Document DDveXZb8r3538d71Qwq6bp63o

FinalCo STUDY SUMMARY FOR WORK PERFORMED DURING 1977-1979 TEST SUBSTANCE Identity:Perfluorooetanesulfonatmea;y also be referredtoas PFOS or FC-95. (1-Octanesulfbniaccid,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8heptadecafluoro-p,otassiumsalt,CAS # 2795-39-3) Remarks field: The testsubstanceisa whitepowder of uncharacte(izepdurity. The attachedisan overviewcreatedin1979 forstudiescompleted from 1977 to 1979. Robust summaries have alreadybeen submittedformany ofthese studies.Othershave not been summarized due tothefactnew studiesexistthatsupercede these ortheyare being repeated. STUDIES Water solubilitbyi;odegradations;oilsorptiono;ctanol/wateprartition coefficienStt;aticAcute Toxicittyo BluegilSlunfish(Lepomis macrochirus);StaticAcute Toxicittyo Rainbow Trout(Salmo gairdnen); StaticAcute Toxicittyo Fathead Minnow (Pimephalespromelas);Static Acute ToxicittyoDaphnia magna; ChronicFlow Through Study on Fathead Minnow (Pimephalespromelas) DATA QUALITY ReliabilityT:hese studieshave been assignedKlimischrankings= 2. They satisfiecdriterifaorqualitytestingatthe timeperformed,but have some deficienciesI.nmany cases actualconcentrationwsere not measured. The valuewas determinedby indirecmteasurement (e.g., solubilitoyr)usingnominalconcentration(se.g.a,quatictoxicityI)n.some cases,the analyticamlethodology itselwfas questionable.Additionally, these studieslacksufficienctharacterizatiofnthetestsubstance purity. OTHER Submifter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St.Paul,Minnesota,55133 Last changed: 5/3/00 MICHIGAN STATE UNIVERSITY DWAXTMU4T OF CITOPMD SOIL SCIENCES MAW agSOM SCMNCU BUUDINCO May 19, 1993 LUT LANSINCR MICMRAN 4m4.ij2s Dr. Robert D. Howell 3M Company 3M Center, Bldg. 2-3E-09 St. Paul, MN 55144-1000 Dear Dr. Howell: Enclosed are my review comments regarding the nine 3M Technicial Reports, recommendationsfor improving the quality of the individual studies, and some recommendations for future research. Please review this information and let me know if I can be of any further assistance. I do have interest in submitting a research proposal to 3H in accordance with the recommendations for future research. Perhaps we could discuss this further. I enthusiasticallysupportyour efforts to obtain information on the environmental fate and behavior of the 3M products. My consulting fee for the work performed to date is $3,200.00 (three and one half days for review of materials and preparationof reports plus one half day consultationwith Dr./Iowellat MSU, at $800.00 per day). Sincerely, te en A. Boyd. P Professor MSUism AffwmstivAoction/EquOdppmanitylossitsiooo Review of TechnicalReport Summary FinalComprehensive ReportFC 95 An octanol-wateprartitiocnoefficieonft 10 would predicta supercooledliquidsolubilitoyf 250 g/L usingtheequation: log Y,..= -0.862 log S,,+ 0.710 Converselyifthewatersolubilitoyf thesolidis286 mg/L, thenthesupercooledliquidsolubility couldbe - 2860 mg/L. Using theabove equationt,hispredictas Y@,.valueof about500. The predictedvaluesare quitedifferentthan the measured values,and the measured K. and S@ valuesseem inconsistenit.,e.,ifthemeasuredK.. iscorrect,I would expecta higherwater solubilitayn,d ifthemeasured solubiliitsycorrectIwould expecta higherK... The valueslook suspicious. FC 95 isdescribedas an anionicsurfactantI.fso,does itform miceflesand exhibita well definedcriticamlicelleconcentratiosnimilatro SDS forexample. Ifso,thenI'm notcertain taildngabout watersolubilitiiessappropriate.Ratherbehaviorabove and below theCMC shouldbe examined. Table2 presentssoilsorptiondatawhich isvirtuallmyeaningless.The percentsorbedisgoing tovarydependingon theexperimentalvariableosfamount ofsoil,typeof soilv,olume ofwater, concentratioonf FC 95. You need tomeasure theentiresoilsorptionisothermand obtaina sorptioncoefficientT.his shouldbe done on severalsoils.Again, ifFC 95 isa conventional micefleformingsurfactanItwould expectdifferenstoilsorptionbehaviorabove and below the CMC. -I would not expectlinearisotherms. A Y...valueof 45 isreportedbasedon datafrom anotherreport(referenc3e). To evaluatethe appropriatenesosf thisvalue,itshouldbe obtainedon severaldifferenstoilsand be relatively constanto,r be consistenwtithK, valuespredictedfrom empiricalrelationshipssuch as: logY%,.