ECO-TOXICOLOGICAL EVALUATION OF PERFLUOROOCTANE SULFONATE (PFOS) IN THE ENVIRONMENT John P. Giesy, Ph.D., FRSC Dept. Biomedical Veterinary Sciences and Toxicology Centre, University of Saskatchewan, Saskatoon, Saskatchewan, Canada Department of Zoology, Michigan State university, East Lansing, Michigan, USA Department of Biology and Chemistry, and State Key Laboratory in Marine Pollution, City University of Hong Kong, Kowloon, Hong Kong, SAR, PR China School of Biological Sciences, University of Hong Kong, Hong Kong, SAR, PR China F F FF FF F F F C C C C O C C C C S F F F FF FF FO O International Conference on Environmental Safety and Ecological Criteria, Nanjing, China June 30-July 2, 2013 City University of Hong Kong Affiliations- Thanks for the support!!!!! Professor & Canada Research Chair University of Saskatchewan Emeritus Distinguished Professor of Zoology Michigan State University Honorary Professor, School of Biological Sciences University of Hong Kong Chair Professor at Large, Dept. Biology and Chemistry City University of Hong Kong Concurrent Professor, School of the Environment Nanjing University Guest Professor Xiamen University Einstein Professor Chinese Academy of Sciences Support Marine Pollution Conference Canada Research Chair program Program of 2012 "High Level Foreign Experts" (#GDW20123200120) funded by the State Administration of Foreign Experts Affairs, the P.R. China to Nanjing University Einstein Professor Program of the Chinese Academy of Sciences Visiting Distinguished Professorship in the Department of Biology and Chemistry and State Key Laboratory in Marine Pollution, City University of Hong Kong International Conference on Environmental Safety and Ecological Criteria Presentation There is a lot more detail in the presentation than I can show today I will go over many things quickly More important to get overview than details Copy of the presentation can be obtained by the conference organizers Key references are listed at the end of the presentation—they can be obtained by number from my web site Properties of Fluorinated Organic Compounds F is the most electronegative element. This confers a strong polarity to the C-F bond. C-F bond is the strongest of known covalent bonds (~110kcal/mol). Even in the high-energy environment of the stratosphere, the C-F bonds in CFCs are exceptionally stable. Three non-binding electrons in F atom can form a protective sheath that yields PFCs very stable. C-F bond can withstand boiling with 100% sulfuric acid without any defluorination. Structures of Sulfonated Fluorochemicals POSF: Perfluorooctanesulfonylfluoride POSF is the starting material for polymer production O C8F17 S - F O PFOS: Perfluorooctanesulfonate PFOS is the ultimate degradation product of POSF-based compounds and the compound found in the environment F F F C F C F F F C F F F F C FF C C FF F O C C S O F O O C8F17 S - O O Biologically produced fluorochemicals contain only one fluorine atom e.g., MFA Most fluorochemicals in the environment are anthropogenic PFOS and POSF-based chemicals are on Annex B of Stockholm Convention Still produced in China Uses of Fluorinated Surfactants Adhesives : Wetting agents. Antifogging : Glass surfaces exposed to humid atmospheres - mirrors in bathrooms, automobile windshields, eyeglass lenses, plastic (or polyethylene) cover sheets in agriculture. Antistatic agents : Antistatics prevent the buildup of static electricity and dissipate the electric charge formed on the substrate—Important for microchips. Cement additives : Reduce shrinkage of cement. Uses of Fluorinated Surfactants Cleaners for hard surfaces: Automotive waxes, cleaning outside of airplanes, degreasing of