Perfluorinated Compounds in the Environment: Where are we, how did we get here and where are we going

Transcription

1 Perfluorinated Compounds in the Environment: Where are we, how did we get here and where are we going John P. Giesy Gordon Conference Environmental Sciences: Water June 30, 2004 Plymouth, NH

2 Colleagues and Cooperators J.P. Giesy 1,2, P. D. Jones 1, P.K.S. Lam 2, I.M.K. So 2, G.J. S. Zheng 2, J.L. Newsted 3, B.S.H. Im 4 N. Yamashita 5 and S. Taniyasu 5, 1 Zoology Department, National Food Safety and Toxicology Center, Center for Integrative Toxicology, Michigan State University, MI, USA 2 Dept. Biology and Chemistry, City University of Hong Kong, Kowloon, Hong Kong, China 3 ENTRIX, Inc., East Lansing, MI, USA 4 DK Science, R & D Center, Gongduck-dong, Mapo-gu, Seoul , Korea 5 National Institute of Advanced Industrial Science and Technology (AIST), Japan

3 Availability of Information Reports containing detailed information are available at docket EPA AR226. Information is available electronically from the EPA docket staff in the form of pdf files. To request the index or any document listed on the docket, send an e- mail message to the docket staff at or call The docket staff will send the index and any documents to you via . Additional details regarding the Pollution Prevention and Toxics Docket Can be Obtained online at Send a blank CD to the public reading room at the following address: Public Reading Room, Room B102 EPA West Building 1301 Constitution Avenue, NW Attn: OPPT Docket Staff

4 Previously Published Papers-I Giesy, J. P. and K. Kannan Global Distribution of Perfluorooctane Sulfonate and Related Perfluorinated Compounds in Wildlife. Env. Sci. Technol. 35: Kannan, K., et al Perfluorooctane Sulfonate and Related Fluorinated Organic Chemicals in Marine mammals. Environ. Sci. Technol. 35: Kannan, K., et al Perfluorooctane Sulfonate in Fish-Eating Water Birds Including Bald Eagles and Albatrosses. Environ. Sci. Technol. 35: Kannan, K., et al Perfluorooctane Sulfonate in Oysters (Crassostrea virginica), from the Gulf of Mexico and Chesapeake Bay, USA. Arch. Environ. Contamn. Toxicol. 42: Kannan, K., et al Perfluorooctane Sulfonate and Related Fluorinated Hydrocarbons in Marine Mammals, Fish and Birds from Coasts of the Baltic and The Mediterranean Seas. Environ. Sci. Technol. 36:

5 Previously Published Papers II Kannan, K., et al Concentrations of Perfluorinated Acids in Livers of Birds from Japan and Korea. Chemosphere, 49: Kannan, K., J.L. Newsted, R.S. Holbrook and J.P. Giesy Perfluorooctanesulfonate and Related Fluorinated Hydrocarbons in Mink and River Otters from the United States. Environ. Sci. Technol. 36: Giesy, J.P. and K. Kannan Perfluorochemical Surfactants in the Environment. Environ. Sci. Technol. 36:146A-152A.

6 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.

7 Most fluorochemicals in the environment are anthropogenic. There are many perfluorinated compounds produced and used Biologically produced fluorochemicals contain only one fluorine atom e.g., MFA

8 Structures of Sulfonated Fluorochemicals POSF: Perfluorooctanesulfonylfluoride POSF is the starting material for polymer production PFOS: Perfluorooctanesulfonate PFOS is the ultimate degradation product of POSF-based compounds and the compound found in the environment O C 8 F 17 S - F O O C 8 F 17 S - O - O F F F F F F C C C C F C C F F C C F S F F F F F F F O O O

9 Structures of Sulfonated Fluorochemicals O FOSA: Perfluorooctanesulfonamide C 8 F 17 S - NH 2 O PFOA or POAA: Perfluorooctanoic acid O C 7 F 15 CO -

