Document JJ7pg1zZmEjm8Z1gnwmm3ERa6

IOCS' 17(f THE OCCURENCE OF PERFLUOROOCTANOATE IN ENVIRONMENTAL, DIETARY AND HUMAN SAMPLES PREPARED BY: ro hO - CC t o oo " c r n " J, c J 0 1 ; ` J - 1 2 CO ; ") C J TO 03 iO THE ASSOCIATION OF PLASTIC MANUFACTURERS IN EUROPE (APME) AD HOC APFO TOXICOLOGY WORKING GROUP VERSION 1: JANUARY, 11 2002 CONTAIN NO CRf INTRODUCTION AND SUMMARY Several studies have been undertaken under the sponsorship of 3M to understand the distribution of perfluorooctanoate (PFOA) in the environment. This document summarizes results from several of these studies that have been placed on EPA Docket Number AR-226. The general conclusion that can be drawn from this summary is that PFOA is not broadly dispersed in the environment, and, in those cases where it is detectable, typically occurs at low (< 1 ng/g (ppb) or < 1 pg/L (ppb)) concentrations. It is not possible from the results of these studies to draw conclusions as to the source of PFOA in those instances where PFOA has been detected in the environment. Summary of a Survey of Perfluorooctanoic Acid (PFOA) in Wildlife Five studies conducted by J.P. Giesy and K. Kannan of the Michigan State University determined the worldwide occurrence and accumulation of perfluorooctanoic acid (PFOA) and several other perfluoro compounds in aquatic wildlife and fish-eating water birds. PFOA did not seem to be widely distributed and was not present at concentrations above the limit of quantitation (LOQ) levels in many of the species studied. Species in which PFOA was detected above the LOQ levels are listed in Table 1. Various species in which PFOA was below the LOQ are listed in Tables 2 (mink and river otter), 3 (fish species), 4 (marine and mammal species), 5 (fish-eating water birds) and 6 (American oyster species). PFOA was found in 18/31 mink livers from Massachusetts (30) at concentrations ranging from 18.4 to 108 ng/g, dry wt with a mean for the positive samples of 319.7 ng/g, dry wt. PFOA was below the LOQ in the mink liver samples from Louisiana (7), South Carolina (9) and Illinois (30). PFOA concentrations in 5 river otter livers from Washington and Oregon were less than the LOQ of 36 ng/g, wet wt. In fish, PFOA was found to be above LOQ levels only in muscle tissue obtained from various species obtained from the Scheldtz River Estuary in Belgium with a range of 7.5 - 46 ng/g, wet wt (mean = 17). Muscle tissues of freshwater fish from several inland lakes of Michigan as well as marine fish from the Baltic Sea, and the North Pacific and Antarctic oceans did not contain detectable concentrations of PFOA. Liver and / or blood samples of marine mammals were collected from Florida, California and Alaskan coastal waters, the northern Baltic Sea, the Mediterranean Sea, and the Arctic. PFOA was found in 1/6 California sea lions, 1/26 grey seals (Baltic Sea), 6/109 Ringed seal samples (Baltic Sea) and in 3/8 Caspian seals (Russia). Examples of marine and polar mammals with tissues that do not contain PFOA (at levels above the LOQ) include polar bears, Baikal seal (Russia), and striped dolphins (Mediterranean). Measurements of perfluoro compounds in liver, kidney, blood or egg yolk of fish-eating water birds in the United States including albatrosses from Sand