metals. Coatings: Paint additives - to improve dust repellency, floor waxes. Cosmetics: Hair-conditioning formulations to improve lubricity, and render hair oleophobic. e.g., POAA. Electronics: Insulators for wires and cables. Electroplating: Chromium, copper and nickel plating. Uses of Fluorinated Surfactants Etching: Glass articles are polished and etched with solutions containing H2SO4, HF and a fluorinated surfactant. Fire-Fighting Foams: Formulated to float on flammable liquids and extinguish flames. FS in Aqueous Film-Forming Foams (AFFF) reduce the surface tension of water and form a film on the fuel surface. Herbicides and Insecticides: Wetting agents, ant baits. Leather: Provide water and oil repellency Uses of Fluorinated Surfactants Paper: Oil and water repellency. Used in folding cartons for snack foods, carry-out fast food, cake mixes, margarine, candy, bakery products and pet foods. Polishes and waxes: In floor waxes. Textiles: Polyester etc. to impart soil, oil and water repellency. Major use is in carpeting. SUMMARY - Environmental Fate PFOS is ubiquitous in the global environment in both urban and remote locations PFOS accumulates into human and wildlife tissues PFOS can be toxic to invertebrates and vertebrates under laboratory conditions Issue: Are current concentrations of PFOS in the environment expected to cause any adverse effects on wildlife Ecotoxicological Evaluation •Determine target tissues & key effects of PFOS •Elucidate modes of action of PFOS •Determine critical effect concentrations of PFOS •Determine concentrations of PFOS in the environment •Calculate Hazard Quotients (HQs) and Margins of Safety (MOSs) Perfluorooctane sulfonate PFOS is a fatty acid analogue Not metabolized Amphiphilic Preferentially retained in plasma and liver binds to protein Affects membranes Ecotoxicological Assessment For PFOS Rationale for Testing Discovery of PFOS in environmental Samples Reliable, sensitive analytical methods now available Generate hazard data for environmental risk evaluation Approach Determine Toxicity Reference Values (TRVs) based on standard practices Calculate threshold water concentrations for protection of aquatic life based on the US EPA-GLI methods and OECD, PNEC Determine tissue concentrations to protect predatory birds and mammals Compare measured concentrations in water or tissues to TRVs HQ = Concentration/TRV; MOS = 1/HQ Threshold Screening Concentrations for the Protection of Aquatic Life Great Lakes Initiative (GLI) US EPA GLI used to calculate acute & chronic concentrations Semi-probabilistic approach Requires acute and chronic toxicity results for aquatic species of various orders and families Uses species and genus geometric means Uses Acute to Chronic Ratios Can calculate Tier I and Tier II GLI values Similar to method of Stephan et al (1985) Conservative (Protective) Derivation of Water Values Aquatic Ecotoxicology Data Beach, SA., Newsted, JL., Coady, K., and Giesy, JP. (2006). Ecotoxicological evaluation of perfluorooctane sulfonate (PFOS). Rev. Environ. Contam. Toxicol. 186: 133-174. Assessment Approach Great Lakes Water Quality Initiative or GLI (USEPA 1995) Comprehensive approach used by regulatory agencies Utilizes environmental properties of chemical Utilizes Environmental Fate Properties Toxicological data for both humans and ecological receptors Approach assumes primary exposure pathways to receptors of concern is from water through species specific food chains Great Lakes Water Quality Initiative Derivation of Water Quality Criteria (WQC) is a two tier process depending on the availability of toxicity data. If all data requirements set out in the GLI are met, a Tier I value