10 Some Compounds of Interest Compound Formula Tridecafluoroheptanoate (C7) C 6 F 13 COO - Pentadecafluorooctanoate (C8; PFOA) C 7 F 15 COO - Heptadecafluorononoate (C9) C 8 F 17 COO - Nonadecafluorodecanoate (C10) C 9 F 19 COO - Perfluoroundecanoate (C11) C 11 F 21 COO - Perfluorododecanoate (C12) C 12 F 23 COO - Perfluorooctane sulfonate (PFOS) C 8 F 17 SO - 3

11 Production Electrochemical fluorination 2C 8 H 17 SO 2 F + 34 HF ( V) 2 C 8 F 17 SO 2 F + 17 H 2 1-Octanesulfonayl fluoride Perfluorooctanesulfonayl fluoride (POSF) The product is not pure, but rather a mixture of isomers and homologues. Commercial POSF is approx. 70 % straight chain and 30 % branched

12 Production Telomerization YZ (Telogen) + na (Taxogen) Y - (A)n-Z (Telomer) This process results in only molecules containing only even numbers of carbon atoms

13 Production Total production of carboxylated and sulfonated PFCs is unknown 3M Produced 6.5 X10 6 pounds in % used in surface treatments 42 % used on paper products for oil and grease resistance Fire fighting foams (AFFF) was 6.8X10 6 liters in 1985 (3 and 6 % concentrates)

14 Perfluoroalkane Surfactants Used singly or in combination with other compounds to make polymers

15 Uses of Fluorinated Surfactants Adhesives: Wetting agents Antifogging: Glass surfaces Antistatic agents: Microchip manufacture Cement additives: Reduce shrinkage of cement Cleaners for hard surfaces: Floor Polishes Coatings: Paint additives, waxes Cosmetics: Hair-conditioning Electronics: Insulators Electroplating: Chromium, copper and nickel Etching: Glass Fire-Fighting Foams: Formulated to float on flammable liquids Herbicides and Insecticides: Wetting agents Leather: Provide water and oil repellency Paper: Oil and water repellency Textiles: Polyester etc. to impart soil, oil and water repellency. Major use is in carpeting.

16 Papers coated with PFOS-based fluorochemicals

17 Scotchguard-Major Use

18 How Did We Get Here? PFFAs were persistent and bioaccumulative PFFAs were primarily used in polymers and thought to be inert and were not expected to enter the environment and be accumulated in biota PFFAs were thought to be nontoxic PFFAs have a fundamentally environmental profile tha chlorinated hydrocarbons There was a lack of a suitable method and standards to allow for monitoring of the environment

19 How Did We Get Here? 1950 Large scale production begins with many uses Organic fluorine found in human blood University of Rochester (UR) Dr. Travers (UR) confirms earlier UR studies, tentatively identifies PFOS in human blood Early 1990s - 3M uses advanced mass spectrometry to scan worker s blood - detects with MDL of 0.5 mg/l (ppm) Univ. Minnesota reports no effects in PFOSexposed workers. Elsewhere PFOS linked to cancer in rodents and changes in reproductive hormones in humans

20 How Did We Get Here? Rsearchers at (MSU) report finding organic fluorine compounds in water, air and soil May, M advises US EPA that it found organic fluorine in blood bank samples - decides to move away from this chemistry Sept M reports to US EPA results of studies in which offspring of rats die within days February, MSU reports PFOS found in a variety of wildlife species from many locations around the world

21 How Did We Get Here? March, M and US EPA discuss latest finding, including chronic studies of reproduction in monkeys May 16, M and US EPA announce that the company will voluntarily phase out manufacture and use of PFOS Improvements in methods for abiotic and abiotic matrices MSU, 3M and EPA conduct toxicity studies to determine mechanisms of action and thresholds for effects of PFOS Many laboratories around the world begin to report concentrations of PFFAs in biota, water and air