Island, Midway Atoll in 2- - the central North Pacific Ocean were performed. Similarly, tissues of birds collected from the Baltic and the Mediterranean Seas and from the Japanese and Korean coasts were also analysed. PFOA was detected in all 12 cormorant (Mediterranean) livers and was also detected in the following birds: Stenella clymene (Gulf of Mexico), Layasan albatross (Sand Island, Midway Atoll), double crested cormorant (Lake Winnipeg and St. Martin Island, Great Lakes, black billed gull (Sulphur Island, Great Lakes) and sea eagles (Japan). With the exception of the Japanese sea gull (two out of six blood samples contained 4.5 and 6.2 ng/mL PFOA), PFOA was rarely found in Japanese and Korean birds. Oysters were collected from 77 locations in the Gulf of Mexico and Chesapeake Bay of the US coast. PFOA was not found in quantifiable concentrations. In conclusion, PFOA is not widely distributed in aquatic (freshwater and marine) life and in mammals and birds that feed on fish. Summary of Survey of PFOA in Municipalities Samples were taken from six cities and included samples of publicly owned treatment works (POTW) effluent, POTW sludge, drinking water intake, treated drinking water, tap water, landfill leachate, surface water, sediment and quiet (standing) water. In all 101 sets of duplicate samples were analyzed. A summary of these findings occurs as Table 7. In 55 instances both duplicate samples had no detectable PFOA. In 14 instances, at least one replicate sample had detectable but non-quantifiable (< LOQ of 0.025 pg/L (ppb)) PFOA. Of those samples with quantifiable PFOA, eight had concentrations > 1 pg/L, 6 had concentrations < 1 pg/L and > 0.1 pg/L, and 18 had concentrations < 0.1 pg/L. All POTW effluent samples contained PFOA. All but one POTW sludge samples contained PFOA, and the highest PFOA concentrations in the study were found in sludge samples from Decatur, Alabama (244 pg/L (ppb)). With the exception of Columbus, Georgia, all drinking-water-related samples contained non-detectable PFOA. The drinking-waterrelated samples from Columbus, Georgia all contained non-quantifiable PFOA or PFOA concentrations just above the limit of quantitation. PFOA was detected at quantifiable levels in landfill leachate from Decatur, Alabama, Columbus, Georgia, and Port St. Lucie, Florida. Surface waters from Mobil, Alabama and Columbus, Georgia contained low, but quantifiable levels of PFOA. Only the 1999 sediment samples from Port St. Lucie, Florida contained quantifiable concentrations of PFOA. PFOA was not present in sediment from Port St. Lucie in 2000. PFOA was quantifiable in quiet water samples from Decatur, Alabama, Mobil, Alabama and Port St. Lucie, Florida. In summary, with the exception of POTW effluent and sludge from the six cities studied, and landfill leachate from Decatur, Alabama, PFOA is either not detectable or occurs at concentrations generally less than 1 pg/L (ppb). Market Basket Study Summary In over 230 samples of foodstuffs, PFOA was quantitated in only six samples above a quantitation limit of 0.5 ng/g (ppb). PFOA was found in two samples of ground beef 3- - (1.09 and 0.504 ng/g), one sample of bread (0.524 ng/g), two samples of apples (1.13 and 2.35 ng/g), and a sample of green beans (0.543 ng/g). An