can derived Final Chronic Value (FCV) If all data requirements are not met, a Tier II values is calculated Secondary (Screening) Chronic Value (SCV) Great Lakes Initiative (GLI) data requirements GLI Requirements Species Tested Acute Result? Chronic Result? O. mykiss √ P. promelas √ √ 3. Phylum Cordata, 3rd family Xenopus √ √ 4. Planktonic crustacean D. magna √ U. Complamatus √ C. tentans √ 1. Class Osteichthyes, Salmonidae Family 2. Class Osteichthyes, 2nd family 5. Benthic crustacean 6. Insect 7. Family in a phylum other than Arthropoda or chordata 8. Insect family not represented √ Threshold Screening Concentrations for the Protection of Aquatic Life Aquatic Plants relatively tolerant NOAEC values from 5.3 to 150 mg PFOS/l GLI Tier I value could not be calculated due to insufficient number of families and especially chronic data Secondary Chronic Value (SCV) = 1.2 ug PFOS/l (1,200 ng/l, ppTr) See Review by Beach et al, 2005. Rev. Environ. Contam. Toxicol. Acute and subchronic toxicity of PFOS to freshwater phytoplankton Species 96-EC50 96-NOEC Selenastrum capricornutum 68 (63-70) 42 Selenastrum capricornutum 48 (45-51) 5.3 Chlorella vulgaris 82 (70-99) 8.2 Anabaena flos-aque 131 (106-142) 94 Navicula pelliculosa 263 (217-299) 150 * EC50 (mg/L) values with 95% confidence intervals in brackets. * Effect levels bases on growth (cell density) Toxicity of PFOS to macrophytes Species Lemna gibba Lemna gibba Myriophyllum spicatum Myropyllum sibiricum Test Duration EC50 (mg/L) NOEC (mg/L) 7d 108 a 15 7d 59 a 31 b 29 6.6 42 d 13 c 17 d 11.4 11.4 42 d 3.4 c 2.4 d 2.9 0.3 • Effect values based on frond number (b) or biomass (b) • Effect values based on biomass (c) or root length (d) Toxicity of PFOS to aquatic invertebrates Species Daphnia magna Daphnia pulicaria Test Duration 48 hr 48 hr 48 hr 21 d 48 hr Endpoint Immobility Survival Survival Adult survival Immobility NOAE C 0.8 33 32 12 14 EC50/ LC50* 67 130 59 16 134 Crassostrea sp. 96 hr Shell Growth 1.8 >2.9 Unio complamatus 96 hr Survival 20 57 Artemia salina 48 hr Survival - 9.2 Mysidopsis bahia 96 hr 35 d Survival Growth/Repro. 1.1 0.24 3.5 - * All concentrations in mg/L Toxicity of PFOS to aquatic invertebrates (Continued) Species Chironomus tentans Test Duration 10 d Chironomus tentans 20 d Zooplankton 35 d All concentrations given as mg/L NC = not calculated Endpoint NOAEC Survival Growth Survival Growth Emergence Eggs/female Community Structure 0.05 0.05 0.094 0.022 < 0.002 NC 3.0 EC50/ LC50 > 0.15 0.087 0.092 0.094 0.095 No effect - Toxicity of PFOS to fish and amphibians Species Test a NOEC LOEC LC50 Rainbow Trout 96 hr NR NR 7.8 Rainbow Trout 96 hr 6.3 13 22 Fathead Minnow 96 hr 3.2 5.4 9.1 Fathead Minnow 47 d 0.29 0.58 - Fathead Minnow 28 d b 0.3 3.0 7.2 Leopard Frog 16 wk c 1.0 3.0 6.2 Xenopus FETAX 4.8 8.0 16 A Test were either static renewal or flow-through; Concentrations in mg/L. B Microcosm study C Partial life cycle test Derivation of a Screening Plant Value (SPV) for PFOS Guidelines for deriving a SPV • Based on least mean Genus Mean Chronic Value (GMCV) for species tested • Least GMCV was observed with Myriophyllum or water milfoil SPV = 2.4 mg PFOS/L Secondary Acute Value For Aquatic Organisms Secondary Acute Value (SAV) = Lowest Acute Value Secondary Acute Factor (SAF) Lowest species mean acute value (SMAV) is for Chironomus tentans with an EC50 of 0.087 mg/L Secondary Acute Factor (SAF) is an adjustment factor that accounts for various sources of uncertainty and depends on the number of data requirements that have been met. For 6 requirements, SAF= 5.2 SAV = 0.087 mg/L PFOS 5.2 = 0.017 mg/L PFOS Secondary Chronic Value for PFOS Secondary Chronic Value (SCV) = Secondary