22 How Did We Get Here? 2002 Special sessions begin to appear at scientific meetings and the number of publications increases Government agencies conduct inventories of production and use and conduct risk assessments 2003 Workshop on Analytical Methods held in Hamburg Germany 2004 Better analytical standards become available University and government laboratories obtain the necessary instrumentation and begin conducting surveys

23 Currently replacements are being sought for useful products

24 Analytical Procedures

25 Current Methods for Water S.O., M.K., S. Taniyasu, N. Yamashita, J.P. Giesy, J. Zheng, Z. Fang, S.H. Im & P.K.S. Lam Perfluorinated Compounds in Coastal Waters of Hong Kong, South China and Korea. Environ. Sci. Technol. (In Press). Methods for Biological Samples, using KOH solubolization and SPE extraction will be published soon

26 Current Limitations Instrumentation is expensive and many laboratories do not have access to the necessary instrumentation Lack of validated methods new methods are being developed all the time Lack of certified standards, especially stable isotope labeled internal standards

27 Criteria for the Selection of Analytical Methods Sufficiently Sensitive Accurate Reproducible Transportable Simple High Throughput Minimize Interferences

28 Extraction procedures Wash Oasis HLB cartridge with 5ml HPLC MeOH 5ml HPLC distilled water Load 500ml water samples (spiked with THPFOS) Wash cartridge with 5ml 40% MeOH Elute with 10ml 100% MeOH Collect eluate Reduce volume to 0.5ml Injection to LC/MS/MS

29 Extraction Methods for Open Ocean Water Waters Oasis HLB Sep-Pak 40% methanol/water 100% methanol Fraction 2 concentration 0.2mL to 8mL

30 Analytical Procedures Seawater Samples Collection of samples (six liters, each location) Preparation of samples (spiking with 10 µl of 100 ng/ml THPFOS) Extraction using Oasis HLB extraction cartridge (0.2g, 6cc), preconditioned with 5ml HPLC methanol, followed by 5 ml HPLC distilled water at a rate of 2 drops/sec Loading samples (0.2 to 1.0 L, and eluting (1 drop/sec) Discard

31 Analytical Procedures Seawater Samples Washing cartridge (5ml 40% methanol in water, 1 drop/sec) Discard; Let cartridge to run dry Extraction target compounds (10ml methanol, 1 drop/sec), such as PFOS, PFOA, PFOSA, PFNA, PFHS, PFBS, and THPFOS Concentrate to 0.2~0.5ml Analysis using high performance liquid chromatography with high resolution, electrospray tandem mass spectrometry (HPLC-MS/MS). Quantification by External standards.

32 Standards Available Compounds Monitored for PFOS: Perfluorooctanesulfonic acd potassium salt: C8F17SO3 K PFHpS: Perfluoroheptanesulfonic acid potassium salt: PFBS: Perfluorobutanesulfonic acid potassium salt: PFOSA: Perfluorooctanesulfonomide: C8F17SO2NH2 THPFOS: Tetra Hydro PFOS: C8H4F13SO3 PFBA: Perfluorobutyric acid: C3F7COOH PFPeA: Perfluoropentanoic acid: C4F9COOH PFHxA: Perfluorohexanoic acid: C5F11COOH PFHpA: Perfluoroheptanoic acid: C6F13COOH PFOA: Pentadecafluorooctanoic acid (Perfluorooctanoic acd): C7F15COOH PFNA: Perfluorononanoic acid: C8F17C00H PFDA: Perfluorodecanoic acid: C9F19COOH PFUnA: Perfluoroundecanoic acid: C10F21COOH PFDoA: Perfluorododecanoic acid: C11F23COOH N-Et FOSA: Ethyl FOSA Alcohol: N-MeFOSE: Methyl FOSE Alcohol: N-Et FOSE: Ethyl FOSE Alcohol: APFO: Ammonium perfluorooctanoate: C7F15COONH3 4:2FTOH: 1-hydroxyethane-2-perfluorobutane: CF3(CF2)3(CH2)2OH 6:2FTOH: 1-hydroxyethane-2-perfluorohexane: CF3(CF2)5(CH2)2OH 8:2FTOH: 1-hydroxyethane-2-perfluorooctanol: CF3(CF2)7(CH2)2OH PDFO: Pentadecafluoro-1-octanol: CF3(CF2)6CH2OH POSF: Perfluorooctanesulphonyl fluoride: C8F17SO2 F POSF: Perfluorooctanesulphonyl fluoride: C8F17SO2 F 10:2 FT-OH, 1-hydroxyethane-2-perfluorodecanol