= 0.904 log K.. -0.539 (Chiouetal.Environ. Sci.Technol.17:227231) Using theK.. valueof 10, thepredicteKd. valueisabout2 which ismuch lower thanthe measuredvalueof45. Again,thispointstotheinconsistencioefsthemeasuredY.,,S.., and K., values reported. The K.. and/orS. valuesmeasuredare alsobeing used to predict bioconcentratiofnactorsusingempiricalrelationshilpisketheone above. This isa reasonable approachiftheY...or S. valuesare accurate.As mentionedabove X.. and S. reportedseem tobe inconsistensto,I don'thave a lotof confidencein usingthem to predictotherthingslike BCF. Recommendation 1. Need an accuratedeterminatioonfwatersolubiliatnyd octanol-wateprartitiocnoefficient (SeemethodologyofChiou and Schmedding,1980 - giveninpreviousreport.) 2. Determine theCMC of FC 95, and recognizethatitsbehaviorabove and below the CMC willbe different. 3. Obtain soilsorptionisothermson severalsoilsand calculatKe,. valuesfrom these. 4. Check forconsistencybetween S.,Y,,.a,nd K. values. ro@in 6 747-11 A TECHNICA.L REPORT SUMMARY TO: TECHNICAL -COMMUNICATIONS CENTER - 201-2CN (importan-tIfreporitsprintedobnodisiM ofp4w, sfndtv*vcopantoTCC.) 'Pivision Environmental Laboratory-(EE Project Fate of Fluoroctiemicals .-N;Fo-rt-rel-tro Final Comprehensive Report: To & PCi FC 95 opt. um 0535 Project Number 9970612643 KWO" Number Oil R. A. Prokop Aull,orrtl4--. A N...Welter Notebook Reference LRWIOYW Number(s) 09362 No. of Pages Including Cowenhogt SECURITY 10, 0 Open (Company Confidentiall Closed fspecial Authorization) 3M CHEIMICAL REGISTRY 12 Now ChernkWsR*Mrted [3 ya No KEYWORDS: (Selecttornm from 3M Them@rus. Suggest other applicableterms.) CURRENT OBJECTIVE: Final Report: Encompasses all work performed during the period 1977 7 1979. EE&PC - Div. Fluorochemical (analytical) (Aquatic) (Degradation) Soil Toxicity REPORT ABSTRACT: 1200-25w0ords)ThisabstraicntformatiiosdnistribubtyetdheTechnicCaolmmunicatioCnesntetro aler3tM'ortsoCompanyR&D. ItisCompanyconfidentniaatlerial. D. L. Bacon R. L. Bohon V. Pothapragada Information I-iaison Initials: <'. 1, (,11 11 2 Introduction The rationale for performing environmental effectl)studies on fluorochemicals has been discussed previously The subject fluorochemical of this report is FC 95 (an anionic surfactant) which has a potential for widespread distribution in the environment as this material is used by the chrome plating, and etching industries, both domestically and internationally. FC 95 chemically is the potassium salt.of perfluorooctane sulfonic acid. c 8 p 17 so 3 K FC 95 This material is an off-white powder, having a molecular weight of 538 and the chemical structure shown above. This report consolidates all available information in the areas of aquatic toxicity, soil'sorption studies, degradation, water solubility and partition coefficients and defines the probable environmental risk of FC 95. Methods Water solubility, biodegradation and soil ion studies have been the subject of technical reports These -specific experimental methodologys have been defined in these reports and should be consulted for specific details.. A) Aquatic Testing The testing protocols utilized for this stud ere modeled after that described by USEPA (1975)@41 B) Acclimation Procedure The blu'egill sunfish a (Lepomi.9 macrocl@irua) 'rainbow trout'(Saimo gairdneri), and fathead minnows (Pimophales promezaa) used in this study were obtained from private hatcheries. Stock fish were held in fiberglass holding tanks filled with carbon-filtered well water maintained at 14-150C. A daily pbotoperiod of 16 hours light and 8 hours dark, with a 30-minute transition period, was maintained throughout the agelimation and testing period. The fish were fed Tetra-Min daily, food being withheld 48 hours prior to and throughout the test period. Fish were so acclimated for 14 days prior to testing. Acute short-term (96-hour) static bioassays were performed on FC95 Lot 583.Carbon-filtered well water of known composition a. Dale Fattig Fish Farm, Brady, Nebraska b. Dennis Fender Fish Hatchery, Baltic, Ohio C. Tetra-Min - a commercial fish food of known composition was used as the diluent. All glass aquaria (35 x 20 x 20 em), containing i6.1 of diluent or diluent plus toxicant comprised a study chamber. Fathead minnows (Pimephates promela8), bluegill sunfish (Lepomia macrochirua), and rainbow tr out (Salmo uniform in size and weight, were tested ' at each gairdneri), chemical concentration of each test material. Test fish were randomly assigned to various test chambers within 30 minutes following toxicant addition. Test temperatures for the gathead minnow and bluegill sunfish were maintained at 18 C range 17619, while the rainbow trout tests