Acute Value Acute to Chronic Ratio (ACR) Acute to chronic ratio (ACR) based on toxicity studies with D. magna, fathead minnows and mysid shrimp. ACR derived as geometric mean of species specific ACR values. ACR = 13.9 17 ug/L PFOS SCV = 13.9 = 1.2 ug/L PFOS SCV = 1.2 µg PFOS/L Species Sensitivity Distribution (SSD) Water Values Comparisons 1.2 SCV SPV SAV 1 Probability 0.8 0.6 0.4 LC50/EC50 Data NOEC Data 0.2 0 0.001 0.01 0.1 1 PFOS Concentration (mg/L) 10 100 1000 Comparison of PFOS Concentrations in Laurentian Great Lakes to its Chronic Value Lake Erie SCV = 1,200 ng/L Lake Huron Lake Ontario Mich. Waters Niagara River 0.10 1000 1.0 10 100 PFOS Concentrations (ng/L) Comparison of PFOS Concentrations in Michigan Waters Chronic Value Detroit Region SCV 1.0 10 100 PFOS Water Concentrations (ng/L) 10001000 Conclusions Currently there are sufficient data to derive a Tier II water quality criterion for the Laurentian Great Lakes Additional Studies are needed to address data gaps such that a Tier I water quality criterion can be estimated Based on Tier II methodology, current water concentrations that have been measured in the Great Lakes do not pose a significant risk to aquatic organisms Derivation of a Safe Water Concentration for PFOS to Avian Species Derivation of Toxicant Reference Values (TRVs) Bird TRVs based on whole-life in vivo studies with bobwhite and mallards Mammalian TRVs (mink etc) based on pup weight reduction in rats Application of uncertainty factors Northern Bobwhite Quail Northern Bobwhite (Colinus virginianus) • Order Galliformes, Family Odontophoridae • Ground-dwelling upland game bird • Feeds primarily on weeds, woody plants and grasses. Adults and chicks also consume insects and other invertebrates Mallard Mallard (Anas platyrhynchos) Order Anseriformes, Family Anatidae Surface feeding dabbling duck (waterfowl) Feed primarily on aquatic plants and aquatic insects Avian Ecotoxicological Studies • Studies were designed according to OECD, FIFRA and OPPTS guidelines for avian species • All studies conducted with a well characterized PFOS stock • Studies conducted under TSCA Good Laboratories Procedures • Exposure concentrations determined analytically • Dose concentrations (liver and blood) determined analytically • Analytical methods validated for each matrix Northern Bobwhite Reproduction Test Final LOAEL Values Measures of PFOS Exposure ADULT MALES A Dose (mg PFOS/kg in Feed) ADI (mg PFOS/kg body weight/day) over 21-wk period Serum (mg PFOS/mL) at study termination (21-wks) Liver (mg PFOS/g) at study termination (21-wks) NOAEL LOAEL 10 0.77 140 88 ADULT FEMALES Dose (mg PFOS/kg in Feed) ADI (mg PFOS/kg body weight/day) over 21-wk period Serum ( m g PFOS/mL), pre-reproductive phase (5-wks) Serum (m g PFOS/mL), reproductive phase, (21-wks) Liver ( m g PFOS/g) at study termination (21-wks) OFFSPRING Yolk (mg PFOS/mL) A LOAEL was based on a decrease in the 14-d old survivability of offspring All concentrations are reported on a wet weight basis 10 0.77 84 8.7 4.9 62 Mallard Definitive Reproduction Study Final NOAEL and LOAEL Values Measures of PFOS Exposure A NOAEL ADULT MALES Dose (mg PFOS/kg body weight) ADI (mg/PFOS/kg body weight per day) over 21-wks Serum (μg PFOS/ml) at study termination (21-wks) Liver (μg PFOS/ml) at study termination (21-wks) 10 1.5 87 61 ADULT FEMALES Dose (mg PFOS/kg body weight) ADI (mg/PFOS/kg body weight per day) over 21-wks Serum (μg PFOS/ml) pre-reproductive phase (5-wks) Serum ( μg PFOS/ml) at study termination (21-wks) Liver ( μg PFOS/g) at study termination (21-wks) 10 1.5 77 17 11 OFFSPRING Yolk (μg PFOS/ml) A All concentrations given on a wet weight basis 53 Derivation