemp's ridley sea turtles from the southeastern coast of the U.S. Society of Environmental Toxicology and Chemistry North America Annual Meeting, Portland, Oregon. Abstract 810. Lange, F.T., Schmidt, C.K., Metzinger, M., Wenz, M., and Brauch, H.J. 2004. Determination of perfluorinated carboxylates and sulfonates from aqueous samples by HPLC-ESI-MS-MS and their occurrence in surface waters in Germany. Society of Environmental Toxicology and Chemistry Europe Annual Meeting, Prague. Poster MOPO15/006. Loewen, M., Halldorson, T., Wang, F., Tomy, G., Fluorotelomer Carboxylic Acids and PFOS in Rainwater from Urban Center in Canada Environ. Sci. Technol. 39(9): 2944 2951. Martin, J.W., Whittle, D.M., Muir, D.C., and Mabury, S.A. 2004a. Perfluoroalkyl contaminants in a food web from Lake Ontario. Environ. Sci. Technol. 38(20): 5379-85. Martin, J.W., Smithwick, M.M., Braune, B.M., Hoekstra, P.F., Muir, D.C.G., and Mabury, S.A. 2004b. Identification of long-chain perfluorinated acids in biota from the Canadian Arctic. Environ. Sci. Technol. 38(2): 373-380. Moody, C.A. and Field, J.A. 1999. Determination of perfluorocarboxylates in groundwater impacted by fire-fighting activity. Environ. Sci. Technol. 33(16): 2800-2806. Moody, C.A., Martin, J.W., Kwan, W.C., Muir, D.C., and Mabury, S.A. 2002. Monitoring perfluorinated surfactants in biota and surface water samples following an accidental release of fire-fighting foam into Etobicoke Creek. Environ. Sci. Technol. 36(4): 545-51. Moody, C.A., Hebert, G.N., Strauss, S.H., and Field, J.A. 2003. Occurrence and persistence of perfluorooctanesulfonate and other perfluorinated surfactants in groundwater at a fire-training area at Wurtsmith Air Force Base, Michigan, USA. J. Environ. Monit. 5(2): 341-5. Saito, N., Harada, K., Inoue, K., Sasaki, K., Yoshinaga, T., Koizumi, A. 2004. Perfluorooctanoate and perfluorooctane sulfonate concentrations in surface water in Japan. J. Occup. Health. 46: 49-59. Santoro, M.A. 2003. Submission of Monitoring Data Pursuant to the 3M LOI dated March 13, 2003 and APFO Users LOI dated March 14, 2003. U.S. Environmental Protection Agency Administrative Record 226-1482. August 1. Schrap, S.M., de Voogt, P., van Leeuwen, S.P., and Pijnenburg, A.M.C.M. 2004. Perfluorinated compounds in the Dutch aquatic environment. Society of Environmental Toxicology and Chemistry Europe Annual Meeting, Prague. Poster MOPO15/008. May 23, 2006 Page 63 DuPont-19567 Scott, B.F., Spencer, C., Moody, C.A., Mabury, S.A., Mactavish, D., and Muir, D.C.G. 2003. Determination of perfluoroalkanoic acids in the aquatic environment. Society of Environmental Toxicology and Chemistry North America Annual Meeting, Austin. Poster. Scott, B.F., Spencer, C., Durham, L., Jones, K., Mabury, S.A., Furbui, V., Lakaschus, S. , and Muir D.G. 2005. Perfluoroalkanoic acids in the oceans. Society of Environmental Toxicology and Chemistry Europe Annual Meeting, Lille. Abstract MOP-04/17. Sinclair, E., Taniyasu, S., Yamashita, N., Kannan, K. 2004. Perfluorooctanoic acid and perfluorooctane sulfonate in Michigan and New York Waters. Organohalogen Compounds 66: 4069-4073. Smithwick, M., Mabury, S., Solomon, K., Sonne, C., Martin, J.W., Born, E.W., Dietz, R., Derocher, A.E., Letcher, R.J., Evans, T.J., Gabrielsen, G.W., Nagy, J.,Stirling, I., Taylor, M.K. and D.C.G. Muir. 2005a. Circumpolar study of perfluoroalkyl contaminants in polar bears (Ursus martimus). Environ Sci Technol Environ. Sci. Technol. 39(15): 5517-5523 Smithwick, M., Muir, D.C., Mabury, S.A., Solomon, K.R., Martin, J.W., Sonne, C., Born, E.W., Letcher, R.J., and Dietz, R. 2005b. Perfluoroalkyl contaminants in liver tissue from East Greenland polar bears (Ursus maritimus). Environ. Toxicol. Chem. 24(4): 981-986. So, M.K., Taniyasu, S., Yamashita, N., Giesy, J.P., Zheng, J., Fang, Z., Im, S.H., and Lam, P.K.S. 2004. Perfluorinated compounds in coastal water of Hong Kong, South China and Korea. Environ Sci Technol 38(15): 4056-4063. Tomy, G.T., Budakowski, W., Halldorson, T., Helm, P.A., Stern, G.A., Friesen, K., Pepper, K., Tittlemier, S.A., and Fisk, A.T. 2004. Fluorinated organic compounds in an eastern Arctic marine food web. Environ. Sci. Technol. 38(24): 6475-81. Van de Vijver, K.I., Hoff, P.T., Das, K., Van Dongen, W., Esmans, E.L., Jauniaux, T, Bouguegeau, J.M., Blust, R., and de Coen, W. 2003. Perfluorinated chemicals infiltrate ocean waters: Link between exposure levels and stable isotope ratios in marine mammals. Environ. Sci. Technol. 37(24): 5545-5550. Yamashita, N., Kannan, K., Taniyasu, S., Horii, Y., Okazawa, T., Petrick, G., and Gamo, T. 2004a. Analysis of perfluorinated acids at parts-per-quadrillion levels in seawater using liquid chromatography-tandem mass spectrometry. Environ. Sci. Technol. 38(21): 5522-5528. Yamashita, N., Kannan, K., Taniyasu, S., Horii, Y., Hanari, N., Okazawa, T., and Petrick, G. 2004b. Environmental contamination by perfluorinated carboxylates and sulfonates following the use of fire-fighting foam in Tomakomai, Japan. Organohalogen Compounds 66: 4063-4068. May 23, 2006 Page 64 DuPont-19567 4.4 Environmental Concentrations: Appendix A May 23, 2006 Page 65 Appendix A A n ta rc tic a A tla n tic Ocean Belgium Bermuda Canada D en m a rk Faroe Islands Finland G re e n la n d Iceland India Japan Norway Pacific Ocean R e p u b lic of Korea Sweden T a iw a n United States Green Frog > 03 Environ. Sci. Technol. 35(7): 1339-1342 Samples Max Conc Min Conc Nos ND's Nos NQ's 0 0 0 0 00 00 0 0 00 00 0 0 0 04 90 90 4 Total Samples Max Conc 0 0 0 0 00 00 0 0 00 00 0 0 0 04 90 Min Conc 90 Nos ND's All Concentrations reported as ppb and are rounded upward to nearest integer. Values in red indicate Min & Max Conc at reporting limits 4 Am phibian I May 23, 2006 Page 66 A n ta rc tic a O O OO OO O O Appendix A Arch. Environ. Contam. Toxicol. 48, 559-566 Samples Max Cone Min Cone Nos ND's Nos NQ's Bald Eagle Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Bar-tailed godwit Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Pollut. 136(2): 323-329 Samples Max Cone Min Cone Nos ND's Nos NQ's Black Guillemot Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's Bird Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's A tla n tic O O O O O O O O Ocean Page 67 Belgium o o oo oo o o Canada U! 1 0 (0 01 lO NJ NJ lO oo oo o o o O oo oo o o Faroe o Islands o O oo oo o Finland o O oo oo o o O 15 7 7 15 15 7 7 15 Bermuda o o oo oo o o D enm ark G re e n la n d o oo o o Iceland o O oo oo o o India o O oo oo o o Italy o O oo oo o o Japan o O oo oo o o Norway o O oo oo o o Pacific o Ocean o O oo oo o R e p u b lic o o o of Korea o Oo Sweden o O oo oo o o T a iw a n 19 38 19 19 26 90 90 45 45 90 19 64 3 36 36 3 3 36 36 3 o O oo oo o o United States o o oo o Appendix A Black legged kittiwake Black-eared Kite Environ. Sei. Technol. 38(24): 64756481 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Black-footed Albatross Bird Black-headed Gull May 23, 2006 O OO OO A tla n tic O Ocean Page 68 O OO OO A n ta rc tic a O o oo o oo o oo o oo o oo o oo o oo o oo OO OO oo oo oo oo oo oo oo oo oo oo o oo oo oo oo oo o Belgium o oo Bermuda o oo Canada o * O O OO D enm ark O oo Faroe O Islands oo Finland O oo G re e n la n d O oo Iceland O oo India O o oo oo Italy o o oo oo Japan o |0 |0 |0 |0 o Norway o oo Pacific o Ocean oo R e p u b lic o of Korea oo o o oo 2 21 19 1 2 21 19 1 5 36 36 5 5 36 36 5 o oo o o oo o oo 22 90 90 22 22 90 90 22 Sweden o oo T a iw a n o oo United o States oo oo Appendix A Black-necked grebe Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Black-tailed Gull Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Brown Pelican Total Samples Max Cone Min Cone Nos ND's Nos NQ's Bird Common C orm ora nt Chemosphere 49: 225-231 May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's A tla n tic O O O O O O O O Ocean Page 69 A n ta rc tic a OO OO O OO O Belgium oo oo o oo o Bermuda oo oo o oo o Canada oo oo o oo o D enm ark oo oo o oo o Faroe o o o o o o o o Islands Finland oo oo o oo o G re e n la n d oo oo o oo o Iceland oo oo o oo o India oo oo o oo o Italy oo oo o oo o Japan o O (0 (0 0 o o o Norway oo oo o oo o Pacific o o o o o o o o Ocean R e p u b lic of Korea oo o 2 36 36 2 2 36 36 2 22 9 19 36 16 36 14 9 8 24 15 90 90 90 90 14 9 32 15 46 24 90 90 16 36 28 18 40 15 2 90 90 2 2 90 90 2 Sweden oo oo o oo o T a iw a n oo oo o oo o United o o o o o States o Appendix A Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Common Cormorant Organohaloge n Compounds 66: 4079-4085 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Common gull Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Common Loon Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's Bird Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's A tla n tic O O O O O O O O Ocean Page 70 A n ta rc tic a O O OO OO O O Belgium o o oo oo o o Bermuda o o oo oo o o Canada lO N N U1 oi ro ro oi oo oo o o D enm ark O o oo oo o o Faroe O o o o o o o o Islands Finland O o oo oo o o G re e n la n d O o oo oo o o Iceland O o oo oo o o India O o oo oo o o Italy O o oo o Japan o Oo oo Norway o 12 90 90 12 12 450 29 12 24 450 29 24 oO CD CD O o oO o oO o 3 36 36 3 3 36 36 3 Oo oo Pacific o Ocean Oo oo R e p u b lic O o o of Korea Oo o Sweden o Oo oo oO o T a iw a n o Oo oo oO o United o States 00 CD CD O O 00 CD CD o 00 O O 00 o oO o A n ta rc tic a O Appendix A Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Common tern Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Double-Crested Cormorant Total Environ. Pollut. 136(2): 323-329 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's F u lm a r Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Bird Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's OOO OOO OO OO OO OO A tla n tic O Ocean Page 71 ooo oo oo o oo oo oo U! 1 0 ( 0 01 o oi to to a t COD COD COD COD o o ooo oO Oo O Oo 18 7 7 18 20 7 1 38 Belgium o Bermuda o Canada o D enm ark o o ro o ooo Faroe o Islands Finland o oO Oo G re e n la n d o ooo oO Oo Iceland o ooo oO Oo India ooo oO Oo o Italy o ooo oO Oo ooo oO Oo Japan o Norway o ooo oO Oo Pacific o Ocean ooo oO Oo R e p u b lic of Korea ooo oO O ooo oo Oo Sweden o T a iw a n o United o States 1 36 36 1 1 36 36 1 9 90 90 9 9 90 90 9 ooo oo Oo ooo oo Appendix A Environ. Sei. Technol. 39(19): 74397445 Samples Max Cone Min Cone Nos ND's Nos NQ's Glaucous gulls Environ. Sei. Technol. 38(24): 64756481 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Gray Heron Total Samples Max Cone Min Cone Nos ND's Nos NQ's Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Great knot Total Samples Max Cone Min Cone Nos ND's Nos NQ's Bird Greenshank Chemosphere 49: 225-231 May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's OO OO A tla n tic O O O O Ocean Page 72 OO OO A n ta rc tic a OO O O Belgium oo o o oo oo Bermuda oo o o oo oo Canada o oo oo o CO O O * CO O O * D enm ark oo o o oo oo Faroe o o o o Islands oo oo Finland oo o o oo oo G re e n la n d oo o o oo oo Iceland oo o o oo oo India oo o o oo oo Italy oo o o oo oo Japan ooo oo o Norway CO o oo oo o CO CO oo o CO o 2 19 19 2 2 19 19 2 3 36 36 3 Pacific o o o o Ocean oo oo R e p u b lic o o o o of Korea CO CO CO CO -- o> o> - - a> O) .