appropriate conclusion from this study is that PFOA is not distributed widely in foodstuffs. Human Populations Table 8 summarizes results from studies of the presence of PFOA in the sera of human adult and pediatric populations. Among 652 adult Red Cross blood donors, PFOA serum concentration ranged from < the lower limit of quantitation to 57.3 ng/mL (ppb). The geometric mean PFOA concentration in adults was 4.6 ng/ml, and the cumulative 95th percentile concentration was 12.9 ng/mL. Among 599 children aged 2-12 years, serum PFOA concentration ranged from < the lower limit of quantitation to 56.1 ng/mL. The geometric mean PFOA concentration was 4.9 ng/mL and the cumulative 95th percentile concentration was 10.2 ng/mL. In both cases the standard mean concentration was 5.6 ng/mL. From this data, there do not appear to be significant differences between the adults and children with respect to PFOA serum concentration. 4- - Table 1 PFOA Levels in Some of the Species Studied by Giesy and Kannan Species Mink Source Mass. Tissue Liver n S am p les ng/g wet wt LOQ o or m l, ng/g wet wt or <+) m l. 31 18 18.4-108 18.8 (m = 32) (dry wt) (dry wt) Fish Species: Fish Belgium Muscle 26 8 <7.5 - 46 Various species (m=17) Fish Michigan Inland Eggs* 19 1 13.7 Various species Lakes Muscle 103 3 Detected, not quantified 7.5 8.03 20.1 8.03 20.1 M arine and M am m al Species: California Sea California Liver 6 1 41 35.9 Lion Grey Seal Bottlenose Dolphin Baltic Sea Italian Coast Blood Blood 26 4 1 3 6.79 2, 3, 4 4.98 mL Ringed Seal Baltic Sea Blood Serum Liver 18 10 81 17 3 8.3, 14.6, 17.1 2 29.1.39.5 6.22 6.22 18.8 Caspian Seal Caspian Sea, Russia Blood 8 3 7,11,23 5.99 Stenella clymene Gulf of Mexico Liver 3 1 20 7.5 F ish-E ating W ater Birds: Cormorant Mediterranean Sea Liver 12 12 29-444 m = 94) None reported Laysan albatross Sand Island, Midway Atoll Liver 3 1 182 180 Double crested cormorant Lake Winnipeg St. Martin Island, Yolk Blood 4 2 2 1 192,245 48.9 180 29.9 Great Lakes Black billed gull Sea Eagle Sulphur Island, Great Lakes Japan Yolk Blood 3 27* 2 2 196. 197 4.5, 6.2 wet wt 3.35 Kite Japan Liver 2 1 Detected, not 18.8 quantified Black Headed Gull Japan Liver 1 1 Detected, not Not stated quantified * Only 7 samples were analysed: the other 20 samples were lost during extraction (spilled out of tube). 5- - Table 2 Species in Which PFOA Was not Detected Above the Limit of Quantitation (LOQ) Species Mink River Otter Source Illinois Louisiana South Carolina Washington Oregon Tissue Liver Liver Liver Liver n 30 7 9 5 LOQ ng/g wet wt 35.9 18.8 18.8 35.9 6- - Table 3 Fish Species in Which PFOA Was not Detected Above the Limit of Quantitation (LOQ) Species Yellowfin Tuna Chinook Salmon Lake whitefish Source N Pacific Great Lakes, Inland Lakes, Michigan Great Lakes, Inland Lakes, Michigan Carp Brown trout Saginaw Bay, Michigan Great Lakes, Inland Lakes, Michigan Swordfish Tunafish Bluefin Tuna Trematomus pennelli Silver fish Krill Salmon Fish Various Species Mediterranean, Italian coast Mediterranean Italian Coast Antarctica Antarctica Antarctica Baltic/Finnish Poland Fish Various Species Fish Various Species Czech R Michigan inland lakes Tissue Liver Liver Muscle Liver Eggs Muscle Whole Muscle Liver Eggs Muscle Liver Blood Liver