of Toxicant Reference Values (TRVs) Based on whole-life in vivo studies with bobwhite and mallards Application of uncertainty factors Uncertainty Factors for a Generic Trophic Level 4 Predator Exposed to PFOS UNCERTAINTY FACTORS NOTES Inter-taxon Extrapolation (A) Threshold dose derived from northern bobwhite reproductive study. Assume the TRV is derived for a species in the same class but different order, A=5 Exposure Duration (B) The bobwhite quail study used to derive a test dose was a 20 week dietary reproduction study, B=1 Toxicological Endpoint (C) The LOAELvlaues were derived from adult and juvenile bobwhite quail. Significant effects were observed on multiple endpoints including reproduction, C=3 Uncertainty Factors for a Generic Trophic Level 4 Predator Exposed to PFOS (Cont.) UNCERTAINTY FACTORS NOTES Modifying Factors (D) -Threatened Species The bird is not listed or endangered, d1 = 0 - Relevance of Endpoint Endpoints in study include chronic and reproductive measurements d2 =0 - Lab to Field Extrapolation Dietary study was long term, low dose, and simulated year-round exposure. However, the study was not a two generation study, d3 =0.5 - Co-contaminants -Endpoint Clarity Co-contaminants were not present in the study, d4 = 0 Weight gain, and reproductive effects in bobwhite study are mechanistically and ecologically clear, d5 =0 Uncertainty Factors for a Generic Trophic Level 4 Predator Exposed to PFOS (Cont.) UNCERTAINTY FACTORS NOTES Modifying Factors (D) - Species Sensitivity While bobwhite quail were shown to be more sensitive than mallards, the magnitude of the differences was minimal. No other avian data are available, d6 = 1 - Organ Ratios Concentration in liver and serum were directly measured, d7 = 0 - Intraspecies Variability Adult, egg and juvenile life stages were evaluated in the study, d8 = 0 Total Modifying Factors D= (0+0+0.5+0+0+1+0+0) = 1.5 Uncertainty Factors for a Generic Trophic Level 4 Predator Exposed to PFOS (Cont.) UNCERTAINTY FACTORS (UF) Values Inter-taxon Extrapolation (A) Exposure Duration (B) 5 1 Toxicological Endpoint (C) 3 Modifying Factors (D) Overall UF for TRV 1.5 UF= (5 x 1 x 3 x 1.5) = 22.5 Derivation of Uncertainty Factors Calculate a Predicted No Effect Concentration (PNEC) for Avian Species Exposed to PFOS OECD methods • Uncertainty Factors based on “Technical guidance Document in Support of Commission Directive 93/67/EEC on risk assessment for newly notified substances and Commission regulation (EC) No. 1488/94 • Final uncertainty factor (UF) based on: - Chronic reproduction studies conducted with two avian species UF= 30 - NOAEL values were not determined for the most sensitive toxicological endpoint in bobwhite quail. UF = 2 • UF = 30 x 2 = 60 Derivation of Safe Water Concentrations for the Protection of Wildlife Test Dose x BW Overall Uncertainty Factor Wildlife Value = WL W + ∑ FTLi xBAFTLi ( ) Derivation of Safe Water Concentrations for the Protection of Wildlife • WV = Wildlife Value in milligrams of PFOS per liter (mg/L) • TD = Test dose or threshold dose in mg of PFOS per kg per day (mg/kg body weight-day). • UF = Overall Uncertainty factor interspecies, toxicological endpoint and exposure duration extrapolations. • BW = Average body weight in kilograms (kg) for the representative species. • FTLi = Species specific average daily amount of food consumed (kg/day) for trophic level I • W = Species specific average daily amount of water consumed (L/day) • BAFWLTLi =Bioaccumulation factor for wildlife food in trophic level i. For consumption of piscivorous birds by other birds, the BAF is derived by multiplying the Trophic Level 3 BAF by the biomagnification factor (BMF). Avian