-- o Sweden oo o o oo oo T a iw a n oo o o oo oo United o o o o States oo oo Appendix A Greenshank Total Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's G u illem ot Total Samples Max Cone Min Cone Nos ND's Nos NQ's Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Herring Gull Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Little egret Bird Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's A tla n tic Page 73 O Ocean O OO O OO O A n ta rc tic a O OO O OO OO Belgium o oo o oo oo Bermuda o oo o oo oo Canada o oo o oo oo D enm ark o oo o oo oo Faroe o Islands o oo o oo o Finland o oo o oo oo G re e n la n d o oo o oo oo Iceland o oo o oo oo India o oo o oo oo Italy o oo o oo oo Japan o oo o oo oo Norway o oo o oo oo Pacific o Ocean o oo o oo o R e p u b lic of Korea Sweden o T a iw a n o oo o oo oo o oo 3 36 36 3 18 2 2 18 18 2 2 18 10 36 36 10 10 36 36 10 4 36 36 4 4 36 36 4 o oo o o oo oo o 4 90 90 4 4 90 90 4 United o States A tla n tic o Ocean Appendix A Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Polar Skua Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Ring-billed Gull Total Samples Max Cone Min Cone Nos ND's Nos NQ's Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's S a n d e rlin g Total Samples Max Cone Min Cone Nos ND's Nos NQ's Chemosphere 49: 225-231 Samples Max Cone Min Cone Nos ND's Nos NQ's Bird Spot-billed D uck Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's 2 90 90 2 2 90 90 2 Page 74 A n ta rc tic a O O o o o o o o o o o o o o o o o o OO OO oo oo oo oo oo oo oo oo oo oo o oo oo o oo oo oo OO OO oo oo oo oo oo oo oo oo oo oo oo oo oo o oo oo o O Oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo o Belgium o Bermuda o Canada o D enm ark o Faroe o Islands Finland o G re e n la n d o Iceland o India o Italy o Japan o Norway o Pacific o Ocean R e p u b lic o of Korea 3 90 90 3 3 90 90 3 2 36 36 2 2 36 36 2 2 19 16 1 1 2 19 16 1 1 Sweden o T a iw a n o United o States Appendix A Environ. Sei. Technol. 38(20): 53795385 Samples Max Cone Min Cone Nos ND's Nos NQ's A le w ife Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's Arctic Sculpin Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Artie char Fish Artie Cod Total Environ. Sei. Technol. 38(24): 64756481 May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's A n ta rc tic a OO OO O OO O A tla n tic O O O O O O O O Ocean Page 75 Belgium oo oo o oo o Bermuda oo oo o oo o Canada oo o o o o D enm ark oo oo o oo o Faroe o Islands o ww oo Finland oo oo o oo o G re e n la n d O! O O C)T o oo o oo o Iceland oo oo o oo o India oo oo o oo o Italy oo oo o oo o Japan oo oo o oo o Norway oo oo o oo o Pacific o o o o o o o o Ocean R e p u b lic o o o o o o o o o f Korea Sweden oo oo o oo o T a iw a n oo oo o oo o United States oo oo o o Appendix A Artie Cod Total Samples Max Cone Min Cone Nos ND's Nos NQ's Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Atlantic Cod Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Bluefin Tuna Organohaloge n Compounds 66: 4079-4085 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's Brook Trout Fish Organohaloge n Compounds 66: 4069-4073 May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's OO O OO A tla n tic O Ocean Page 76 O OCD COD 00 00 O 00 COD COD 00 O A n ta rc tic a O O O o o o o o o o o o o o o o o o o oO o Oo oO o Oo O o Oo oO o Oo oO o Oo oO o Oo oO o Oo oO o Oo O O o o o o o o o o o o o o o o o o Belgium o Bermuda o Canada o D enm ark o Faroe Islands o Finland o G re e n la n d O l O O 05 Iceland o India oO o Oo o Italy o Oo o Japan oo o oo o Norway oo o oo o Pacific Ocean oo o oo o 16 1 1 16 16 1 1 16 14 72 3 14 14 72 3 14 23 72 72 23 R e p u b lic of Korea oo o oo o Sweden oo oo o T a iw a n oo o oo o United States oo o oo o Appendix A Brook Trout Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Brown Trout Total Samples Max Cone Min Cone Nos ND's Nos NQ's Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Burbot Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Carp Organohaloge n Compounds 66: 4069-4073 Samples Max Cone Min Cone Nos ND's Nos NQ's Fish Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's O OO Page 77 O OO O O o o o o o o o o o o o o o o o o o oo o oo o oo o oo o oo o oo o oo o oo OO OO oo oo oo oo oo oo oo oo oo oo oo o oo oo oo oo o O O o o o o o o o o o o o o o o o o A n ta rc tic a O A tla n tic O Ocean Belgium o Bermuda o Canada D enm ark o Faroe o Islands Finland o G re e n la n d o Iceland o India o oo o Italy o o oo Japan o o oo Norway o oo Pacific o Ocean o oo R e p u b lic o of Korea o oo Sweden o o oo T a iw a n o o oo United States -i, (D (D -a. O OOO o 23 72 72 23 23 90 90 23 23 90 90 23 10 72 72 10 10 20 90 72 10 20 Appendix A Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Chinook Salmon Organohaloge n Compounds 66: 4069-4073 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Dab Total Samples Max Cone Min Cone Nos ND's Nos NQ's D eepwater Redfish Environ. Sei. Technol. 38(24): 64756481 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Fish Eelpout Nordic Council of Ministers, Tromso, Norway May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's A tla n tic O O O O O O O O Ocean Page 78 A n ta rc tic a OO OO OO O O Belgium oo oo oo o o Bermuda oo oo oo o o Canada oo oo oo o o D enm ark o oo oo o o Faroe o o o w w w w o o o Islands Finland oo oo oo o o G re e n la n d o Ot O Ot '4 Ol O Ol -4 o oo o o Iceland oo oo oo o o India oo oo oo o o Italy oo oo oo o o Japan oo oo oo o o Norway oo oo oo o o Pacific o o o o o o o o Ocean R e p u b lic o o o o o o o o o f Korea Sweden oo oo oo o o T a iw a n oo oo oo o o United States oo oo o 12 90 90 12 12 72 72 12 12 24 90 72 12 24 Appendix A Eelpout Total Samples Max Cone Min Cone Nos ND's Nos NQ's Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Flounder Total Samples Max Cone Min Cone Nos ND's Nos NQ's Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Herring Total Samples Max Cone Min Cone Nos ND's Nos NQ's J. Chromatogr. A 1105(2006) 119-126 Samples Max Cone Min Cone Nos ND's Nos NQ's Japanese Seaperch Fish Lake Trout Total Environ. Sei. Technol. 38(20): 53795385 May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's OO OO Page 79 OO OO OO OO oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo o o oo oo oo oo oo oo o 0 1 0 1 -1 0 1 0 1 -1 oo oo oo oo oo oo oo oo O O o o o o o o o o o o o o o o o o A n ta rc tic a O A tla n tic O Ocean Belgium o Bermuda o Canada o D enm ark Faroe o Islands Finland o G re e n la n d o Iceland o India oo oo o Italy o oo oo Japan o oo oo Norway o oo oo Pacific o Ocean oo oo R e p u b lic o of Korea oo oo Sweden o oo oo T a iw a n o 3 340 340 3 340 340 o oo United o States oo oo A tla n tic O O O O O O O Ocean Appendix A Lake Trout Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's Organohaloge n Compounds 66: 4069-4073 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Lake Whitefish Fish May 23, 2006 Page 80 Belgium o o o oo o o Canada 12 72 72 12 2 14 72 2 12 4 A n ta rc tic a O O O OO O O Bermuda o o o oo o o o o D enm ark o o o oo o o Faroe o o o o o o o Islands Finland o o o oo o o G re e n la n d o o o oo o o Iceland o o o oo o o India o o o oo o o Italy o o o oo o o Japan o o o oo o o Norway o oooo Pacific o o o o o o o Ocean R e p u b lic o o o o o o o o f Korea Sweden o o o oo o o T a iw a n o o o oo o o United o States oo o 12 90 90 12 12 90 90 12 Appendix A Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Long-rough dab Total Samples Max Cone Min Cone Nos ND's Nos NQ's Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Perch Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's Pike Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Fish Rainbow Smelt Total Environ. Sei. Technol. 38(20): 53795385 May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's A n ta rc tic a O OO O OO O oo o oo o oo oo o oo o o Ol Ol oo o oo o oo o oo o oo o o oo o oo o oo o oo o oo OO OO oo oo o oo oo oo oo oo oo oo oo o oo oo o oo oo OO A tla n tic O Ocean Page 81 OO Belgium o oo Bermuda o oo Canada o oo D enm ark o oo Faroe o Islands oo Finland o oo G re e n la n d o oo Iceland o Ol Ol Ol Ol India oo o Italy o oo Japan o oo Norway o o Pacific o Ocean oo R e p u b lic o of Korea oo Sweden o o T a iw a n o oo United o States oo A n ta rc tic a O O OO OO OO Appendix A R a in b o w S m elt Total Samples Max Cone Min Cone Nos ND's Nos NQ's Arch. Environ. Contam. Toxicol. 48, 559-566 Samples Max Cone Min Cone Nos ND's Nos NQ's Round Gobies Total Samples Max Cone Min Cone Nos ND's Nos NQ's J. Chromatogr. A 1105(2006) 119-126 Samples Max Cone Min Cone Nos ND's Nos NQ's Seabass Total Environ. Pollut. 136(2): 323-329 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Shorthorn Sculpin Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Fish Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's A tla n tic Page 82 O Ocean O O OO OO O Belgium o o oo oo oo Canada o o oo oo oo Faroe o Islands o o oo oo o Finland o o oo oo oo o o oo o 15 7 7 15 15 7 7 15 Bermuda o o oo oo oo D enm ark o o oo oo oo G re e n la n d o Iceland o oo oo o India o o oo oo oo Italy o o oo oo oo Japan o o oo oo oo Norway o o oo oo oo Pacific o Ocean o o oo oo o R e p u b lic o of Korea o o oo oo o Sweden o o oo oo oo T a iw a n o ooo o 3 340 340 o 12 0 0 12 12 0 0 12 3 340 340 United States o o oo o Appendix A Environ. Sei. Technol. 38(20): 53795385 Samples Max Cone Min Cone Nos ND's Nos NQ's Slim y Sculpin Total Samples Max Cone Min Cone Nos ND's Nos NQ's Arch. Environ. Contam. Toxicol. 48, 559-566 Samples Max Cone Min Cone Nos ND's Nos NQ's Smallmouth Bass Total Samples Max Cone Min Cone Nos ND's Nos NQ's Organohaloge n Compounds 66: 4079-4085 Samples Max Cone Min Cone Nos ND's Nos NQ's S w o rd fis h Total Samples Max Cone Min Cone Nos ND's Nos NQ's J. Chromatogr. A 1105(2006) 119-126 Samples Max Cone Min Cone Nos ND's Nos NQ's Tilapia Fish Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's A tla n tic O Ocean Page 83 A n ta rc tic a O O O o o o o o o o o o o o o o o o o OO OO oo oo oo oo oo oo oo oo oo o oo oo oo oo oo o oo OO OO oo oo oo oo oo oo oo oo oo o oo oo oo oo oo oo o O O o o o o o o o o o o o o o o o o O O o o o o o o o o o o o o o o o o J.S - Belgium o Bermuda o Canada o D enm ark o Faroe o Islands Finland o G re e n la n d o Iceland o India o Italy o Japan o Norway o Pacific o Ocean 14 2 0 14 14 2 0 14 12 36 3 12 12 36 3 12 6 120 100 6 120 100 R e p u b lic o of Korea Sweden o T a iw a n o United States 66- Appendix A Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's White Sucker Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Fish Yellow-fin Tuna Total Samples Max Cone Min Cone Nos ND's Nos NQ's Arch. Environ. Contam. Toxicol. 