Blood Whole Whole Whole Liver Muscle Liver Muscle Muscle Liver Liver Testes n LOQ ng/g wet wt or mL 12 71.9 6 71.9 6 35.9 5 71.9 2 35.9 5 35.9 4 71.9 10 35.9 10 71.9 3 18 10 35.9 5 37.6 7 2.5 8 35.9; 71.8 6 2.5 2 37.4 2 37.4 i 37.4 22 18.8 25 8.3 1 7.5 13 7.5 14 18.8 5 18.8 35 8.03; 20.1 5 8.03:20.1 7- - Table 4 Marine & Mammal Species in Which PFOA Was not Detected Above the Limit of Quantitation (LOQ) Species Source Tissue n LOQ ng/g wet wt or raL Elephant Seal California Coast Liver 5 35.9 Harbor Seal California Coast Liver 3 35.9 Northern Fur Seal California Coast Liver 1 35.9 Sea otter California Coast Brain 2 35.9 Liver 8 35.9 Kidney 3 35.9 Northern Fur Seal Alaskan Coast Liver 14* 71.9 Blood 44 9.58 Polar Bear Alaska Liver 17 71.9 Blood 14 2.4 Stellar Sea Lion Alaskan Coast Blood 12 9.58 Baikal Seal Lake Baikal. Russia Liver 24 35.9; 71.8 Ganges Dolphin River Ganges, India Liver 2 71.8 Bottlenose Dolphin Mediterranean Sea Liver 5 35.9; 71.8 Striped Dolphin Mediterranean Sea Liver 4 71.8 Weddell Seal Antarctica Liver 1 34.7 Ringed Seal Baffin Island, Canada Blood 24 6.22 Spitsbergen Blood 18 6.22 Grey seal Canadian Arctic Blood 12 4.98 Tursiops truncatus Palma Sola Bay. Florida Liver 2 7.5 Sarasota Bay Liver 4 7.5 Anna Maria sound Liver 3 7.5 Gulf of Mexico Liver 9 7.5 Peace river Liver 1 7.5 Stenella coeruleoalba G ulf of Mexico Liver 1 7.5 Venice Inlet Liver 1 7.5 Kogia breviceps Atlantic Ocean Liver 1 7.5 Anclote River Liver 1 7.5 Steno bredanensis Anna Maria Sound Liver 1 7.5 Tampa Bay Liver 1 7.5 Whale Italy Liver 3 37.5 Muscle 3 37.5 Polar Bear Alaska Liver 14 8.03 * One sample was not extracted. 8- - Table 5 Fish-Eating Water Birds in Which PFOA Was not Detected Above the Limit of Quantitation (LOQ) (1) Species Source T issu e n LOQ ng/g w et w t o r mL Double Crested Cormorant Common loon Brown Pelican Black Footed Albatross Little Charity Island, Great Lakes St Martin Island, Great Lakes Lake Charity Island Lake Superior, Great Lakes Scar Crow Island. Thunder Bay Gull Island. Geo Bay Carteret County, NC Monterey Bay, CA Pompano, Florida Several California Locations Unknown E Pascagoula River. Ms Sand Island. Midway Atoll Laysan albatross Sand Island. Midway Atoll Herring gull Great Black-backed Gull Heron Sea Gull Cormorant Blacktailed gull Great Erget Wood Stork White-faced Ibis Black-crowned Night Heron Snowy Egret Franklin's gull White Pelican Brown Pelican Northern Gannet Little Charity Island. Lake Huron, Great Lakes Sacramento, CA Carteret County, NC Carteret County, NC Japan Japan Japan India Korea Hokkaido, Japan Florida (3 Naples, 1 Miami Beach) N Carolina, Louisiana, Montana (Mo) South Carolina Sac valley. CA San Diego, CA Florida Red Rock Lakes, Montana 3 California. 1 Montana Mustang Island. Texas Carteret County. NC Blood Blood Plasma Blood Blood Blood Liver Liver Liver Liver Liver Liver Liver Kidney Serum Kidney Serum Plasma Liver Liver Liver Liver Liver Liver Whole Blood Liver Blood Liver Liver Liver Liver Liver Liver Liver Liver Liver Liver 2 2 4 2 1 1 5 4 5 4 1 2 5 4 7 3 6 4 1 4 2 2 1 10 22 15 24 4 3 1 1 5 3 4 4 1 1 29.9; 35.9 29.9 29.9 35.9 29.9 29.9 180 180 18.7 18.7 18.7 180 180 180 29.9 180 29.9 29.9 18.7 18.7 18.7 18.8 18.8 18.8 6.24 35.9 2.5 18.7 18.7 18.7 18.7 18.7 18.7 18.7 18.7 