Threshold Doses for PFOS Liver Egg Yolk Threshold Average Daily Intake Serum (mg PFOS/kg/d) ( μg PFOS/ml)( μg PFOS/g, wet wt)( μg PFOS/ml) Dose LOAEL TRV PNEC a b 0.77 35 21 62 0.034 1.6 0.93 2.8 0.038 1.7 1.0 3.1 Threshold dose for each end point is based on the geometric mean of female and male values. The LOAEL based on the 10 ppm PFOS treatment in the bobwhite reproduction study. Average daily intake in units of mg PFOS/kg body weight per day TRV calculation based on an overall uncertainty factor (UF) of 22.5 PFOS Biomagnification Factor (BMF) for Avian Species • Biomagnification Factor (BMF) needed to calculate a Wildlife Value (WV) • BMF used to account for the accumulation of PFOS from piscivorous birds consumed by upper trophic level predators (raptors) • No Field Data are available to derive avian specific BMF for PFOS • BMFs were estimated from chronic reproduction studies with mallards and bobwhite quail and based on feed and tissues PFOS concentrations. General BMF Equation: Bird Tissue PFOS Concentration BMF = PFOS Concentration in Diet Biomagnification Factor for PFOS in Avian Species Avian BMF Calculation Assumptions and Criteria • Assumed birds were at steady state • Concentration data was not lipid normalized • Male concentration data was used to estimate the BMF. Female data was not used due to losses of PFOS during egg laying phase of study • Liver concentrations were used to estimate BMF. Serum concentration data was not used used due to the greater variability of this matrix relative to that observed for liver in the same studies • Assumed 100% assimilation of PFOS from diet Biomagnification Factor for PFOS in Avian Species Species Feed Liver (ug PFOS/g) (ug PFOS/g) BMF Mallard 10 61 6.1 Quail 10 88 8.8 Geometric mean 7.3 Geometric mean of mallard and bobwhite quail BMFs used in the calculation of wildlife values. BMF = 7.3 PFOS Bioaccumulation Factors Bioaccumulation Factor (BAF) estimated from Bioconcentration Factors (BCF) derived from laboratory studies Laboratory Studies include: - Bluegill (Lepomis macrochirus) Whole body BCF = 3,614 (Drottar et al. 2001) - Rainbow Trout (Oncorhynchus mykiss) Carcass based BCF = 1,100 (Martin et al. 2003) Assume that predominate route of PFOS accumulation by fish is from water and not through food (BCF ~ BAF) Geometric mean of both species is: BAF = 1,994 Derivation of Safe Water Concentrations for the Protection of Wildlife TD WV = UF BAF • WV = Wildlife Value in ng PFOS per liter (ng/L) • TD = Threshold dose (mg PFOS/kg bw/day) • UF = Uncertainty Factor • BAF = BCF x BMF x food consumption Biomagnification Factor for PFOS in Avian Species Species Feed Liver (ug PFOS/g) (ug PFOS/g) BMF Mallard 10 61 6.1 Quail 10 88 8.8 Geometric mean 7.3 - BMF values calculated from the dietary chronic studies - Geometric mean of mallard and bobwhite quail BMFs used in the calculation of wildlife values. BMF = 7.3 - All measured values reported on a wet weight basis Accumulation of PFOS by birds from water BAF BC Water F BMF Threshold Food Dose 1,994 * 7.3 14,556 * BCF based on geometric mean of rainbow trout (BCF=1,100) and bluegill (BCF=3,614) Surrogate Avian Species Used in Wildlife Value Estimates Herring Gull (Larus argentatus) • Order Charadriiformes, Family Laridae • Feeds on a variety of foods including fish, crustacea, molluscs, insects, small mammals and birds, and garbage Bald Eagle (Haliaeetus leucocephalus) • Order Falconiformes, Family Accipitridae • Opportunistic feeder that consumes fish, birds, and small mammals depending on availability Belted Kingfisher (Ceryle alcyon) • Order Coraciidormes, Family Alcedinidales • Generally feeds only on fish but when available, will