48, 559-566 Samples Max Cone Min Cone Nos ND's Nos NQ's A m p h ip o d s Total Environ. Sei. Technol. 38(24): 64756481 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Invertebrate B lunt Gaper Clam Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's O O OO OO OO OO A tla n tic O Ocean Page 84 A n ta rc tic a O o oo oo o oo oo to o o to to o o to o oo o oo oo o oo oo o oo oo o oo oo o oo oo OO OO oo oo o to oo oo oo oo oo oo oo oo oo o oo oo oo oo Belgium o Bermuda o Canada to D enm ark o Faroe o Islands Finland o G re e n la n d o Iceland o India o oo oo o Italy o o oo oo Japan o o oo oo Norway o o oo oo Pacific o Ocean o oo o 12 90 90 12 12 90 90 12 R e p u b lic o of Korea o oo oo Sweden o o oo oo T a iw a n o o o oo oo United o States o to Ol Ol to W Ol Ol to o Appendix A Arch. Environ. Contam. Toxicol. 48, 559-566 Samples Max Cone Min Cone Nos ND's Nos NQ's C ra y fis h Total Environ. Sei. Technol. 38(20): 53795385 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Diporeia Total Environ. Sei. Technol. 38(24): 64756481 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Greenland Smoothcockle clam Total Environ. Sei. Technol. 38(20): 53795385 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Invertebrate M ysis Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's A n ta rc tic a O O O o o o o o o o o o o o o o o o o w - OO O OO O oo o oo o o CO O O CO CO O O CO oo o oo o oo o oo o oo o O O o o o o o o o o o o o o o o o o CD CD o o - OO A tla n tic O Ocean Page 85 OO Belgium o oo Bermuda o oo Canada o oo D enm ark o oo Faroe o Islands oo Finland o oo G re e n la n d o oo Iceland o oo India oo o oo o Italy o oo o oo Japan o oo o oo Norway o oo o oo Pacific o Ocean oo o oo R e p u b lic o of Korea oo o oo Sweden o oo o oo T a iw a n o oo o oo United w w - o o CD CD o o - CO O O CO CO O O CO S ta te s Appendix A Environ. Sei. Technol. 38(24): 64756481 Samples Max Cone Min Cone Nos ND's Nos NQ's Northern Shrimp Total Samples Max Cone Min Cone Nos ND's Nos NQ's J. Chromatogr. A 1105(2006) 119-126 Samples Max Cone Min Cone Nos ND's Nos NQ's Oyster Total Samples Max Cone Min Cone Nos ND's Nos NQ's Arch. Environ. Contam. Toxicol. 48, 559-566 Samples Max Cone Min Cone Nos ND's Nos NQ's Invertebrate Zebra mussel Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's Mammal Arctic Fox Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's OO OO OO Page 86 OO OO OO oo oo oo oo oo oo 10 2 2 10 10 2 2 10 O O o o o o o o o o o o o o o o o o o oo oo oo oo oo oo oo oo oo oo oo oo oo o Ol -* -4 A n ta rc tic a O A tla n tic O Ocean Belgium o Bermuda o Canada o D enm ark o Faroe o Islands Finland o G re e n la n d Ol O -x -4 Iceland O India O Italy o Japan o Norway o Pacific o Ocean R e p u b lic o of Korea Sweden o T a iw a n o United o States oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo o o 12 180 130 12 180 130 o 05 Ol Ol O) 05 Ol Ol 05 o oo Appendix A Beluga Whale Environ. Sei. Technol. 38(24): 64756481 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Environ. Sei. Technol. 36(12): 25662571 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 39(17): 65916598 Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Organohaloge n Compounds 66: 4079-4085 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Bottlenose Dolphin Mammal A tla n tic O Ocean O O OO 5 90 90 5 5 90 90 5 May 23, 2006 Page 87 A n ta rc tic a O O O O OO O Belgium o o o o oo o Bermuda o oo oo Canada o o o o o - Ol - W Ol D enm ark o o o o oo o Faroe o o o o o o o Islands Finland o o o o oo o G re e n la n d o o o o oo o Iceland o o o o oo o India o o o o oo o Italy o o oo o Japan w - o o o w - o o Norway o o o o oo o Pacific o o o o o o o Ocean 107 72 6 10 72 3 6 10 107 72 72 36 6 R e p u b lic o o o o o o o o f Korea Sweden o o o o oo o T a iw a n o o o o oo o United o States oo oo Appendix A California Sea Lion Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Organohaloge n Compounds 66: 4079-4085 Samples Max Cone Min Cone Nos ND's Nos NQ's Common Dolphin Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Elephant Seal Total Samples Max Cone Min Cone Nos ND's Nos NQ's Organohaloge n Compounds 66: 4079-4085 Samples Max Cone Min Cone Nos ND's Nos NQ's Mammal Fin Whale Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's O O OO OO A tla n tic O Ocean Page 88 A n ta rc tic a O o oo o oo o oo o oo o oo o oo o oo o oo OO OO oo oo oo oo oo oo oo oo oo o oo oo o oo oo oo oo OO OO oo oo oo oo oo oo oo oo oo o oo oo o 0 5 COD COD 0 5 oO oO oO oO Belgium o Bermuda o Canada o D enm ark o Faroe o Islands Finland o G re e n la n d o Iceland o India o oo o Italy o CwO CwO --` CCOO CCOO - k o o oo Japan o Norway o 6 90 90 6 2 38 38 2 2 38 38 2 5 90 90 5 5 90 90 5 o oo Pacific Ocean oo o oo o oo R e p u b lic o of Korea Sweden o T a iw a n o United o States o oo o oo Appendix A Ganges R iver Dolphin Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Environ. Sei. Technol. 37(24): 55455550 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Gray Seal Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Total Environ. Sei. Technol. 37(24): 55455550 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Mammal H arbor Porpoise Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's A tla n tic O Ocean 12 110 110 12 12 110 110 12 2 110 110 2 2 110 110 2 Page 89 OO O Belgium o oo o o oo o 12 90 90 12 12 90 90 12 A n ta rc tic a O OO O O OO O Bermuda o oo o o oo o Canada o oo o oo D enm ark o oo o o oo o Faroe o o o o o o o o Islands Finland o oo o o oo o G re e n la n d o oo o o oo o Iceland o oo o o oo o India o oo o o o 2 90 90 2 2 90 90 2 26 90 90 26 26 90 90 26 Italy o oo o oo Japan o oo o o oo o Norway o oo o o oo o Pacific o o o o o o o o Ocean R e p u b lic o o o o o o o o o f Korea Sweden o o - w w - isi w o oo o T a iw a n o oo o o oo o United o o o o o o o o States OO O oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo o O o o o o o o o o o o o o o o o o o oO oo oo oo O O o o o o o o o o o o o o o o o o A n ta rc tic a O A tla n tic O Ocean Belgium o Bermuda o Canada o D enm ark oe^ ^ oe Appendix A Harbor Seal Environ. Sei. Technol. 39(18): 69786984 Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Total Environ. Sei. Technol. 37(24): 55455550 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Hooded Seal OO 2 110 110 2 2 110 110 2 OO Mammal Human May 23, 2006 Page 90 oo oo o o 00 to O 05 Ol 87 6 0 164 Faroe o Islands Finland o G re e n la n d o Iceland o India oo o Italy o oo Japan o oo Norway o oo Pacific o Ocean o R e p u b lic o of Korea oo Sweden o oo 3 90 90 3 3 90 90 3 356 6 2 T a iw a n o oo United o States oo A tla n tic O O O O O O O Ocean Appendix A Human Chemosphere 54: 1599-1611 Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 37(21): 888-891 Samples Max Cone Min Cone Nos ND's Nos NQ's J. Occup. Health. 46: 141-147 Samples Max Cone Min Cone Nos ND's Nos NQ's Organohaloge n Compounds 66: 4079-4085 Samples Max Cone Min Cone Nos ND's Nos NQ's Organohaloge n Compounds 66: 4041-4045 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Organohaloge n Compounds 66: 4029-4034 Samples Max Cone Min Cone Nos ND's Nos NQ's Mammal Japanese Black Cattle May 23, 2006 Page 91 A n ta rc tic a OO O O O O O Belgium oo o o o o o Bermuda oo o o o o o Canada oo o o o o o D enm ark oo o o o o o Faroe o o o o o o o Islands Finland oo o o o o o G re e n la n d oo o o o o o Iceland oo o o o o o India oo o o o o o Italy ooo oo Japan o W O O Ol Norway oo o o o o o Pacific o o o o o o o Ocean R e p u b lic o o o o of Korea o 360 12 0 50 3 3 50 50 360 3 12 30 50 oo 1,200 88 15 925 1,200 88 15 925 ooo 62 47 8 60 656 47 0 60 o Sweden oo o o o o o T a iw a n oo o o o o o United States o CO O O 00 A n ta rc tic a O OO O O OO Bermuda o oo o o oo O Ocean A tla n tic O O O Appendix A Japanese B lack Cattle Long Finned P ilot Whale Total Environ. Pollut. 136(2): 323-329 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Organohaloge n Compounds 66: 4079-4085 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 36(12): 25662571 Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's M in k OO O Mammal May 23, 2006 Page 92 Belgium o oo o o oo Canada o oo o o oo 30 7 7 30 4 2 0 30 34 7 0 60 Faroe o Islands oo o Finland o oo o o oo Iceland o oo o o oo India o oo o o oo Italy o oo o o Japan 15 0 0 3 2 38 38 2 2 38 38 2 D enm ark o oo o o oo G re e n la n d o oo o o oo o oo o o o Norway o oo o o oo Pacific o oo o o o o Ocean R e p u b lic o oo o o o o of Korea Sweden o oo o o oo T a iw a n o oo o o oo United o o o o o States 112 20 4 16 18 90 90 16 18 Appendix A Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's M in k Total Environ. Pollut. 136(2): 323-329 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 37(24): 55455550 Samples Max Cone Min Cone Nos ND's Nos NQ's Minke whale Nordic Council of Ministers, Tromso, Norway Samples Max Cone Min Cone Nos ND's Nos NQ's Total Environ. Sei. Technol. 38(24): 64756481 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Mammal N a rw h a l Total May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's OO O O OO 11110011 1 110 110 1 Page 93 OO OO O O o o Ol o o o o o o o o o o o o o o A n ta rc tic a O A tla n tic O Ocean Belgium o Bermuda o Canada oo o o oo oo o o oo Ol o o oo D enm ark o oo o o oo Faroe o Islands oo o o oo Finland o oo o o oo G re e n la n d o o Ol S S Ol o o Ol --j --4 Ol o Iceland o o Ol Ol Ol Ol o Oo India oo o o oo o Italy o oo o o oo Japan o oo o o oo Norway o oo o o oo Pacific o Ocean oo o o oo R e p u b lic o of Korea oo o o oo Sweden o oo o o oo T a iw a n o oo o o oo United o States 130 90 4 32 18 oo o oo A n ta rc tic a O O O O OO O A tla n tic O O O O O O O Ocean Appendix A Northern Fur Seal Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Environ. Pollut. 136(2): 323-329 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Toxicol. Chem. 24(4): 981-986 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Samples Max Cone Min Cone Nos ND's Nos NQ's Polar Bear Mammal May 23, 2006 Page 94 Belgium o o o o oo o Canada o CD CD --J o CD CD -4 o oo Faroe O o O o o o o Islands Finland O o O o oo o 10 12 12 10 1 10 10 10 11 12 10 20 Bermuda o o o o oo o D enm ark O o O o oo o G re e n la n d o Oo o Iceland o o O o oo o India o o O o oo o Italy o o O o oo o Japan o o O o oo o Norway o o O o oo o Pacific o o O o o .J.eS- 0CD 0CD -4^X .J.S 0CD 0CD 4i^-- O cean R e p u b lic o o O o oO O of Korea Sweden o o O o oO O T a iw a n o o O o oO O United O States oO oO 17 90 90 17 17 90 90 17 O O o o o o o o o o o o o o o o o o A n ta rc tic a O A tla n tic O Ocean Belgium o Bermuda o Canada o D enm ark o Faroe o Islands Finland o G re e n la n d OO O O O OO O O O Appendix A Ringed Seal Environ. Pollut. 