were conducted at 14 C. Mortality, temperature, dissolved oxygen level, and pH of all test solutions were measured at 24-hour intervals or until total mortality had occurred. General observations relative to behavioral changes were similarly recorded when appropriatlz. Organisms used in this study were considered to be generally healthy and free of disease. Instrumentation used included a tetpgrature compensating Orion pH meter, ASTM thermometers -@-IC. for temperature monitoring, and a Yellow Springs Dissolved Oxygen meter. All aquatic studies were replicated. LC values with 95% confidence limits were calculated usirg the USEPA (Duluth) Probit computer program on the 3M TRAC System. C) Aquatic Invertebrates - 48 hour Static LC 50 Daphnia magna, 20 organisms per test, were exposed to PC 95, lot 583 at varying concentrations for 48 hours. First instars were counted and placed in carbon filtered well water, with chemical added and solubilized prior to the.addition of the Daphnia magna. Test concentrations were 42, 56, 75, 100 and 135 mg/l. LC' values with 95% confidence usirg the USEPA (Duluth) Probit the 3M Trac.System. limits were calculated computer program on The test protocol utilized for this taldy was modeled after that described by USEPA (1975) Results Table 1 lists water solubility and partition coefficient data obtained using radi07libelled FC-95: This material is water soluble, 286 ppm' , sll5htly lipid soluble having a partition coefficient of 7-10 Based on these data it can be concluded that FC .45would not bioconcentrate to an appreciable extent in the environment. Chiou et al (6) have described an emperical relationship between watj-r - solubility of a chemical and its bioconcentration factor. In this system the ascribed error is considered to be one order of magnitude. When applying the data generated for PC 95 to this proposed relationship this chemical would be projected to possess a bioconcentration factor of approximately 200. 4 TABLE 1 - Physicochemical Characterization of FC-95 Parameter Solubility Partition Coefficient Test Veith Method n-octanol/water Results 286 ppm 7-10 PC-95 was found to be completely rristant to biodegradation under the test conditions employed This 2 1/2 - month shake culture biodegradation study utilized microbial test cultures derived from activated sludge inocula obtained from the waste trb@atment sys' tems of Chemolite, Decatur, And the Twin Cities Metro plants. During the period of this study, a strain of microbes which could degrade FC-95 did not develop,.hence this material would be expected to persist in the environment for extended periods of time unaltered by microbial catabolism. In working-with fluorochemicals, it has been suggested that if these materials do degrade either chemically or biolog:Lcally that one degradation product would be FC-95. We have never observed the formation of FC-95 by either of these routes; therefore, the environmental levels of FC-95 are 'not anticipated to increase as a result* of the exogenous production .of this material. Soil sorption studies have shown that approximately 18.8% (range 14.6-27.0) of the FC 95 is'adsorbed to the Brill sandy loam soil used in these studies (Table 2)(3). Complete desorption of the FC 95 which had been adsorbed to soil was accomplished within three (3) desorption tr.ials, (Table 2). Mobility of FC.95 calculated utilizing the scheme devised by Hamaker (Ilwshereby adsorption coefficients are converted to-a constant Koc, which reflects the organic content of the soil. Hamak;r has shown that the relative Mobility of a group of pesticides could be determined in this fashion and that a relative ranking, moving from highly mobile to immobile materials would result. In applying this test, FC 95 had aK oc value of 45, being considerably more mobile than Paraquat,- K 20,000 and slightly less mobile when compared to Chlo?Emben, K 12.8. These data indicate that those forces which bind oc FC 95 to soil are weak, hence the complete desorption of material adsorbed to the soil and secondarily the fact that this material is highly mobile.