Document Edb7kjbLNLBe0dVYx9QbdZMY4

>ff 3M 3M Specialty Materials 3M Center St. Paul, MN 55144-1000 651 733 1100 F ys- osoo- /37f May 15, 2000 FYI-00-001378 /)RX&-203 RECEIVED O H f it Z S f t | | . f1 Vfy Dr. Charles Auer FYI -0 0 -0 0 1 3 7 8 Director Chemical Control Division Office o f Pollution Prevention and Toxics United States Environmental Protection Agency 401 M Street, Southwest Room 403 East Tower (Mail Code 7405) Washington, D.C. 20460 C, A /Vu1 RE: Supplemental Information on Perfluorooctane Sulfonates a /n a Dear Charlie: 3M is enclosing additional information on perfluorooctane sulfonates to supplement our submittal dated May 4, 2000. The supplemental information consists o f the following: 1. Four pages o f executive summaries that were included in the May 4, 2000 submittal as introductions to the environmental science areas. However, our cover letter to you o f May 4 also indicated that we would provide copies as part o f the cover letter. We inadvertently failed to include them as part o f the attachments to the cover letter, and do so now. 2. A summary entitled "26-Week Capsule Toxicity Study with Perfluorooctanesulfonic Acid Potassium Salt (PFOS) in Cynomolgus Monkeys, Current Summary as o f May 4, 2000." It is our understanding that this summary was hand-delivered to you by Dr. Larry Zobel at a recent meeting between 3M and EPA, but we supply another copy to complete the filing. 3. The cover page to the resubmittal o f confidential information previously submitted on May 4. We inadvertently failed to provide both a sanitized and confidential copy, and Terry O'Brien asked that we resubmit this information to the Document Processing Center. Please do not hesitate to contact me at 651-733-6374 should you have any questions. Very truly yours, William A. Weppner, Ph.D Director o f Environmental, Health, Safety & Regulatory Affairs Specialty Materials Markets 3M Center, Bldg 236-1B-10 St. Paul, MN 55144-1000 85000000009 cerr>a 0^0 CaO -"tQ?3mmO O pl co ro CT 850100000009 PHYSICAL - CHEMICAL PROPERTIES A Robust Summary, Final Report, and Protocol on the physical-chemical properties of perfluorooctanesulfonate are included for each o f the following parameters: PARAMETER DATE OF REPORT RESULTS Melting Point/Melting Point Range Vapor Pressure n-Octanol/Water Partition Coefficient Air-Water Partition Coefficient . Solubility in pure water SolubQity Measurements on FC-95 2/24/99 5/5/99 2/11/00 3/19/00 5/3/99 2/6/81 2 400C 3.31 x 10"4P@20C Not calculable; three phases 0(<2xl0-*) 570mg/l 1080mg/l The data presented in the study "Solubility Measurements on FC-95," was determined by indirect measurement, not by actual analysis. Therefore, the data is not reliable. Please note that the March 1,2000 submittal to EPA entitled "Sulfonated Perfluorochemicals in the Environment Sources, Dispersion, Fate and Effects" included solubility data on water other than pure fi.e.. fresh water; filtered sea water; unfiltered sea water). These data were developed, however, in support of other studies and not producedusing GLP Standards. For this reason, Robust Summaries, Final Reports, or protocols for this specific data are not being provided. ENVIRONMENTAL FATE AND TRANSPORT This section presents information and test results from abiotic, and biotic degradation and soil adsorption studies. Degradation studies include hydrolysis, photolysis, and biodegradation. Much of this work is in progress with final reports scheduled for the June to August, 2000 timeframe. As these studies progress, there are certain key findings that can be presented as prelim inaiy results: 1. There has been no indication that perfluorooctanesulfonate undergoes any degradation from hydrolysis, photolysis, or biodegradation mechanisms. 2. In all hydrolysis and photolysis studies, perfluorooctanesulfonate has not been detected as a degradation product in any conclusive experiment This preliminary finding calls into question the assumption o f expected degradation of other fiuorochemicals to perfluoroctanesulfonate, 3. In the studies focused on hydrolysis o f fluorochemical polymers that form the structure of the specific industrial and consumer products, it has been determined that these materials are relatively stable in the environment For example, the following half-lives are estimated for various polymers: POLYMER HALF-LIFE Acrylate and ester 1-5 years Polyethylene glycol based 3-50 years Urethane >500 years For hydrolysis to occur, polymers m ust be subjected to an aqueous, environment, which is not expected to occur in a municipal or industrial landfill 4. Relative fo photolysis, the current data suggests a hypothesis that these materials will pbotolyze to carboxylate structures. These structures have much different properties then sulfonates in that they are much less bioaccumulative in ecological species. Additional discussion of these results and ongoing studies will be presented in subsequent submissions and reports. 