136(2): 323-329 Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 39(19): 74167422 Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 38(2): 373-380 Samples Max Cone Min Cone Nos ND's Nos NQ's Total Environ. Sei. Technol. 36(12): 25662571 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Mammal R iver Otter May 23, 2006 Page 95 oo o o o oo o o o oo 24 90 90 24 19 2 2 33 43 90 2 57 oo o o o oo o o o oo o o o 35 12 7 30 5 75 1 1 105 5 110 12 1 135 10 o oo Iceland o oo o o o India oo o o o o Italy o o 00 COO COO --00^ o 00 OCD OCD --0*0 o Japan o oo o o o Norway o CO CO --^ -i, CD CD -a. o 00 O O 00 o 00 O O 00 o Pacific o Ocean oo o O o R e p u b lic o of Korea oo o O o Sweden o oo o O o T a iw a n o oo o O o United o States ooO o 14 13 8 12 5 90 90 17 Appendix A R iver Otter Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Sea Otter Total Environ. Sei. Technol. 37(24): 55455550 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Sperm Whale Total Environ. Sei. Technol. 37(24): 55455550 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Striped Dolphin Environ. Sei. Technol. 35(7): 1339-1342 Samples Max Cone Min Cone Nos ND's Nos NQ's Mammal Organohaloge n Compounds 66: 4079-4085 May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's A tla n tic O Ocean 1 110 110 1 1 110 110 1 4 110 110 4 4 90 90 4 4 Page 96 O O O A n ta rc tic a O O OO OO OO Belgium o o oo oo oo Bermuda o o oo oo oo Canada o o oo oo oo D enm ark o o oo oo oo Faroe o Islands o o oo oo o Finland o o oo oo oo G re e n la n d o o oo oo oo Iceland o o oo oo oo India o o oo oo oo Italy o o oo oo o 4 72 72 4 Japan o o oo oo oo Norway o o oo oo oo Pacific o o oo o 00 COD COD 00 COD COD 00 o Ocean 00 R e p u b lic o of Korea o o oo oo o Sweden o o oo oo oo T a iw a n o o oo oo oo United o o oo oo o rCoD 0 0 cOd CD S ta te s Appendix A Environ. Sei. Technol. 37(24): 55455550 May 23, 2006 Mammal W hite-sided dolphin W hite-beaked dolphin Ho i- h 0)_ W eddell Seal Ho i- h 0)_ W alrus Ho i- h 0)_ S trip e d Dolphin Ho i- h 0)_ Environ. Sei. Technol. 38(24): 64756481 Environ. Sei. Technol. 35(7): 1339-1342 Environ. Sei. Technol. 37(24): 55455550 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's 4 110 110 4 Page 97 OO o o oo O -i, COD OCD -* O O oo O oo oo oO oO oo oo oO oO oo oo oO oO oo oO oo oO oo oO oo oO oo oO oo oO oo oO oo oO oo oo oo oo oo oo COD OCD O O O O O O O O O O O O O O O o o o O O o o O Ol o o o o o o o o o o o o o o O O o o O - O l o o o o o o o o o o o o o o A n ta rc tic a O A tla n tic 00 COD O 00 O ce a n Belgium O Bermuda O Canada O D enm ark O Faroe o Islands Finland o G re e n la n d o Iceland o India o Italy fc* M IO t* Japan O Norway O Pacific o Ocean R e p u b lic o of Korea Sweden o T a iw a n o United o States Appendix A W hite-sided dolphin Total Samples Max Cone Min Cone Nos ND's Nos NQ's Environ. Health Perspect. 112(6): 681-686 Samples Max Cone Min Cone Nos ND's Nos NQ's Mammal Wood Mice Total Environ. Sei. Technol. 38(24): 64756481 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Plankton Zooplankton Total Samples Max Cone Min Cone Nos ND's Nos NQ's Arch. Environ. Contam. Toxicol. 48, 559-566 Samples Max Cone Min Cone Nos ND's Nos NQ's Plant Benthic algae Reptile Loggerhead Turtle Total Environ. Sci. Technol. 39(23): 91019108 May 23, 2006 Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's A n ta rc tic a O OO OO oo oo oo oo oo oo oo oo OO OO OO OO oo o oo oo o M W lO NO CO lO o oo Oo oo Oo oo Oo oo Oo oo oo O O o o o o o o o o o o o o o o o o A tla n tic Ocean 4 110 110 4 21 110 110 21 21 110 110 21 Page 98 Belgium o Bermuda o Canada o D enm ark o Faroe o Islands Finland o G re e n la n d o Iceland o India oo oo oo o Italy o oo oo oo oo oo oo Japan o Norway o oo oo oo Pacific o Ocean oo oo oo oo oo oo oo oo oo R e p u b lic o of Korea Sweden o T a iw a n o United o States oo oo oo oo .. --<o4 CO O O CO CO O O CO o Appendix A May 23, 2006 Reptile Yellow-blotched Map Turtle Snapping Turtle Loggerhead Turtle Total Environ. Sei. Technol. 35(7): 1339-1342 Total Environ. Sei. Technol. 35(7): 1339-1342 Total Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Samples Max Cone Min Cone Nos ND's Nos NQ's Page 99 OO OO oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo oo CT> OCD OCD CD CD COD COD CD O O o o o o o o o o o o o o o o o o 5 90 90 5 5 90 90 5 A n ta rc tic a OO A tla n tic O O Ocean Belgium oo Bermuda oo Canada oo D enm ark oo Faroe o o Islands Finland oo G re e n la n d oo Iceland oo India oo Italy oo Japan oo Norway oo Pacific o o Ocean R e p u b lic o o of Korea Sweden oo T a iw a n oo United U i* CD S tates Appendix B Distribution of Measurement Type Atlantic Ocean Canada Denmark Faroe Islands Finland Iceland Japan Norway Pacific Ocean South Korea Sweden Taiwan United States C7B4uo:lnl6.t4aE-m6n9vTirooxni.col Nos Min Conc Max Conc Nos ND's Nos NQ's 0 0 0 0 0 0 28 0 0 0 0 0.0000 0.0009 Total 5< Nos Min Conc Max Conc Nos ND's Nos NQ's J11.21C605h(r2o0m0a6t)og1r1.9A Nos Min Conc Max Conc Nos ND's Nos NQ's 0 0 0 0 0 0 28 0 0 0 0 0.0000 0.0009 00000000000 Fresh Water Effluent Total Nos Min Conc Max Conc Nos ND's Nos NQ's 00000000000 Ambient Results only. All Concentrations reported as ppb and are rounded upward if necessary. Values in red indicate Min & Max Conc at reporting limits May 23, 2006 Page 100 0 0 4 0.0008 0.1700 1 4 0.0008 0.1700 1 0 0 0 0 Atlantic Ocean Canada Denmark Faroe Islands Finland Iceland Japan Norway Pacific Ocean South Korea Sweden Taiwan United States Dpendix B T8E6en7cvh8irn-o8on6l..8S33c9i.(22): T4E0en6cvh4irn-o4on0l..7S30c8i.(15): NNMooinrrwidsitaceyrCs,ouTnrocmil soof, ASTCEomonhxcveeiiimcerroiotciynslaomtorgAyfeynnNantoanurldathl Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's 0 0 0 0 0 0 0 0 0 0 0 0 11 0.0001 0.0194 3 0 0 0 0 0 0 0 0 0 0 0 0 16 0.0150 0.0700 3 0000000500000 0.0048 0.0082 0000000000008 0.0023 0.0110 7 3 Total _l<D Nos Min Conc Max Conc Nos ND's Nos NQ's 0 0 0 0 0 0 0 5 0 0 0 0 35 0.0048 0.0001 0.0082 0.0700 7 9 NNMooinrrwidsitaceyrCs,ouTnrocmil soof, Nos Min Conc Max Conc Nos ND's Nos NQ's c Q) 3 n-- Total LU Nos Min Conc Max Conc _lo c Nos ND's as Nos NQ's 0000300600000 0.3000 0.0913 0.3990 0.5160 0000300600000 0.3000 0.0913 0.3990 0.5160 J4.6:O4c9c-u5p9. Health. Nos Min Conc Max Conc Nos ND's Nos NQ's 0000001000000 0.0038 0.0038 Fresh Water o c AUPRd.reSomc.toeinErcditnsiovt2rni2aro6tAin-vg0mee6en7nc0tyal Nos Min Conc Max Conc Nos ND's 0000000000002 0.0250 0.0250 o CL Nos NQ's 2 May 23, 2006 Page 101 Atlantic Ocean Canada Denmark Faroe Islands Finland Iceland Japan Norway Pacific Ocean South Korea Sweden Taiwan United States Dpendix B AUPRd.reSomc.toeinErcditnsiovt2rni2aro6tAin-vg0mee6en7nc2tyal AUPRd.reSomc.toeinErcditnsiovt2rni2aro6tAin-vg0mee6en7nc3tyal Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's 0000000000002 0.0573 0.0631 2 0000000000002 0.0249 0.0270 3 Total o c o CL T2E9en4cv4hir-no2on9l..5S13c9i.(9): Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's 0 00000 100 0006 0.0038 0.0249 0.0038 0.0631 7 0300000000000 0.0072 0.0072 3 Total acTO: Nos Min Conc Max Conc Nos ND's Nos NQ's 0300000000000 0.0072 0.0072 3 NNMooinrrwidsitaceyrCs,ouTnrocmil soof, <D Total to 'gacto: Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's 0 00 0 20 00 0 04 0 0 0.0082 0.0107 0.0131 0.0168 0000200000400 0.0082 0.0107 0.0131 0.0168 AC48roc,nh5t.a5mE9n-.5vT6iro6oxni.col. Nos Min Conc Max Conc Nos ND's Nos NQ's 0000000000004 0.0044 0.0147 Fresh Water > T5E5en2cvh4irn-o5on5l..3S03c9i.(15): <u Nos Min Conc Max Conc Nos ND's 0000000000003 0.0087 0.0087 k Nos NQ's May 23, 2006 Page 102 Atlantic Ocean Canada Denmark Faroe Islands Finland Iceland Japan Norway Pacific Ocean South Korea Sweden Taiwan United States Dpendix B T8E6en7cvh8irn-o8on6l..8S33c9i.(22): TE1e6n8cvh1irn-o1on6l..8S35c6i.(8): J11.21C605h(r2o0m0a6t)og1r1.9A J4.6:O4c9c-u5p9. Health. OC40org6ma9p-n4oo0uh7na3dlosg6e6n: AUPRd.reSomc.toeinErcditnsiovt2rni2aro6tAin-vg0mee6en7nc0tyal AUPRd.reSomc.toeinErcditnsiovt2rni2aro6tAin-vg0mee6en7nc2tyal AUPRd.reSomc.toeinErcditnsiovt2rni2aro6tAin-vg0mee6en7nc3tyal Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's 0000000000001 0.0012 0.0012 0 0 0 0 0 0 0 0 0 0 0 0 18 0.0250 0.0250 18 0000000000060 0.1130 0.1810 0 0 0 0 0 0 129 0 0 0 0 0 0 0.0001 19.4000 0 0 0 0 0 0 0 0 0 0 0 0 24 0.0056 0.0216 18 0000000000006 0.0236 0.0267 18 0000000000006 0.0092 0.0250 24 0000000000006 0.0255 0.0828 24 Fresh Water Total <D > k May 23, 2006 Nos 0 0 0 0 0 0 129 0 0 0 0 6 68 Min Conc 0.0001 0.1130 0.0012 Max Conc 19.4000 0.1810 0.0828 Nos ND's Nos NQ's 102 Page 103 ft) p IC--lL. X dd Atlantic Ocean oo oo oo oo o Canada oo oo oo oo o Denmark Salt Water Fresh Water Bay Wastewater Influent Wastewater Effluent Tap Water Sewage Effluent N o rdic C ouncil of M inisters, Trom so, N orw ay Total J. O ccup. H ealth. 46: 49-59 Total E n viron. Sci. T echnol. 39(15): 5 5 2 4 -5 5 3 0 Total E n viron. Sci. T echnol. 39(15): 5 5 2 4 -5 5 3 0 Total E n viron. Sci. T echnol. 38(21): 5 5 2 2 -5 5 2 8 May 23, 2006 Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Page 104 oo o o o o o o oo o o o CO CO --^ CO CO 5 0.0199 0.0228 5 0.0199 0.0228 o 3 0.0202 0.0225 3 0.0202 0.0225 7 0.0001 0.0400 7 0.0001 0.0400 o oo o oo oo oo o 3 0.1543 0.1920 oo oo oo oo o Faroe Islands Finland Iceland oo oo oo oo o Japan o Norway oo oo oOO Pacific Ocean o o o o o O Oo o South Korea o o o o o O Oo o Sweden o o o o o O Oo o Taiwan o o o o o O Oo o United States 3 0.0220 0.0220 3 0.0220 0.0220 3 0.0040 0.0040 3 3 0.0040 0.0040 3 o O Oo o Dpendix B J11.21C605h(r2o0m0a6t)og1r1.9A J4.6:O4c9c-u5p9. Health. NNMooinrrwidsitaceyrCs,ouTnrocmil soof, Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's 0 0 0 Total C>rc T4E0en5cv6hir-no4on0l6S33c8i(15): T5E5en2cvh2irn-o5on5l..2S83c8i.(21): J4.6:O4c9c-u5p9. Health. NNMooinrrwidsitaceyrCs,ouTnrocmil soof, Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's Nos Min Conc Max Conc Nos ND's Nos NQ's 0 0 3 0.0001 0.0002 0 0 Salt Water Total c ( <v o O May 23, 2006 Nos Min Conc Max Conc Nos ND's Nos NQ's 3 0.0001 0.0002 Page 105 0 0 0 0 0 0 0 0 0 Atlantic Ocean Canada Denmark Faroe Islands Finland Iceland Japan Norway Pacific Ocean South Korea Sweden Taiwan United States 00 00 00 00 00 00 00 03 0.0036 0.0072 03 0.0036 0.0072 000 003 0.0021 0.0322 04 0.0035 0.0040 0 046 0.0035 0.0021 0.0040 0.1920 000 000 002 0.0115 0.4477 000 002 0.0115 0.4477 000 000 000 000 0 0 11 0.0002 0.3200 07 0.0000 0.0001 0 000 000 0 7 11 0.0000 0.0002 0.0001 0.3200 02 0.1300 0.2700 00 00 02 0.1300 0.2700 00 00 00 00 00 0 0 0 0 0 0 0 0 0 Solids Sewage o o o o o o o o o o ft) p Sewage Sludge 1C--`L. X Sediment oo oo o O oO o oo oo o oO o H | B3 dd hoi* O " i f a sa Atlantic Ocean o o o o o o o O Oo Canada O Oo Denmark Nos Min Cone Max Cone Nos ND's Nos NQ's zO9 z0sfflX)s3=z(/o) zzo j DO m ra <pTT ccon.P ICCUD CT>7 8a 1= 0Z =S 0Z ill SO o Solids Sludge T o ta l E n v iro n . Sei. T echnol. 