also consume crayfish. Exposure Parameters for Three Surrogate Avian Species Identified for Deriving Wildlife Values Species Herring gull Adult Body wt. (kg) Water ingestion rate (L/day) Food ingestion rate of each prey in each trophic level (kg/day) Trophic level of prey 1.1 0.063 TL3: 0.192 Fish: 90 (TL3: 80; TL4: 20) TL4: 0.0480 Other: 10 (% diet) Other: 0.0267 Bald Eagle 4.6 0.160 TL3: 0.371 Fish: 92 (TL3: 80; TL4: 20) TL4: 0.0929 Birds: 8: (PB: 70; other: 30) PB: 0.0283 Other: 0.0121 Belted Kingfisher 0.15 0.017 TL3: 0.0672 TL3: 100 Note: TL3 or TL4 = trophic level 3 or 4 fish; PB= piscivorous birds; Other = non-aquatic birds and mammals PFOS Wildlife Values Concentration for Avian Species Species Herring Gull Wildlife Value (μg PFOS/L) 0.079 Bald Eagle 0.026 Kingfisher 0.038 Geometric Mean 0.043 Effects Ranges: Birds/Water 3,797 ng/L – Lethal to Adults 1,725 ng/L – Subtle effects on testes without any effects on survival, growth or reproduction of quail (LOAEL) TRV: 50 ng/L – No effects, includes safety factor of 36 (EPA GLI) PNEC: 30 ng/L – No effects, includes safety factor of 60 (OECD) Assessment of Current Concentrations of PFOS Water concentrations compared to: Protection of aquatic life Protection of predatory birds and mammals Tissue concentrations Blood Liver Egg Bird Egg MOS Minimum = NIL (0.51) Geomean = 13.38 Exceedence Cormorant MI G.H. Owl MI Caspian Tern MI N = 60 TRV 1.7 Frequency Minimum = 0.008 Maximum = 3.35 Geomean = 0.127 20 15 10 5 0 0.01 0.1 1.0 10.0 PFOS (mg/ml, ww) Bird Liver MOS Minimum = NIL (0.34) Geomean = 8.61 Exceedence Bald Eagle MI B. Pelican MS C. Loon NC R.T. Loon NC B.B. Gull NC G. Egret FL B.C.N.H. CA Osprey FL Cormorants Japan N=219 TRV= 0.6 50 Frequency Minimum = 0.001 Maximum = 1.740 Geomean = 0.0697 60 40 30 20 10 0 0.001 0.01 0.1 1.0 10.0 PFOS (mg/kg ww) Bird Blood Plasma Minimum = 0.001 Maximum = 2.57 Geomean = 0.108 MOS Minimum = NIL (0.38) Geomean = 8.98 Exceedence Bald Eagles AL, WI, SC Frequency 16 N = 61 TRV 0.97 12 8 4 0 0.001 0.01 0.1 1.0 10.0 PFOS (mg/kg, ww) Water vs. Bird TRV 60 MOS Minimum = NIL (0.022) Mean = 2.80 Exceedence FL, AL Lake Ontario Canada TRV = 50.0 50 Frequency Minimum = 0.00004 Maximum = 2210 Mean = 17.87 40 30 20 10 0 0.001 0.1 10 1000 PFOS (ng/L) Sampling in South Bohai coastal rivers of China. PFCs in Estuarine and Coast of North Bohai Sea North Bohai Bay, especially Liaoning Province PFCs in Water from North Bohai Bay Potential Ecological Risk to Aquatic Animals General Conclusions PFCs-China Significant concentrations of PFCs were found in water (mean: 18.4 ng/l) and biological samples (fish: 265 ng/g dw). While concentrations of PFCs in soils and sediments were less. The predominately detected compound was PFOS, with a maximum of 30.9 ng/l in water and 791 ng/g dw in fish. PFCs were significantly greater in Liaohe River system, which suggests point sources in this urbanized and industrialized region. PFOS concentrations in water and biota were both less than the reported threshold concentrations. General Conclusions Concentrations in water or tissue are generally less than the thresholds Thresholds are exceeded only in a few industrial areas Thresholds are conservative (protective) such that exceedences do not necessarily indicate the potential for population level effects Nanjing Questions ??????? Thank You!!!!! Questions???? John P. Giesy, Ph.D. Professor & Canada Research Chair in Environmental Toxicology Dept. Veterinary Biomedical Sciences & Toxicology Centre University of Saskatchewan Saskatoon, SK, Canada Tel: (306) 966-2096 Fax: (306) 931-1664 Email: John.Giesy@usask.ca WebSite: http://ww.usask.ca/toxicology/faculty_profiles/giesy_john.html