18.7 18.7 9- - Table 5 Fish-Eating Water Birds in Which PFOA Was not Detected Above Limit of Quantitation (LOQ) (2) S p ec ies Source T issu e Osprey Florida Liver Ohio Liver N Carolina Liver Red-Throated Loon Carteret County', NC Liver San Diego. California Liver Skua Antarctica Liver Heart Kidney Eggs Sea Gull Japan Liver Spotted Duck Japan Liver Bald Eagle Great lakes. Midwestern Plasma states Alabama Plasma South Carolina Plasma Oregon Liver Savannah, Illinois Liver Durham. California Liver Michigan Liver Michigan Muscle Michigan Kidney Michigan Gall bladder Michigan Testes Michigan Ovary Great Horned Owl Michigan Eggs Tree Swallow Michigan Composite Adelie Penguin Antarctica Eggs Caspian Tern Michigan Eggs DC Cormorant Michigan Eggs Herring Gull Michigan Eggs Chicken Michigan Eggs Liver Sea Eagle Poland Liver Baltic sea, Germany Liver Mediterranean. Italy Blood Mediterranean, Italy Serum * One sample was not analysed. ** Two samples were lost during extraction (spilled out of tube). n 2 1 1 2 1 1 1 1 4 21 1 26 4 12 2 1 1 6 6 4 1 1 1 3 5 10 4 6 2* 3 3 6 44 52** 1 LOQ ng/g w et wt or mL 18.7 18.7 18.7 18.7 18.7 18.8 37.4 37.4 18.8 18.8 18.8 29.9 6.24 6.24 18.7 18.7 18.7 18.8 37.4 37.4 37.4 37.4 37.4 18.8 18.8 18.8 18.8 18.8 18.8 18.8 18.8 8.03 40.2 3.35 3.35 - 10- Table 6 Oyster Species in Which PFOA Was not Detected Above Limit of Quantitation (LOQ) S p ec ies American Oyster Source Gulf of Mexico and Chesapeake Bay T issu e Whole No. of L ocation s 77 LOQ ng/g wet wt 7.5; 18.7 - 12 - Table 7 Multi-City Study Data from Table 4 of Executive Summary Sample Decatur, AL Cleveland, TN Mobil, AL Columbus, GA Pensacola, FL POTW Effluent 2.14,2.42 0.655, 0.674 0.067, 0.088 0.139, 0.147 ug/L POTW Sludge, 101,244 3.11,2.82 NQ 16.5, 16.3 Dry ug/Kg Drinking Water, ND ND ND 0.026, NQ Intake ug/L Drinking Water, ND ND N D 0.025, 0.029 Treated ug/L Drinking Water, ND ND N D 0.026, NQ Tap 1 ug/L Drinking Water, NA ND N D 0.026, NQ Tap 2 ug/L Drinking Water, NA ND N D 0.025, NQ Tap 3 ug/L Landfill Leachate 48.1,46.8 NC N D NQ, 0.028 ug/L Surface Water 1 NQ, ND NQ, ND 0.026, 0.027 0.026, 0.026 ug/L Surface Water 2 ND, NQ ND 0.054, 0.060 0.026, 0.027 ug/L Surface Water 3 ND N D 0.083, 0.083 NQ ug/L Sediment, Dry 1 ND, NQ ND NQ ND ug/Kg Sediment, Dry 2 NQ NQ ND ND ug/Kg Sediment, Dry 3 NQ ND NQ ND ug/Kg Quiet Water ug/L 0.057, 0.063 NC NQ, 0.027 ND ND = Not detected; NQ = Not quantifiable; NC = Not collected; NA - Not analyzed 0.084, 0.090 2.51,2.40 ND ND ND ND ND ND ND ND ND ND NQ, ND ND ND Port St. Lucie, FL (1999) 0.041,0.044 NQ ND ND ND ND ND 0.953,0.939 ND NQ ND 0.370, 0.326 0.316, 0.294 1.68, 1.75 0.737, 0.760 Port St. Lucie, FL (2000) 0.043, 0.040 ND ND ND ND ND ND 1.03, 1.02 ND ND ND ND ND ND 0.097, 0.097 -13 - Table 8 Human Serum Concentrations of PFOA Number of Samples Range of Measured Values (ng/ml, ppb) Mean Median Geometric Mean Cumulative 95th Percentile Adult Red Cross Blood Donors (ng/mL) 652 <LLOQ - 57.3 5.6 4.7 4.6 12.9 Children Aged 2-12 (ng/mL) 599 <LLOQ - 56.1 5.6 5.1 4.9 10.2 - 14 - - 15 - SOURCE The information contained in this document has been extracted from numerous studies submitted by 3M Company to the U. S. Environmental Protection Agency in June of 2001, and available on the AR-226 public docket. - 17 -