39(11): 3 9 4 6 -3 9 5 6 N o rdic C ouncil of M inisters, Trom so, N orw ay Total N o rdic C ouncil of M inisters, Trom so, N orw ay Total Tay 23, 2006 3 3 Nos M in C o n e M ax Cone N os N D 's N es N Q 's oO Nos M in C o n e M ax Cone N os N D 's N os N Q 's Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Nos Min Cone Max Cone Nos ND's Nos NQ's Page 106 oo 03/90 09020e 03/90 090S0 S 3800 0 2900 0 e 3800 0 2900 0 0 o o s 00020 0002 0e s 0002 0 0002 0 s O oo oo oo (>(> 9 Q 0 .0 0 0 2 0 .0004 Q 0.3770 0.3910 Q 0.3770 0.3910 8 0 .0 0 0 2 0.0019 o o oo ob so so o oO o oo oo ss O O IG D o o o P 0002 0 0002 0 P P 0002 0 0002 0 P / 0002 0 0002 0 L / 0002 0 0002 0 / 1 1.0750 1.0750 1 1.0750 1.0750 4 0.2 0 00 0.2980 2 4 0.2 0 00 0.2980 2 2 0.2780 0.3120 2 0.2780 0.3120 O o Faroe Islands ooo Finland 2 0/ 0 /0 0002 0 a 2 0/ 0 /0 0002 0 B Iceland Japan Norway o o O oo 0oo1-oo^0 o o oo 0ooo1-ooo^0) Pacific Ocean South Korea o oo ooo Sweden s 0002 0 0 0 0 2 0e s 0002 0 0002 0 s V 0 6 //0 0002 0 0 V 0 6 //0 0002 0 e oo o Taiwan oo oOO United States 51 0.0110 0 .6 2 5 0 6 3 51 0.0110 0 .6 2 5 0 6 3 o ooo 5.0 Analytical: Approaches and Challenges In Environmental Matrices May 23, 2006 Page 107 5.1 Analytical Determinations of Perfluorooctanoic Acid 5.1.1 From Total Fluorine to Low-Level Speciation In 1954 W ickbold com m ented that the difficulty in determ ining fluorine in organic substances is primarily in the data interpretation since very energetic agents must be used to destroy the carbon fluorine bond (Wickbold 1954). His development of the oxyhydrogen torch combustion system allowed the determination of fluorine-containing com pounds, in som e cases, to levels as low as the 20-m g/kg level. In this method, however, only total fluorine is determ ined and no speciation is possible. In 1968, Taves determ ined the level of fluorine in hum an blood serum by com paring the levels in ashed and unashed sam ples to dem onstrate that there w ere two form s of fluorine in blood, "exchangeable and non-exchangeable" (Taves 1968). The latter, he suggested, might be organically-bound fluorine. In 1980 Belisle and H agen developed a gas chrom atographic m ethod to determ ine perfluorooctanoic acid (P F O A ) in blood and other biological sam ples (Belisle et al. 1980). Their method required the use of diazom ethane to form the methyl ester of PFOA. The method was able to measure PFO A levels as low as 15 ug/L. Introduction of liquid chrom atography tandem m ass spectrom etry (L C /M S /M S ) in the 1990s m ade possible the determ ination of P FO A in various m atrices without derivitization. As reported by Martin e t al. after a 2 0 0 3 P FO A workshop, there are still many analytical chemistry challenges to obtaining scientifically defensible data due to a variety of matrix and analytical methodology considerations (Martin et al. 2004). 5.1.2 Water M oody and Field reported the first m easurem ents of P FO A in groundw ater in 1999 (M oody et al. 1999). They used a G C /M S method and obtained a limit of quantitation (LO Q ) of 36 ppb and a limit of detection (LO D ) of 18 ppb. R ecent publications in w ater matrices using LC/M S or LC /M S/M S report LOQs ranging from 0.1 ppt to 1 ppb and LODs ranging from 5 ppq (pg/L) to 7.8 ppt (ng/L). Appendix A-Table 1 summarizes P F O A m easurem ents in the w ater matrix. In general, natural w ater m atrices are sim pler m atrices than m ost other natural matrices (e.g., sludge, soil) for the determination of water-soluble species such as PFOA. Since P F O A or its salt is often used as a fluoropolym er processing aid in the production of perfluoropolym ers and since perfluoropolym ers are used in laboratory equipm ent, sample preparation and background level determination issues are important to address (Fluoropolymers Manufacturers Group 2003). Good chromatographic separation (to assure there are no co-eluting peaks) or use of isotopically enriched standards is important, especially at low quantitation levels. Isotopically enriched standards were used in a rainw ater study (Loew en e t al. 2 0 0 5 ) although only one rainfall event w as captured. W hen extensive concentration of sam ples is involved in the analytical method, a validation using spiked standards is necessary to show effects of sam ple May 23, 2006 Page 108 concentration and extraction. In seaw ater (Y am ashita e t al. 2004), coastal w ater (So e t al. 2004), and surface w ater (Saito et al. 2004) exam ples, standards w ere not processed through the sam ple concentration step. In the seaw ater exam ple, spike recovery w as determ ined for laboratory w ater at 1 ppt. In this exam ple background levels of a perfluorinated compound w ere found but could not be explained by instrumental or laboratory equipm ent background. In the coastal w aters exam ple, the field quality samples appeared to have come from a different batch of samples from those reported and analyte recoveries were determined from distilled water. Recoveries ranged from 160 to 190% , suggesting a possible problem with this method. In the surface w ater exam ple, blanks w ere concentrated less than the samples (i.e., samples and blanks w ere not treated the sam e w ay) and an external calibration w as used. In m any cases not enough information is available in publications to understand the level of analytical method validation. A wastewater treatment plant (influent, effluent, and river water at point of discharge) was screened for eight perfluorooctane surfactants including perfluorooctanoate (Boulanger et al., 2005). G reater than 80% PFO A signal suppression was observed for the influent sample extracts. Field spike recovery was only 16%. Additional filter steps were able to remove the signal suppression problem but the recoveries w ere still too low to report. Effluent and river w ater did not experience signal suppression. Six-wastewater treatment plants w ere studied to determine the mass loading and fate of several perfluoroalkyl surfactants (Sinclair et al., 2005). Since matrix effects are known to cause either ionization suppression or enhancem ent in electrospray M S/ MS, both standard addition and post-column infusion were used to investigate this phenom enon. In this study only ionization suppression w as observed for som e of the long-chain perfluorocarboxylic acids, but it did not significantly affect quantitation. In all cases perfluorooctanoate (P F O ) w as consistently found in the procedural blanks and the inter sam ple m ethanol injections. This background was subtracted from the calibration curves and the sam p les. A global survey of perfluorinated acids in oceans reviewed sources of background levels of perfluorooctanoate observed in ocean w ater sam pling and analysis (Yam ashita e t al., 2005). Fluoropolym ers w ere not used in the analytical system since they could be a potential source of perfluorooctanoate (PFO ) background since perfluorooctanoate salts are often used as fluoropolymer processing aids. Procedural blanks were used to identify the sources of contamination and to help eliminate them. LC tubing was replaced with either stainless steel or polyetheretherketone (PEEK) tubing and solvent degasser hardware and valves w ere isolated from the LC system. Vial caps w ere replaced with polyethylene and polypropylene tubes w ere used for sample preparation. Solid-phase extraction (SPE) cartridges and filters w ere also checked and w ashed as necessary to reduce or elim inate background levels. In addition to the precautions introduced into the sampling and analysis equipment, matrix May 23, 2006 Page 109 spikes, field blanks, procedural blanks, instrument blanks, and continuing calibration verification with every set of 20-25 samples was used to determine the background and interferences. The highest concentration of PFOA found in procedural blanks passed through the entire analytical procedure including SPE cartridges was 5.2 pg/L. The ratio of perfluoroheptanoic acid (PFHpA) to PFOA in surface waters was suggested as a means of differentiating between atmospheric and non atmospheric deposition sources (Simcik et al., 2005). Samples were filtered through 0.4-pm filters then extracted with a C18 SPE dried with nitrogen, then eluted with methanol. The residue was reconstituted with methyl t-butyl ether then cleaned up via liquid/solid chromatography (fluorous silica gel). The sample was eluted from that column with methanol and PFO determined via LC/MS. Extensive quality assurance data was reported to demonstrate the viability of the method. 5.1.3 Air Techniques for measuring perfluorinated compounds in air are still under development. The determination of fluorine-containing compounds in air had been generally limited to charcoal adsorption followed by Wickbold torch determination of total fluorine (Kissa 1986) or measurements of volatile hydrofluorocarbons, chlorofluorocarbons, or chlorofluorocarbons, either directly or after adsorption, via gas chromatography (Bertsch et al. 1974, Cox et al. 1982, Grunsrud et al. 1975, 1975a, Lovelock 1972, Reinke at al. 1985, Russell et al. 1977, Schlitt et al. 1980). Martin et al. 2002 reported a method for the collection and determination of nine fluorine-containing neutral compounds by high volume air sampling followed by extraction and then gas chromatography mass spectrometry. In 2004 Shoeib et al. investigated perfluoroalkyl sulfonamides in indoor and outdoor air (Shoeib et al. 2004). Stock et al. reported data from a six-city sampling campaign in North America where both perfluorinated alcohols and amides were found (Stock et al. 2004). PFOA was not determined in any of these studies. PFOA was measured in airborne dust collected on quartz membrane filters near two Japanese cities (Harada 2005). Although no data were available for the blank concentrations, PFOA levels were reported to be significantly higher than the blanks. No particle size speciation was performed. Another method for the determination of PFOA in air samples (Kaiser et al. 2005a) was used to measure perfluorooctanoate in ambient air near a manufacturing facility (Barton et al. 2005). Since PFOA has a vapor pressure of 128 Pa at 59C (Kaiser et al. 2005b), this method also allowed for the determination of PFOA in the vapor phase. Size speciation was accomplished using a high-volume cascade impactor. A summary of PFOA measurements in air is given in Table 2. Determination of PFOA in air involves a higher level of complexity compared with determinations in water. Since PFOA has a finite vapor pressure near ambient May 23, 2006 Page 110 tem peratures (Kaiser 2005b ), it is important that the m ethod validation include analyte breakthrough evaluation. Since P F O A is also very soluble in w ater (4.4 g/L at 25C ) (Shinoda et al. 1972), analyte retention at the expected relative humidity range of the m easurem ent should also be determined. An evaluation guideline that includes these and other m easurem ent considerations is available (U .S. O S H A 2002). 