(3). Results of the acute static aquatic tests are tabulated (Table 3). Based on aquatic toxicity criteria established by NIOSH FC 95 would be considered slightly toxic IR)the vertebrates and invertebrate utilized in this test It is noted that the invertebrate data correlate well 5 with those data obtained when testing both warm water species. This observation has been made repeatedly, therefore, one may consider Daphnia magna data as a valid predictor.of chemically induced toxicity to warm water vertebrate species (9,10). A statistical analysis will be utilized to validate this concept. Egg-fry studies were contracted to EG&G.Bionomics Laboratory, and their results comprise Tables 4 and These studies were undertaken to assess-the.effee.t of 14 C PC 95 at.sublethal levels on hatchability, survival, weight and length changes (Table 4). It is generally accepted that the immature or young of a species are quite sensitive indicators of chemically induced toxicity. 'In the parameters under investigation the percent survival was 'statistically reduced (P.05) at a PC 95 concentration of 1.9 mg/l. The remaining test parameters were unaffected by this chemical. The mechanism responsible for the increased mortality observed at the highest test concentration can not accurately be determined based on these studies, although it is to be noted that .hatchability was not affected at this dose level. In the contracting laboratory's report, the.observation was made that the fish in the 1.9 mg/l tank were exhibiting. stress behavior; erratic swimming, darkened coloration. A similar observation was made of a few fish in tlle.1.0 mg/l tank suggesting that the toxic action of PC t*5 is cumulative.' Based on the results of the hittopathological examination, a 30-day exposure to 1.9 mg/l C PC 95 did not contribute to abnormal histopathology (Table 5). TABLE 2 Parameter Soil Sorption Test Test on PC 95 . Solut ion Soil Sorption Adsorption Water Desorption Water K oc Results 18.8% 100% of amount adsorbed 45 6 TABLE 3 FC 95: 96 Hour Acute Static Testing Test Organism 96h LC nig/l 50 lower mg/l Fathea:d Minnow 37.6 51 28.4 46 Blu6giii 8unfish 68 62 Rainbow Trout 8.6 B. Invertetirate48 Hour' Static Test'.' Daphnia liagna 50 49.2 42.8 38.7 Limits Upper mg/l. 50.2 56 74 12.5 56 56.6 7 TABLE 4 Percentage Hatch, -Percentage Survival, Mean Total Length and.Average Wet Weight of Fathead Minnow Fry (PimephaZda promezaa) uring Eip gsure to Varying Concentrations ofitc FC 95. Concentration Hatch mg/l % 1.9 95 1.0 96.5 0.45 96.5 0.28 95.5 0.12 97.5 -Control 98 Solvent-Control 89 Survival % 42 c .86 90 94 95 93 100 30 Days Post Hatch Total Length Wet Weight mm mg 20..5 72 20 62.'s 20.5 ra6 21 64 20 63 20 61.5 21 64.5 a Work performed by EG&G tionomics Laboratory, Inc. b Summary table submitted to Environmental 3M, gt. Paul, as part of final report. Laboratory, c Significantly reduced at. P 0.05 TABLE 5 Histopathological Examination of Pathead Minnow (Pimei@gZe8 pro.melael exposed 30 OAY to 14 1.9 mg/i c FC-95 . Test Material Number of Observations Histopatholdgical Findings Control .14 CFC 9'5 10 9/10 fatty liver change f 1/10 bacter ial gill disease 9/10 tissue.' aut'olysis' 10 8/10 fatty liver'change 2/10 normal a Work p erformed by EG&G Bionomics Laboratory, Inc. b Summary table submitted to Environmental Laboratory, 3M, St. Paul, as part of final report. Both groups of organisms exhibited-fatty liver changes, control, 9/10, and dosed organisms 8/10. Evidence of tissue@ autolysis in the conttol group is indicative of a delay in histological preparation of tissues following death of the organism. Discussion The primary purpose of this report is to provide a single source for all environmental.data generated relating to PC 95 and to provide an analysis of potential environmental risk.- The environment may be considered to be a closed system which-can be depicted as follows:. Air -------------%-. ----Soil Water;;@@@ it, therefore, follows that chemicali@entering this system may establish an equilibrium, remain within a single environment, or impact on all phases of the depicted cycle. In the specific case at hand we can represent the impact of PC 95 in the following manner: No Photodegradation Air Volatility? Soil___.%.No volatility Rate? ccmpi d .01 19% Adsorbed tion 7bxic to Fry 1.9 ng/l Wftater Sedi t PPM Projected to minimallybioconcentrate,low lipophilicity As schematically represented above PC 95 enter s the environment primarily by means of the waterways and second'arily via the terrestrial ecosystem and atmosphere. PC 95 does not adsorb permanently to either soil and/or sediment. Complete desor on of FC 95 from soil did ' occur in the laboratory model . It is unknown whether or not this material volatilizes, a fact which assumes importance in lighIlyi the finding that PC 95 does not undergo photolysis. Based on the foregoing it appears that waterways are the environmental sink for FC 95 and aquatic organisms are the intermediate 9 receptors. It is in the@aquatic area that a Possible deleterious action of PC 95 may be found. As noted above, reduced survival rates of fathead minnow fry were recorded.at PC 95-concentrations of 1.9 ppm. The no efflect level of PC 95 may be assumed to be approximately 0.19 ppm. These data may serve in a predictive fashion, hence the above noted levels of PC 95 may impact on a human' food source by significantly reducing the survival rates.of these organisms. It*is to be emphasized that the environmental of PC 95 more accurately describes the degree wit' h this chemical. . concent ration of risk associated We have made soveral-assumptions which are basic to the simplistic model used in our calculations: 1) Total production is at Chemolite and it is discharged in.its entirety. 2) No PC 95 is removed by the treatment facility. 3) All effluent is discharged to the Mississippi River. 4) PC 95 is discharged uniformly. 5). River flow and all other parameters are.constant, hence not subject to seasonal and/or climatic conditions. the formulae 1) MG/min used in these projections include.: (River Flow,.CFM)(Conversion,gallft 3 )(Time,min)Production, per annum 2) MG/min X 1440 MG/Day 3) Lbs/day (mg/l X wt. lbs. H 2 0 per ga 1)(MG/Day) Mississippi River.flow at Hastings, MN, based on a 10 year low flow record.is 10,000 CFS. The total 5-year production figures were provided by D. R. Ricker, Commercial Chemicals Division. In utilizing these iigures an estimated Invironmental concentration of PC 95 -in the.Mississippi River below ChemZ;lite was calculated. During the period 1973-1978, the EEC for PC 95 was calcul'ated to be 5 ng/l at Hastings, MN, while the EEC projected for the period 1978-1983 is projected at 7 ng/l. Sin'de the water compartment is'the environmental sink for PC 95 it is determined that at the present and projected levels of production, PC 95 will not present an unreasonable environmental risk. 10 Conclusions Under the test conditions employed in characterizing the physicochemical and environmental properties of PC 95 it has been determined that this material: 1) is water soluble, 286 ppm 2)- has an n-octanol/waterpartition coefficient of -10 3) is resistant to microbial degradation 4) is highly mobile in Brill sandy loam soil 5) In a contracted study, survival rate of.the fathead minno' w fry was reduced to a statistically significant extent when the exposure concentration was 1.9 mg/l FC 95. No other parameters were.adversely affected nor was abnormal histopathology observed at this dose level. 6) would have'an estimated environmental concentration of approximately 7 ng/l under conditions.-wherein all, FC 95 were manufactured at Chemolite and would-be discharged uniformly into the.HigsissippiRiver. 7) may not be a metabolite as a*result-of chemical or biological degradation, hence no increase in environmental levels of FC 95. 8) FC 95, under the test conditions described will not present an unreasonable environmental risk. Bibliography 1. Mendel, A., Technical Report. "Analytical Methodology and Support", January 17, 1979. 2. Reiner, E.A., Technical Report: Biodegradation Studies of Fluorocarbons III, July 19, 1-978. 3.. Welsh, S.K., Technical Report. Adsorption of PC 95 and FC 143 on Soil, February 27, 1978. 4. US/EPA - Methods for Acute Toxicity T4istwith Fish.' Mactoinver'tebrates and Amphibians, Ecological Research Series 660/3-75-009, 1975. 5. Unpublished data 6. Chiou, Cary T., Virgil H. Freed, David W. Schmedding, and Rodger L. Kohnert: Partition Coefficient and Bioaccum'ulationof Selected Organic Chemicals Environmental Science and Technology 11(5): 475-478, 1977. 7. Hamaket, J.W., "Interpretation of Soil Leaching Experiments" Chemicals, Human Health and-the Environment, A Collection of Dow Scientific Papers, Vol. 1, Dow Chemical USA, Midland, Michigan 48640. 8. Regis@try of Toxic Effects of.Chemicai Substances, -176 Edition, Christensen,H.E. and E.J. Fairchild, Eds. P.xvand Ci, U.9. Department of Health, Education* and Welfare; National Institute for OCCUpational Safety and Health,-Wishington, D.C., June,..1976., 9. Welter, A.N., Technical Report: Aquatic Toxicity'Studies: PC 214-30 Lot 56.6, February 16, 1979. 10. Welter, A.N., Technical Report:. Aquatic Toxi.eity:;3tudies:.FC;232'Lot 610,..!anuary 17,*.1979.1 ii. Todd,.,J.W., TechniciLl@Report: -,.FC'95/Photolyni's Study Using Simulated Su**6'light;January 9. 1979;-..