3 ECOTOXIC1TY ELEMENTS This section presents information and test results from a series of ecotoxicity studies on perfluorooctanesulfonates. The information is presented as Robust Summaries, Final Report and Protocol for each ecotoxicity elem ent The studies performed during 1999 and in early 2000 were carried out using GLP Standards. In contrast ecotoxicity studies performed during the period 1974 to 1998 were conducted using protocols and analytical methodologies available at the time of the study. In addition, in these older tests, the sulfonated perfluorochemical products were variable mixtures and contained more impurities. Several tests were hampered by the insolubility of the perfluorochemical and results are expressed as "greater than" the measured solubility. Therefore, the data presented in these historical reports may not be reliable. ENVIRONMENTAL MONITORING; PART ONE - MULTI-CITY STUDY The multi-city study was designed to obtain preliminary data about dispersion of fluorochemicals in the environment, uptake into foods and presence in drinking water to understand the potential sources of human and environmental exposures that might result from this type o f dispersion. The multi-city study paired a city having manufacturing or commercial use o f fluorochemical products based on customer sales with a city that does n o t Initially six cities, (three pairs) are being examined. The study may be expanded depending on further results. The multi-city study will yield environmental distribution data as well as data on potential sources of human exposure. The cities were selected to represent urban locations with various levels of fluorochemical releases and various types of municipal water supplies. The samples to be obtained, where possible, include: urban air, surface water column and surface microlayer, sediment, river fish, drinking water intake, treated drinking water, tap water, the influent to and effluent from publicly-owned waste treatment works, sludge, and municipal landfill leachate. Additionally, a "market basket" o f several food products will be sampled. These include: beef, pork, chicken, hot dogs, catfish, eggs, milk, bread, green beans, apples from grocery stores and, if possible, produce from local farmers* markets. The attached material data provides more detail on the design and structure o f the study and represents the first results from the multi-city study. Included are reports on the quality assurance plan and field sampling procedures used and the results of the drinking water samples taken from the six cities. The results indicate that drinking water in four cities (Decatur, Alabama; Cleveland, Tennessee; M obile, Alabama; and Fort S t Lucie, Florida) did not contain detectable levels of fluorochemicals. Only two cities (Columbus, Georgia, and Pensacola, Florida) contained detectable levels of sulfonated fluorochemicals in the drinking water. The results show that the levels are in the range of 40-60 parts per trillion of perfluoroctane sulfonate. Only one city, Columbus, Georgia, showed very low detectable levels of perfluorooctanoate. Also included is a copy o f a draft "lifetime** drinking water health advisory developed for PFOS. This advisory reflects a very conservative approach based on application of "safety factors.** The advisory level of 1 part per billion should not be misconstrued as threshold for danger or concern, but only a reference point based on application of conservative methods and the information available to date. A comparison of the drinking water data from the multi-city study indicates that there are two orders of magnitude of safety between the draft drinking water advisory and the results from these two cities in the multi-city study. ENVIRONMENTAL MONITORING: PART TWO - BIOSPHERE SAMPLING AND ANALYSIS A plan to assess potential environmental exposure to perfluorooctanesulfonate and other fluorochemical substances has been developed by 3M and outside experts. One component of this plan involves characterization of the geographic distribution of fluorochemicals in biotic and abiotic receptors. Two studies are in progress, one focused in the vicinity o f the 3M Decatur, Alabama manufacturing facility, and the other a much more comprehensive global biosphere monitoring program. The preliminary results obtained to date have been reported in the 3M Environmental White Paper entitled "Sulfonated Perfluorochemicals in the Environment: Sources, Dispersion, Fate and Effects.'* The study in the Decatur, Alabama area is being designed to understand the impact, if any, o f production operations in the local environm ent Samples of the groundwater, surface water, sediments and fish and bird species w ill be collected in May and June, 2000 for analyses. This data will be used to evaluate the environmental presence of fluorochemicals and to assess the potential of any effects using ecotoxicological test results. The Biosphere monitoring program was designed in consultation with Dr. John Geisy o f Michigan State University. This plan is being viewed as an iterative process to assess global distribution of fluorochemicals. As results are obtained from the global environment, the plan is to concentrate on those areas where fluorochemicals are detected in samples and focus on additional sampling and analyses in those specific locations. Initially, samples of tissues and blood plasma are being collected from archived specimens covering different species and locations. Areas of focus include North America (Great Lakes and coastal marine locations), the arctic region, and Europe. Species to be studied include lake trout, walleye, salmon, catfish, and brown trout; cormorants, eagles and albatross; mussels and shellfish; marine mammals; and other species. This sampling plan is in progress and as data is obtained and reports generated, additional submissions will be made to EPA. Included in this section are the following documents: 1. LCMSMS Analysis o f Extracts reported in: "Preliminary Report Analysis