5.1.4 Biota A wide variety of biological matrices have been analyzed for PFO A (See Table 3 and also "Environmental Concentrations" section.) M any of the initial methods focused on other perfluorinated compounds and were not optimized for PFOA determination. Initially methods w ere not available to address the interference from blank levels of P F O A in the analytical systems. Standards w ere not well characterized and researchers may not have known the distribution of branched and linear PFO A present in standards and sam ples. Also with m obile sources (wildlife), it is often difficult to determ ine the source of the analytes. For soil and sediment measurem ents, hom ogeneity is often a com plicating factor in determ ining a representative sam ple. In reviewing the literature it is obvious that there is little agreem ent on the specification of reporting levels (LOD, LOQ). Details on spike recovery and blanks are often not included. As the analytical techniques continue to evolve, as isotopically enriched standards are introduced into the m easurem ent protocol, and as round-robin studies give an indication of the quality of the m easurem ents, the confidence level in the m easurem ent s of P F O A in the environm ent will be better defined. A screening method was developed using polar cod and glaucous gull livers (Berger et al., 2005). The method uses an extraction solvent with the sam e composition as the LC mobile phase to avoid the reconstitution step. The extract is coarsely filtered first through a facial tissue covering the tip of a Pasteur pipette, then through a centrifugal filter. The method works well for PFO but did not work well at low levels for the less polar analytes. An ion-pairing m ethod w as used to determ ine perfluorocarboxylic acid levels in bottlenose dolphin plasm a (Houde et al., 2005). Either dual l3 c PFO A or perfluoroheptanoic acid was used as an internal standard. Polar bear liver was analyzed for PFO using an ion-pairing agent and LC/M S/M S (Sm ithwick et al., 2005). Background levels w ere subtracted from the sam ple concentrations. 5.1.5 Soil, Sludge, and Sediment P FO and other perfluoroacid anions w ere m easured in sludge from six w astew ater treatm ent plants (Sinclair et al., 2006). The extraction method was similar to that used by Higgins et al. (Higgins et al., 2005). As noted above, PFO background w as found in all sam ples and in solvent blanks, so it w as subtracted from the samples and calibration curves. May 23, 2006 Page 111 A simple and efficient method for extraction of domestic sludge and sediment was developed that uses a liquid solvent extraction (1% acetic acid then 90:10 methanol and 1% acetic acid)(Higgins et al., 2005). After centrifugation the samples are passed through a C18 SPE extraction cartridge, washed, then a dual 13C internal standard added prior to LC/MS/MS determination. A summary of the soil, sludge, and sediment reports is given in Table 4. 5.1.6 Other Media and related reports Although not developed for determining PFOA in the natural environment, several methods have appeared in the peer-reviewed literature that might provide useful information. Water, methanol, sweat simulant, and saliva simulant were used to extract PFOA from textile and carpet (Mawn et al. 2005). A method to optimize PFOA extraction from polytetrafluoroethylene polymer was developed using pressurized solvent extraction and reflux extraction (Larsen et al, 2005). A capillary electrophoresis with ultraviolet detection method was developed to measure higher levels of PFOA (Wojcik et al. 2005). A LC/MS method for the determination of the ammonium salt of PFOA in air was also reported (Reagen et al. 2005). One paper was published on the physicochemical properties of perfluorocarboxylic acids (Kaiser 2005b). Studies involving gas-phase thermolysis of ammonium perfluorooctanoate (APFO) (Krusic et al. 2004) and PFOA (Krusic et al. 2005) and using gas-phase nuclear magnetic resonance (NMR) were reported. A different NMR study used 19 F NMR to correlate PFOA structure with environmental properties (Ellis et al. 2004). A thermal degradation study of treated textiles showed no detectable PFOA was formed under incineration conditions (Yamada et al. 2005). 5.1.7 Analytical Determination of Perfluorooctanoic Acid Uncertainty Despite the limitations of the analysis and the number of investigations reported, the trend is to strive to lower reporting limits. Determination of PFO in different sample types (tissue, blood, etc.) measurement of temporal trends, and correlation with abiotic environmental concentrations are essential to our understanding the disposition of PFOA in the environment. At higher concentration levels (e.g., >10x LOQ) the data reported to date are probably quite reliable. At the lower levels (<3X LOQ) the analytical issues need to be addressed thoroughly and reported to ensure data reliability and accuracy. Low-level determination of any analyte necessitates special attention. Fluorinated surfactants exhibit chemical and physical properties quite different from their hydrogenated analogs, with important implications for the analysis of these materials (Kissa 2001). Sample-collection and sample-preparation protocols must be carefully designed to ensure that no analyte is lost and that no interfering contaminants are May 23, 2006 Page 112 introduced. The limits on reliable quantitation must be rigorously defined and observed, based on determination of suitable standards and blanks. The fitness of the method for measurement of fluorosurfactants must be objectively evaluated (Thompson 1996) and the method thoroughly validated, including an investigation of subtle effects, such as sorption losses or contamination from containers, reagents, or laboratory equipment. Validation considerations should include a matrix-based standard curve with a minimum of five points, accuracy and precision demonstration at low, middle, and high concentration levels, and storage stability (e.g., U.S. FDA 2001). Since PFOA may be present in the fluoropolymer parts of laboratory equipment, blanks (e.g. solvent, reagent, method, field, trip) are essential. Since co-eluting peaks can cause suppression or enhancement of the PFOA peak via LC/MS/MS, it is essential that a good separation is achieved or that an isotopically enriched PFOA is used to demonstrate if suppression or enhancement occurs. The selection of a standard is also important since PFOA can be synthesized by either electrochemical fluorination (ECF) or by the telomerization process. The ECF process can form from 20 to 30 % branched "impurities" (Abe et al. 1982). Telomerization produces impurities differing by two-carbon atoms (Kissa 2001a). Ideally a secondary method should also be used to evaluate the dependence of the method on the quantification. The secondary method should rely on a different property of the analyte. Moody (Moody et al.2001) used nuclear magnetic resonance spectroscopy (NMR) and LC/MS/MS to compare analytical method results from samples from a spill of 22,000 L of fire-fighting foam into a creek. Although the levels of fluorine-containing species were high, the NMR and LC/MS/MS results varied from approximately a factor of 3 to 7 within a sample pair. Note that the literature references included here covered a long time period in which an evolution in equipment and methods occurred. Since many of the issues concerning measurement of PFOA were unknown, insufficient information was available to evaluate methods properly. When all the studies are assessed according to today's criteria for sampling protocol, technique suitability, and method validation, earlier studies may appear to suffer by comparison. 5.1.8 Round Robin and ISO Standard Methods In 2005 thirty-eight laboratories participated in the first worldwide interlaboratory study on perfluorinated compounds in human and environmental matrices (Van Leeuwen et al., 2005). The study included the determination of perfluorooctanoate and other perfluorinated compounds in aqueous standards, fish muscle tissue, fresh water, clean fish extract, human plasma, and whole blood. The data were evaluated by determining "z" scores based on the Cofino model (de Boer et al., 2002). Laboratories from Belgium, Canada, Denmark, Germany, Italy, Japan, Norway, Sweden, Switzerland, The Netherlands, the United Kingdom, and the United States participated. Experience ranged from just a few months to over five years in handling the types of samples provided. May 23, 2006 Page 113 In general the results indicated that the m ore com plex the matrix, the m ore difficult it w as for the laboratories to obtain satisfactory data as indicated by a z score of <2. On the 8.4 ng/mL (ppb) study standard, 21 of 33 reporting laboratories got satisfactory scores, 2 obtained "questionable" scores (viz., 2<z<3), and 10 received an unsatisfactory score (viz., z>3). For fish liver extract, 10 of 25 participating laboratories got satisfactory scores; for fish tissue, 5 of 20 got satisfactory scores; and for fresh water, 4 of 18 got satisfactory scores. Laboratories did not tend to show consistent performance across the sample types, sometimes doing well with one matrix and poorly with another. There was no correlation between the level of experience and performance. There was also no bias between laboratories that used MS versus those using M S/M S. Differences between laboratories on extraction and clean-up procedures were thought to have a large effect, especially for the more complex matrices. Another study is being planned for 2006. T hese results of the interlaboratory study suggest that m ore work is needed to establish appropriate, rugged and reliable analytical methods for perfluorooctanoic acid determinations, even for the simpler matrices. The statistics noted above are a best case scenario, that is, laboratories that provided data undoubtedly did their best to get accurate and precise results. Som e laboratories delayed or withdrew from the study after having paid the fee due to "technical problem s or tight schedule" so that their results are not included in the report. S ince a w ell-d efin ed valid ated m ethod is n ecessary to get good interlaboratory ag reem en t, scientists from tw elve countries g ath ered at an IS O m eeting in T sukuba, Japan, in June 2 0 0 5 to ad d ress this task. T h ey accep ted a w ork item proposal to produce a standard method for the determ ination of both PFO S and P F O A in unfiltered w a te r sam ples using so lid -p h ase extraction and L C /M S . T h at task is still underw ay. T h e next m atrix that they will address will probably be air. May 23, 2006 Page 114 5.2 Analytical: Literature Cited Additional Literature Cited DuPont-19567 Begley, T.H., White, K., Honigfort, P., Twaroski, M. L., Neches, R., and Walker, R. A. 2005. Perfluorochemicals: Potential sources of and migration from food packaging. F o o d A d d it. C ontam . 