33 LC Separations LC: Agilent 1100 Series

34 Instrumental Analyses MS: Micromass Quattro Ultima Pt Triple Quadrapole; MassLynx Ver. 3.5 Sciex API 4000 with collision energy of -10 (ev) for PFOA results in approximately 10X lesser LOQ.

35 Compounds Studied Compound Molecular Weight Tridecafluoroheptanoate (C7) 363 Pentadecafluorooctanoate (C8; PFOA) 413 Heptadecafluorononoate (C9) 463 Nonadecafluorodecanoate (C10) 513 Perfluoroundecanoate (C11) 563 Perfluorododecanoate (C12) 613 Perfluorooctane sulfonate (PFOS) 499

36 Unextracted Standard 100 PFHS (399 > 99) 6.43 Time (min) % % PFOSA (498 > 78) PFOS quantification (499 > 99) 6.80 % % PFOS Confirmation (499 > 80) % PFOA (413 > 169)

37 SPE Standard Extracted from DI Water 100 PFOSA (498 > 78) 7.22 Time (min) % PFOS Quantification (499 > 99) 6.80 % PFOS Confirmation (499 > 80) 6.83 % PFOA (413 > 169) 6.69 %

38 Spiked Water Sample Extracted by SPE 100 PFOSA (498 > 78) 7.16 Time (min) % PFOS Quantification (499 > 99) % PFOS Confirmation (499 > 80) % PFOA (413 > 169) %

39 Background Reduction Components of the LC can contribute PFCs to the blank. Almost all of the newest instruments use fluorochemical materials in some of their parts. We checked a few LC, and selected the Agilent LC, because it was easy to change these components. We used stainless or peek tubing instead of Teflon tubing, stainless solvent inlet filter instead of Teflon. Degasser and solvent selection valves were not used. because they also contain Teflon. ~INSTRUMENTAL BLANK~ Stainless tubing No degasser Stainless solvent inlet filter No solvent selection valve Polyethylene septum Polypropylene vial Polypropylene insert

40 Background Reduction Another source of PFCs was the septum. Polyethylene (cyan trace above), Teflon (pink) and Viton (yellow) septa were compared. PFCs other than the target compounds, PFBS and PFOSA were also checked for. A chromatogram of the standards is also given (white). The Teflon and especially Viton septa contributed PFCs to the blank. Therefore, PE septum was selected for PFC analyses

41 Background Reduction

42 Background Reduction H2O/MeOH Blank 100 % % % % 0 PFOS PFOA PFHS BEFORE MRM of 5 Channels ES > e4 MRM of 5 Channels ES > e6 MRM of 5 Channels ES > e3 MRM of 5 Channels ES > e Time MeOH 100 % % % % PFOS PFOA PFHS PFBS AFTER MRM of 5 Channels ES > MRM of 5 Channels ES > e3 MRM of 5 Channels ES > e3 MRM of 5 Channels ES > Time Background is a serious problem, when we measure low-levels of PFCs. These chromatograms of MeOH before and after we changed all the components. Before changing, when only MeOH was injected, high concentrations of PFCs were detected. After changing, PFCs in the blank decreased dramatically, however PFOA remained at a trace level. In general, this removed the background problems. Use of a clean room is recommended.