of Perfluorinated Compounds in Environmental Samples'*by P. Jones and K. Kannan - 4/7/99 2. Final Laboratory 3M Reports on Analysis of Fluorochemicals in Wild Bird Livers - 4/28/993 3. Screening of PFOS levels in Eagle and Albatross - 5/8/98 26-Week Capsule Toxicity Study with Perfluorooctanesulfonic Acid Potassium Salt (PFOS) in Cynomolgus Monkeys Current Summary as of May 4, 2000 The purpose o f this study was to identify the earliest clinically measurable biological response from repeated daily exposure to potassium perfluorooctane sulfonate (PFOS) and to correlate this response to serum concentrations for purposes o f risk assessm ent and m edical monitoring o f exposed populations. Groups o f m ale and fem ale Cynomolgus monkeys received daily doses o f 0 (six per sex), 0.03 (four per sex ), 0 .1 5 (six per sex), or 0.7 5 (six per sex) m g/kg/day potassium perfluorooctane sulfonate for 26 w eeks by capsule via gastric intubation. Two m ales and tw o fem ales in each o f the 0 , 0.15 and 0.7 5 m g/kg/day dosed groups were follow ed for one year after cessation o f dosing to observe depuration o f compound and reversibility o f effects. There were no recovery animals in the 0.03 m g/kg/day dose group. This report covers the 26 w eeks o f dosing. A separate report w ill detail the findings from 52 w eeks o f recovery. Effects occuring in the 0 .7 5 m g/kg/day dose group which are believed to be compound related include: 1) severe illness o f tw o m ales which died or were sacrificed in extremis within the last month o f treatment; 2) low er body w eight in m ales and fem ales; 3) increased liver w eight and hepatocellular hypertrophy and vacuolation in animals; 4) low ering o f serum cholesterol in correlation to increasing serum PFOS levels during treatment; 5) low ered triiodothryonine (T3) values in both m ales and fem ales; 6) low ered estradiol (E2) levels in m ales. N o significant compound-related effects w ere observed in monkeys treated w ith 0.03 or 0 .1 5 m g/kg/day over 26 w eeks. Serum PFOS values increased linearly to an average o f 18 and 90 in the 0 .03 and 0 .1 5 m g/kg/day dose groups, respectively. The increase in serum PFOS in the 0.75 m g/kg/day dose group w as not linear during the dosing period and reached an average o f 215 ppm after 26 w eeks o f dosing. Liver PFOS levels averaged 25, 80 and 415 ppm for 0 .0 3 , 0 .1 5 , and 0.75 m g/kg/day dose groups, respectively. Cholesterol values returned to pre dose levels within 36 days o f recovery, without correlation to serum PFOS. Serum PFOS had an apparent elim ination half-life o f 275 and 128 days over the first six-m onths o f recovery in the 0 .1 5 and 0 .75 m g/kg/day dose groups, respectively. The decrease in total serum cholesterol observed in high-dose animals was confirm ed as the earliest measurable clinical response. The lowering o f total serum cholesterol occurred only at serum PFOS concentrations greater than 100 ppm. The biological responses observed in this study are consistent with prior rodent and monkey studies with the exception that hepatocellular peroxisom e proliferation, as observed in rodents, was not observed in this study. H ealth effects have not been observed from years o f m edical m onitoring o f 3M chem ical workers with occupational exposure resulting in average serum concentrations o f approximately one to two ppm, and generally less than six ppm (O lsen et a l., JOEM Sept., 1999). Therefore, non-occupationally exposed populations with pooled average serum PFOS concentrations that are one to two orders o f magnitude low er than average worker serum concentrations (3M , "Perfluorooctane Sulfonate: Current Summary o f Human Sera, Health and Toxicology Data", January 2 1 ,1 9 9 9 ) have a margin o f safety o f 103 to 104 w ith respect to the first clinically measurable biological response to perfluorooctane sulfonate exposure, cholesterol lowering. 7 Corporate Health Physics Corporate Industrial Hygiene & Ergonomics Corporate Occupational Medicine Corporate Toxicology 3M Medical Department 3M Center, Building 220-2E-02 PO Box 33220 St. Paul, MN 55133-3220 651 733 1110 May 15, 2000 Document Processing Center (Mail Code 7407) Information Management Division Office o f Pollution Prevention and Toxics United States Environmental Protection Agency 401 M Street, SW Room 699 East Tower Washington, D. C. 20460 Attn: FYI Dear Sir/Madam: This submission is being made per the phone conversation between Terry O'Brien (EPA) and Dan Hakes (3M) on May 10,2000. Terry requested a non-confidential version o f a specific toxicological study. I would like to confirm that portions o f the "Exploratory 28Day Oral Toxicity Study with (various fluorochemicals) By Daily Gavage in the Rat Followed by a 14/28-Day Recovery Period", plus the associated laboratory report submitted to Dr. Charles Auer on May 4, 2000 is considered TSCA Confidential Business Information. Attached for your review is a new copy o f the above mentioned study to be included with the submittal on perfluorooctane sulfonates made by 3M to Dr. Charles Auer dated May 4, 2000. Attached to this letter is a complete non-confidential report with the TSCA Confidential Business Information redacted. In a separate envelope is the same report with the TSCA CBI included and highlighted. Very truly yours, John L. Butenhoff, Ph.D., C.I.H., D.A.B.T. Manager, Corporate Toxicology Corporate Toxicology 3M Medical Department Building 220-2E-02 3M Center St. Paul, MN 55144 651-733-1962 /