22: 1023-1031. Berger, U., and Haukas, M. 2005. Validation of a screening method based on liquid chromatography coupled to high-resolution mass spectrometry for analysis of perfluoroalkylated substances in biota. J. C hro m a to g r. A. 1081: 210-217. Boulanger, B., Vargo, J. D., Schnoor, J. L., and Hornbuckle, K. C. 2005. 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Risha, K.J., Flaherty, J., Willie, R., Buck, W., Morandi, F., and Isemura, T. 2005. Method for trace level analysis of C8, C9, C10, C11, and C13 perfluorocarbon carboxylic acids in water. A nal. C h e m . 77:1503-1508. Russell, J. W. and Shadoff, L. A. 1977. The Sampling and Determination of Halocarbons in Ambient Air Using Concentration On Porous Polymer. J. C h ro m a to g r. 134: 375. Saito, N.K., Harada, K., Inque, K., Sasaki, K., Yoshnaga, T., and Koizumi, A. 2004. Perfluorooctanoate and perfluorooctane sulfonate concentrations in surface water in Japan. J. O ccup. H e a lth 46: 49-59. Schlitt, H., Knoeppel, H., Versino, B., Peil, A., Schauenburg, H., and Vissers, H. 1980. "Organics in Air: Sampling and Identification" in S a m p lin g a n d A n a ly s is o f T o xic O rg a n ic s in th e A tm o s p h e re , ASTM ATP 721, American Society for Testing and Materials, p. 22. Shinoda, K. Masakatsu, H., and Hayashi, T. 1972. The physical properties of aqueous solutions of fluorinated surfactants, J. P hys. C h e m ., 76(6): 909-914. Shoeib, M., Harner, T., Ikonomou, M., and Kannan, K. 2004. Indoor and Outdoor Air Concentrations and Phase Partitioning of Perfluoroalkyl Sulfonamides and Polybrominated Diphenyl Ethers. E n viro n . Sci. Technol. 38: 1313-1320. Sinclair, E., Taniyasu, S., Yamashita, N., and Kannan, K. 2004. Perfluorooctanoic acid and perfluorooctane sulfonate in Michigan and New York waters. O rg a n o h a lo g e n C o m p o u n d s , 66, 4019-4023. Smithwick, M., Muir, D.C.G., Mabury, S.A., Solomon, K.R., Martin, J.W., Sonne, C., Born, E., Letcher, R.J. and Dietz, R. 2005. Perfluoroalkyl contaminants in liver tissue from East Greenland polar bears (Ursus Maritimus), E nviron. Toxicol. C h e m ., 24(4), 981-986. May 23, 2006 Page 124 So, M .K ., Taniyasu, S., Yam ashita, N., Giesy, J.P., Zheng, J. ,Fang, Z., Im, S.H ., and Lam, P.K .S. 2004. Perfluorinated com pounds in coastal w aters of Hong Kong, South China, and Korea. Environ. Sci. Technol. 38: 4056-4063. Stock, N. L., Lau, F. K., Ellis, D. A., Martin, J.W ., Muir, D. C. G., Mabury, S. A. 2004. Polyfluorinated Telom er Alcohols and Sulfanom ides in the North Am erican Troposphere. Environ. Sci. Technol. 38: 991-996. Taniyasu, S ., Yam ashita, N., Kannan, K., Horii, Y., Sinclair, E., Petrick, G., and Gam o, T. 2004. Perfluorinated carboxylates and sulfonates in open ocean w aters of the Pacific and Atlantic oceans. O rganohalogen C om pounds 66: 3985-3990. Taves, D. R . 1968. Evidence that there are two forms of fluoride in hum an serum. Nature 217: 1050-1051. Thom pson, M. and Fearn, T. 1996. W hat exactly is fitness for purpose in analytical measurem ent? The Analyst 121: 275-278. Tom y, G .T ., Budakowski, W ., Halldorson, T., Helm , P.A., Stern, G.A., Friesen, K., Pepper, K., Tittlem ier, S.A. and Fisk, A .T. 2004. Fluorinated organic com pounds in an Eastern Arctic m arine food web. Environ. Sci. Technol. 388: 6475-6481. U . S. Food and Drug Administration. 2001. "Guidance for Industry: Bioanalytical Method Validation", Departm ent of Health and Human Services, Center for Drug Evaluation and Research, Center for Veterinary Medicine. May. U. S. Occupational, Safety and Health Administration. 2002. Evaluation guidelines for air sampling methods utilizing chromatographic analysis. September. V an de Viiver, K .I., Hoff, P.T., Das, K., van Dongen, W ., Esm ans, E., Jauniaux, T., Bouquegneau, J.-M., Blust, R. and de Coen, W. 2003. Perfluorinated chemicals infiltrate ocean waters: link betw een exposure levels and stable isotope ratios in m arine m am m als. Environ. Sci. Technol. 37: 5545-5550. Wickbold, R. 1954. Quantitative combustion of organic substances containing fluorine. Angew. Chem. 66: 173-174. W ojcik, L., Szostek, B., M aruszak, W ., and Trojanowicz. M. 2005. Separation of perfluorocarboxylic acids using capillary electrophoresis with UV detection. Electrophoresis 26: 1080-1088. Yam ashita, N ., Kannan, K., Taniyasu, S., Horii, Y., O kazaw a, T., Petrick, G., and Gam o, T. 2004a. Analysis of perfluorinated acids at parts-per-quadrillion levels in seaw ater using liquid chrom atography-tandem m ass spectrometry. Environ. Sci. Technol. 38: 5522-5528. May 23, 2006 Page 125 Yam ashita, N ., Kannan, K., Taniyasu, S., Horii, Y, Hanari, N., O kazaw a, T. and Petrick G. 2004b. Environmental contamination by perfluorinated carboxylates and sulfonates following the use of fire-fighting foam in Tom akom ai, Japan. 2004. O rganohalogen Compounds 66: 4063-4068. May 23, 2006 Page 126 5.3 Analytical: Appendix A (Tables 1-5) May 23, 2006 Page 127 Table 1: Determination of PFOA in water Matrix (reference) Technique* LOD LOQ Ground water (Moody et al. 1999; Moody 2003) Etobicoke Creek (Moody et al. 2002) Tennessee River(Hansen et al. 2002) Great Lakes (Boulanger et al. 2004) Seawater (Yamashita et al. 2004) and (Taniyasu et al. 2004a) Coastal water (So et al. 2004) GC/MS LC/MS/MS LC/MS/MS LC/MS/MS LC/MS/MS LC/MS/MS 18 ppb 36 ppb 1 pg 9 ppt 5 ng/L 10-to 25 ng/L 6pg/mL 13 5 ppq 1 or 100 ppt not 0.02 ppt reported Surface water (Saito et al. 2004) Rainwater (Loewen et al. 2005) Water (Risha et al. 2005) Water (Alzaga et al. 2004) Water sea, lake, snow, run-off (Yamashita et al.2004b) LC/MS LC/MS/MS LC/MS/MS GC/NCI-MS* LC/MS/MS 0.06 ppt 7.2 ppt Not reported 0.1 pg/L not reported 0.1 ppt 1 ppb 25 ppt 0.34 pg/L not reported Concentration Factor 55-200 100 8 2500 2000-5000 400-2500 1000 4000 8 SPME** not reported Calibration Range 3.6 to 1080 ug Spike Recovery % 73-90 0.46 to 325 80-100 ppb 10 to 5000 112 ng/L 1 to 500 ng/L 109 1 to 500 ppt; 0.1 to 20 ppb 124 (C18); 147 Oasis 0.02 pg/mL (upper level not reported) 0 to 2 ppt; 5-150 ppt 170 92-99 1 to 50 ppb not detected 25 to 1000 ppt 0.035 to 150 pg/L not reported 73 to 90 not reported not reported May 23, 2006 Page 128 W ater: lake (S inclair e t al. 2004) W ater: sea (C alieb e e t al. 2004) W ater: rain, sea, lake, effluents (B erg er e t al. 2004) W astewater (Boulanger et al. 2 0 0 5 ) Ocean water (Yamashita et al.2005) Surface water (Simcik et al., 2005) LC/M S/M S LC/M S/M S L C /M S L C /M S /M S L C /M S /M S L C /M S W astewater (Sinclair et al., 2005) W ater (Taniyasu et al., 2005) Freshwater and marine water (deVoogt et al., 2005) W ater (Kurunthachal am et al., 2005) W astewater (Crozier et al., 2005) Lake water (Furdui et al., 2005) S tream s (Rostkowski et al., 2005) Shallow sea L C /M S /M S L C /M S /M S L C /M S L C /M S /M S L C /M S /M S L C /M S /M S L C /M S /M S L C /M S /M S 8 ng/L 25 ng/L 50 not 0.05 to 45,000 reported 0.5 ng/L not not not reported reported reported not reported Not reported not reported not reported not reported not reported not 6 pg/mL reported (ppt) not not reported reported 0.29 and 0.58 ng/L (ppt) not reported not reported 2.5 ng/L not several reported pg/L 0.08 not ug/L reported 200:1 and 600:1 not reported 8888:1 and 17777:1 not reported not reported 0.5 ng/mL to 250 ng/mL (ppb) not reported 5 to 100 ng/mL (ppt) 0.1 to 100 ng/mL (ppt) not reported not reported 16 - 86 not reported 93 -112 70 - 130 >80 not reported not not 500:1 reported reported 1ng/L not reported 1 - 4 not ng/L reported not 0.5 ng/L reported 0.8 - 10 not not reported 1:1 not reported not reported not reported 91 -114 not reported 92 -106 0.5 - 100 ng/L not reported not reported 95 not reported not May 23, 2006 Page 129 water (Nakata ng/L reported reported et al., 2005) W ater LC/M S/M S 0.02 pg 0.02 pg not reported not (Taniyasu et reported al., 2005a) Ground water LC /M S/M S 10 ppt 50 ppt 8:1 25 ppt to 70-130 (Kaiser et al., 1000 ppt 2005a) W astewater not reported not not not reported not reported not (Sinclair et al., reported reported reported 2005) Sea water LC/MS/MS not 5 - 30 not reported not reported not (Theobald reported pg/L reported 2005) Lake water LC/MS/MS not ppt (Furdui et al., reported not reported 1:01 not reported 2005a) W ater LC/MS/MS not 1 pg (Taniyasu et reported not reported not reported >80 al., 2005b) River water not reported not 0.1 ng/L not reported not reported not (Falandysz et reported reported al., 2005) Rain water GC/M S not not not reported not reported not (Scott et al., reported reported reported 2005) *G C /M S , gas chrom atography/ m ass spectrom etry; LC /M S / MS, liquid chrom atography tandem m ass spectrom etry; N C I-M S , Negative ion chem ical ionization mass spectrometry; SPM E, solid-phase microextraction May 23, 2006 Page 130 Table 2: Determination of PFOA in air Media Validated ranae Technique Quartz filter not reported LC/MS* (Harada et al., 2005) OVS tube (Kaiser 0.474 to 47.4 LC/MS et al. ug/m3 2005a,c,d,e) Cellulose filter 1 pg/m3 to 50 LC/MS (& OVS tube, see pg/m3 (24 hour above) (Barton et sample at 1.2 al. 2005) m3/min) *LC/MS, liquid chromatography/mass spectrometry ** s.d., standard deviation Spike recovery (% +/- s.d.