43 Blank Concentration Target analyte Range Blank (pg/ml; µg/l) Mean S.D. n PFOSA <5.0x10-3 <5.0x PFOS <5.0x10-3 <5.0x PFNA <2.0x x x x10-2 PFOA 3.2x x x x PFBS <5.0x10-3 <5.0x PFHS <5.0x10-3 <5.0x

44 LOQ for PFFAs in Water pg/l = PPQ Compound PFOS PFOSA PFHS PFBS PFNA PFOA THPFOS LOQ 5.0 pg/l 5.0 pg/l 5.0 pg/l 5.0 pg/l 20.0 pg/l 20.0 pg/l 20.0 pg/l LOQ = 2X Signal to Noise, <30% Precision

45 Recovery (%) Target analyte Range Mean Recovery (%) S.D. n PFOSA PFOS PFNA PFOA PFBS PFHS

46 PFCs In Open Ocean Water concentrations [pg/l]

47 PFCs In Open Ocean Water concentrations [pg/l]

48 PFCs In Sea Water concentrations [pg/l]

49 PFCs In Open Ocean Water MID-ATLANTIC OCEAN Oct Nov concentrations [pg/l] PFOA PFOS PFHS

50 Results of Ocean Monitoring COASTAL AREAS OF JAPAN All target PFCs were found in all samples. PFOA concentrations ranged from 3 to 180 ng/l, PFOS: from 40 pg/l to 30 ng/l and PFHS: from 50 pg/l to 40 ng/l. PFOA was the predominant PFC compound in water. Concentrations in urban areas in Japan such as Tokyo and Osaka were greater than in rural areas. Concentrations of PFOA and PFOS in Tokyo Bay and Osaka Bay water were similar to those reported for waters collected upstream (PFOA:<25 ng/l, PFOS:17-54ng/L) but less than those found downstream (PFOA: ng/L, PFOS:75-144ng/L) of a fluorochemical manufacturing facility in the Tennessee River, USA (Hansen et al., 2002).

51 Results of Ocean Monitoring OPEN OCEAN AREAs Japan PFOA concentrations ranged from 140 to 1060 pg/l, PFOS: from less than 40 to 78 pg/l and PFHS: from 0.4 to 6 pg/l. Concentrations of PFCs in open Ocean water were 3 to 2000 times less than those in coastal waters of Japan. South China Sea and Sulu Sea PFOA concentrations ranged from 90 to 510 pg/l, PFOS: <17 to 110 pg/l and PFHS: <0.2 pg/l Mid Atlantic Ocean PFOA concentrations ranged from 100 to 440 pg/l, PFOS: from <48 to 73 pg/l and PFHS: from 3 to 12 pg/l. Open ocean water concentrations were similar to each other.

52 VERTICAL PROFILE OF PFOS & PFOA Vertical profiles of PFC concentrations, were determined in discrete water samples from surface to bottom were collected at the South China Sea and Sulu Sea. We measured water from 10 m to 1000 m depth in site A and 10 m to 3500 m depth in site D. The greatest concentrations of PFOA and PFOS were observed in surface water.

53 Summary of Results PFC BLANK Selection of Septum was important: Teflon and Viton septas contaminated samples. Many fluorinated materials in LC equipment such as tubing, degasser, pump mixer, inlet solvent filter etc Blank levels of water procedure were PFOA:30~60pg/L PFOS:10~20pg/L PFHS:<0.2pg/L COASTAL SURFACE SEA WATER Concentrations of PFCs in coastal seawater were at the ppt-level. Concentrations of PFCs in urban areas were 50 to 70 times greater than those in rural areas. OPEN OCEAN SURFACE SEA WATER Concentrations of PFCs in open ocean water samples were in the ppq-level and similar among locations. Concentrations of PFCs in open ocean water were 3 to 2000 times less than in coastal waters. Concentrations of PFOA were greater than those of PFOS. VERTICAL PROFILE PFOA and PFOS were ubiquitous in sea water

54 PFCs in Korean Seawater Sampling Sites Concentrations of PFCs (ng/l) PFOS PFOA Total PFCs Site 8 : Estuary and lake with a number of local industries. Site 6 : Port area, highly populated and many commercial activities. Site 4, 5 : Open Ocean possibly affected by industrial activities. Site 11 : Open ocean sample, possibly affected by industries. Site 2 : Open oceanic.