**) 89.4 +/- 3.91 97.7 +/- 6.28 96 May 23, 2006 Page 131 Table 3: Determination of PFOA in biota Matrix (reference) W ildlife (Giesy et al. 2 0 0 1 ) Liver: mink; otter (Kannan et al. 2 0 0 2 ) Liver: m arin e m am m als; fishes; birds Blood: fish (Kannan et al 2002a) Liver: mink and river otters (Kannan et al. 2 0 0 2 b ) Liver: rat; rabbit (Hansen et al. 2 0 0 1 ) Liver: rat (O h ya e t al. 1998) Tissues: rat (K udo e t al. 1998) Sludge (Schroder e t al. 2 0 0 3 ) Liver, various (Martin et al. 2 0 0 4 a ) Technique LC/M S/M S LC/M S/M S LC/M S/M S LC/M S/M S LC/M S/M S LC with fluorescenc e detection GC with electroncapture detection L C /M S LC/M S/M S LOD not reported not reported not reported not reported 1.0 ppb 1 pmol/mg 1 ng /injection 0.48gg/m L 2 ng/g LOQ 2.5 to 180 ng/g wet 4.5 to 75 ng/g 2.5 ng/mL 4.5 to 75 ng/g 5.0 ppb not reported not reported 10 mg/kg not reported Calibration Range not reported not reported not reported not reported 50 to 1000 ppb 0.1 to 10 nmol not reported 2 to 25 p g /m L 2.5 to 1000 pg Spike Recovery % not reported 53 to 140 <40 (salm o n ); 90 (sea eagle); 70 (seal) 53 to 140 87 +/- 12 93.6 to 94.0 30 6 to 319 >80 May 23, 2006 Page 132 Liver: m arin e m am m als; fishes; birds (Bossi e t al. 2 0 0 5 ) Liver: polar bear (DeSilva et al. 2 0 0 4 ) Eggs: G u illem o t( H o lm stro m e t al. 2 0 0 5 ) Liver: mice (H o ff e t al. 2004) Tissues: fishes, pelicans (Johnson et al. 2 0 0 4 ) Liver: fish and marine mammal (K a lle n b o rn e t al. 2 0 0 4 ) P lasm a: turtle (Keller et al. 2 0 0 4 ) Food web (Martin et al. 2 0 0 4 ) Liver: polar bears (S m ith w ick e t al. 2 0 0 5 ) Food web (Tom y et al. 2 0 0 4 ) Liver: m arin e mammal (De Vijver e t al. 2 0 0 3 ) LC/M S/M S GC/M S LC/M S/M S LC/M S/M S not reported L C /M S LC/M S/M S LC/M S/M S LC/M S/M S LC/M S/M S LC/M S/M S 7ng/g 0.02 pg 3 ng/g not reported not reported 0.6 to 1 ng/g not reported 2 ng/g 2 ng/g 0.2 ng/g not reported 12 ng/g 10-1000 ng/g 105 not not reported not reported reported not not reported not reported reported not reported not reported not reported not reported not reported not reported not not reported 40 to 72 reported not not reported not reported reported not reported not reported not reported 96 to 101 not reported 99.9 Not reported 10 to 110 ng/g wet w e ig h t 10 to 300 98 to 110 pg/pL not reported not reported May 23, 2006 Page 133 Blood: bovine (Guruge et al. 2 0 0 4 ) M a rin e : liver and blood (Corsolini e t al. 2 0 0 4 ) Polar cod and glaucous gull livers (Berger et al., 2005) Bottlenose dolphin p lasm a (Houde et al., 2005) Polar bear liver (S m ith w ick et al. 2005) Harbor seal tissues (Van de Vijver et al., 2005) Glaucous gull plasma, liver, brain, and eggs Lake aquatic o rg an ism s (Kannan et al., 2005) Blood and liver (Taniyasu et al. 2005) W ater (Kurunthach alam et al., 2005) Shallow LC/M S/M S LC/M S/M S LC ToF MS L C /M S /M S L C /M S /M S L C /M S /M S L C /M S /M S L C /M S /M S L C /M S /M S L C /M S /M S L C /M S /M S not reported not reported 1.25ng/g (cod); 1.28 ng/g (pl) not reported 2.3 ng/g not reported not reported not reported not reported not reported 3.0 ng/g not reported 3 to 20 n g /m L not reported 0.5 ng/g not reported 1.39 - 62 ng/g not reported not reported several pg/g not reported not not reported 92 0.5 to 100 Not n g /m L reported not reported 84 (cod); 83 (gull) not reported 89.4 not reported 53 - 130 not reported not reported not reported 59 - 134 0.10 - 750 <50 n g /m L not reported >80 not reported 80-108 not reported not May 23, 2006 Page 134 coastal water o rg an ism s (Nakata et al., 2005) Burbot liver (Tomy et al., 2005) Beluga liver (Tom y et al. 2005a) M u ssels and oysters (So et al., 2005) Calf serum and liver (Guruge et al., 2005) Fish and bird livers (Sinclair et al., 2005) Biological m atrices (M a rlin s k y 2005) Plant tissue sam p les (Powley et al., 2005) Fish and water fowl blood (Gulkowska et al., 2005) L C /M S /M S L C /M S /M S not reported 0.3 ng/g LC/MS/MS not reported LC/M S/M S 49 pg/mL not reported not reported G C /M S not reported LC/MS/MS not reported LC/MS/MS not reported reported not reported not reported not reported not reported not reported not reported 5 ppb 0.05 ng /m L reported not reported >85 not reported not reported not reported 92.5 not reported 96, 98 not reported not reported not reported not reported not reported 80 - 110 not reported not reported May 23, 2006 Page 135 Table 4: Soil, sludge and sediment Matrix Technique LOD (reference) LOQ Concentr Calibratio Spike ation n Range Recovery Factor % W astewater LC/M S/M S not 2.5 ng/L 0.1g:1m L 0.1 to 100 not sludge reported ng/mL reported (Sinclair et (ppt) al., 2006) Sludge and sed im en ts (Higgins et al., 2005) LC/M S/M S 0.011 not 1g:10 mL 0.01 to 50 88 -94 ng/g reported pg/uL (sediment) sed im en t ; 71 - 80 ; 1.0 ng/g (sludge) sludge Sediments LC/M S/M S not not 5g:0.5 not (Lucaciu et reported reported mL reported al., 2005) Sediments LC/MS (de Voogt et al., 2005) 0.4 ng/g not not not reported reported reported Sediment(K LC/M S/M S not not 15g: 1 urunthachal reported reported mL: am et al., 2005) not reported W astew ater LC /M S/M S 0.1 ng/g not not not (Crozier et reported reported reported al., 2005) Sediment LC/M S/M S 0.10 ng/g not not not (Nakata et reported reported reported al., 2005) Sludge and LC/M S/M S 0.7 - 2.2 not not not sed im en ts ng/g reported reported reported (Higgins et al., 2005a) W astewater LC/M S/M S not not not not (Schultz et reported reported reported reported al., 2005) Sediments LC/M S/M S not not not not (Lucaciu et reported reported reported reported al., 2005a) 50-80 not reported 81 -109 not reported not reported not reported not reported not reported May 23, 2006 Page 136 Sediments not and soils reported (Ellington et al., 2005) not not not not reported reported reported reported Soil and not sediment reported (Szostek et al. 2005) not not not not reported reported reported reported Sludge LC/M S/M S not not not not (Crozier et reported reported reported reported al., 2005a) not reported 70 - 120 not reported *Liquid chromatography (LC) Mass Spectrometry (MS) Tandem MS (M S/M S) Gas chromatography (GC) May 23, 2006 Page 137 Table 5: Other media Matrix Technique LOD (reference) Extraction of PTFE* po lym er (Larsen e t al. 2005) Extraction of textile and carpet (M aw n e t al. 2005) A P F O ** in air (Reagen et al. 2 0 0 4 ) C E *** (W ojcik e t al. 2005) House dust (Kubwabo et al., 2005) Food packaging (Begley et al., 2005) Paper, textile, and carpet (L 'em p ereu r et al., 2005) P lasm a (Hoppe et al., 2005) House dust (Strynar et al., 2005) Consumer articles (Powley et al., 2005 a) Consumer articles (L 'em p ereu r Reflux and pressurized solvent; LC/M S/M S LC/M S/M S L C /M S CE L C /M S /M S L C /M S L C /M S /M S NCI GC/MS L C /M S /M S L C /M S /M S L C /M S /M S not reported not reported 144 n g /m L 13p g /m L 2.29 ng/g not reported 10 ppt not reported not reported not reported not reported LOQ Calibration Range 0.5 ppb 0.1 ppb to 150 ppb 0.08 0 to 50.0 ng/mL ng/mL 479 Not ng/mL reported not 0.1 to 9.5 reported m M/L 7.29 25 to 1000 ng/g ng/g not not reported reported 50 ppt 25 - 500 ng/L 1 ug/L 1 - 100 ug/L 0.1 ug/g not reported not not reported reported not not reported reported Spike Recovery % 0 to 106% 95.1 to 112 81 to 90 not applicable 100.7 >90 70-120 not reported not reported 88, 84-98 98.9 May 23, 2006 Page 138 et al. 2005a) Food (S ch lu m m er et al., 2005) L C /M S /M S 1 - 2 ng/g not not reported 80 - 120 reported *PTFE, polytetrafluoroethylene **APFO , ammonium perfluorooctanoate ***CE, capillary electrophoresis May 23, 2006 Page 139 6.0 Summary / Conclusions May 23, 2006 Page 140 6.1 Summary / Conclusions Based on studies in the available literature, P F O A will m eet international criteria (see page ix, Table 1) for persistence based on expected half-lives of P F O A via biodegradation, hydrolysis, and photolysis under environmentally relevant conditions. It is anticipated that w ater will be the predom inant environm ental com partm ent in which P F O A resides. In regards to sludges, soils, and sedim ents, the expectation is that adsorption will be very limited and any PFO A associated with these environmental m atrices will likely be found in the w ater phase of sludges, soils, and sedim ents and/or perhaps weakly adsorbed by electrostatic interactions. However, there are still significant uncertainties in regards to the environm ental fate of P F O A including: 1) sources of P F O A in the environm ent; 2) potential for biotransform ation in soil and sedim ents under varying environm ental conditions and anaerobic sludges; 3) transport / distribution mechanisms; and 4) potential for oceans to be predominant sinks. The available data indicate that BAF and BCF values for PFO A are below all regulatory levels that would trigger concern for bioconcentration and bioaccum ulation. In addition, the available evidence indicates that PFOA does not biomagnify through the foodchain. Therefore, while P F O A appears to be environm entally persistent, P F O A is not bioaccumulative based on relevant data and regulatory B criteria. Based on international PB T criteria such as the EC criteria for Inherent Toxicity (T i), which indicate that a substance is inherently toxic if its acute toxicity is < 1 m g/L or its chronic toxicity is < 0.1 mg/L, P F O A is not inherently toxic. The available acute and chronic aquatic toxicity data for P F O A also indicate that it is of low to medium concern for toxicity (i.e., hazard) to freshwater algae, invertebrates, and fish based on data from laboratory studies and the ranking schem e used by U.S. EPA. However, no data are available to assess the aquatic toxicity of PFO A to marine algal, invertebrate or fish species. There are also no PFO A toxicity test data available for either terrestrial wildlife or avian species. Current analytical m ethods m ake it possible to detect extrem ely low concentrations (i.e., high parts-per-trillion to low parts-per billion range) in various environm ental m atrices. The first reports of P FO A in environm ental sam ples in 1999 have been followed by reports using continuously improving analytical sensitivity, hence the num ber of non-detects is being replaced by m easurable, but very small am ounts being detected. Although the total num ber of environm ental sam ples analyzed is growing, there currently is not enough data in any one m atrix with significant samples to clearly define temporal or geographical trends among the various environmental media (including biota). Continuing studies, which incorporate more defined sampling strategies employing currently available analytical technology, should help define temporal / geographic trends. The data available to date do not May 23, 2006 Page 141 seem to indicate that P F O A collects in any environm ental m edia other than the aquatic environment, which appears to be the likely sink. Analytical m ethods for the determ ination of P FO A in various m atrices continue to evolve. It is difficult to m ake com parisons betw een literature reports, especially over time, since details such as types of standards, methods for determining LO D and LOQ, spike recovery and blank types and results are not available or are defined inconsistently. Generally the reports at the higher levels are probably reliable. At lower levels, however, analytical issues concerning reporting limits, blanks, standards, and representativeness of sample need to be addressed. May 23, 2006 Page 142 7.0 Acknowledgements May 23, 2006 Page 143 7.1 Acknowledgements The authors of this paper would like to acknowledge the invaluable contributions to this paper from the following people: Nancy S. Selzer Gerald L. Kennedy, Jr. Robert W. Rickard May 23, 2006 Page 144