55 PFCs in Korean Seawater Total concentrations of PFCs in the sample from site 8 (1120 ng/l), which has a number of industries, is greater than that of site 6 (2.63 ng/l), near Pusan city Korea s 2 nd largest city.

56 PFCs in Korean Seawater Industrial activities could affect sites 4 and 5, although those samples are collected from the oceanic areas and may be diluted with open ocean seawater, the total concentrations of PFCs (11.8 ng/l and 8.34 ng/l, respectively) are still greater than that of samples from site 6 (2.63 ng/l)

57 Concentrations of PFCs in Korea All water samples collected from 11 sampling locations in Korea contained most of the Perfluorinated compounds, including PFOSA, PFOS, PFNA, PFOA, PFHS and PFBS Total concentrations of PFCs in samples from Korea ranged from 0.28 ng/l to 1120 ng/l Total concentrations of PFCs varied considerably among sampling sites, The two predominant PFCs, PFOS and PFOA were present in 76% and 100% of water samples, respectively

58 Sampling Locations in China Sampling stations in 2003 (Hong Kong: July; Pearl River Delta: September) Sampling stations in 2004 (Hong Kong and Pearl River Delta: January)

59 PFOS and PFOA concentration in Chinese waters during winter 18 Concentration (pg/ml) PFOS PFOA CH1 CH2 CH3 CH4 CH5 CH6 Sampling locations

60 PFOS concentrations in Hong Kong waters PFOS concentration (pg/ml) Summer Winter HK1 HK2 HK3 HK4 HK5 HK6 Sampling locations

61 PFOA concentrations in Hong Kong Waters 7 PFOA concentration (pg/ml) Summer Winter HK1 HK2 HK3 HK4 HK5 HK6 Sam pling locations

62 PFOA:PFOS Ratios Location Mean Range Hong Kong Winter (8) Summer (6) China Winter (6) Summer (6) Korea Except station 8 (10) Station

63 Other Possible PFCs of Interest 8:2 telomer B Alcohol (8-2 TBA): F(CF2)8CH2CH2OH: CAS# Three transformation products of PFOA have been identified: CF3(CF2) 6 CF2CH2COOH (2-perfluorooctyl ethanoic acid), CF3(CF2)6CF=CHCOOH (2H-hexadecafluoro-2-decenoic acid), CF3(CF2)6COOH (perfluorooctanoic acid), A fourth possible transformation product is: CF3(CF2)6CH2CH2COOH (2H, 2H, 3H, 3H-perfluorodecanoic acid)

64 Where are We? PFFAs are widely distributed in the environment, including the open and deep ocean PFOA is the predominant PFFA in ocean water in most locations Additional work is needed on toxicity of PFOA Additional work is needed to determine the sources of PFOS in Korea

65 Where are we Going? To further assess the environmental fates and potential effects of PFCs we need Better instrumental techniques More authentic standards More information on chemical and physical properties of PFCs More information on mechanisms of action Additional information on the accumulation of various PFCs, particularly PFOS More information of the threshold for effect Assessment of mixtures (equivalency approach?)

66 Where are we Going? Some questions Do we need to consider the different isomers of each PFC? What proportion of the total organically bound Fluorine has been identified? What are the degradation and transformation pathways? What are the transport pathways? What are tissue distributions? What are the target tissues for accumulation and effects? Can QSAR relationships be developed to deal with complex mixtures? What are global inventories, production and use? Others???????

67 Questions??????? City U

68 Thank You John P. Giesy Dept. Zoology East Lansing, Michigan, 48824, USA Tel: (517) Fax: (517) Web Site: