Document 0OBZ08k47B5xVJ9JeEEBdk9O

STUDY SUMMARY FOR WORK PERFORMED DURING 1977-1979 TEST SUBSTANCE Identity:Perfluorooctanoiaccid,ammonium salt;may alsobe referredto as PFOA ammonium salt,Ammonium perfluorooctanoateP,FO, FC116, FC-126, FC-169, or FC-143. (Octanoicacid,pentadecafluoroammonium salt,CAS # 3825-26-1) Remarks: The subjectmaterialisFC-143. It'psuritywas not sufficiently characterizedatthe timethese testswere conducted,though current informationindicatesitisa mixtureof96.5 - 100% testsubstance and 0 3.5% Cr,,C7,, and Cg perfluoroanalogue compounds. The attached isan overview createctin 1979 thrstudies completed from 1977 to 1979. Robust summaries have already been submiffecfthrmany of these studies. Others have not beensummadzect due to the factthat the originalstudies were not found. STUDIES Water solubilitdye;gradation;soilsorptionp;arfitoncoefficienatq;uatc tox Remarks: The attacheddocument includesa solubilivtaylue and an octanol/waterpartitiocnoefficienvtalue thatcould not be confirmedthrough our availablearchivedreports.Theiroriginisthereforeunknown. DATA QUALITY ReliabilityT:hese studieshave varyingKJimischrankings,though most would be designateda "3".Inmany cases actualconcentrationswere not measured. The valuewas determinedby indirecmteasurement (e.g., bioconcentrabonanalyzingforFl or usingnominalconcentrations(e.g., aquatc to)dcityO)f.ten thetestproceduremethodology was not noted. In some cases,the analyticamlethodology itselwfas quesfionable.Additionally, these studieslacksufficienctharacterizatioonfthe testsubstance purity. REFERENCES 3M TechnicalReport "FinalComprehensive Report: FC 143.m A. N. Welter, Project9770612643, Report number 012, March 23, 1979 OTHER Submitter: 3M Company, Environnienta.L1aboratory,P.O. Box 33331, St. Paul,Minnesota,55133 Last changed: 5/25/00 IA TECHNICAL REPORT TO: TECHNICAL COMMUNICATIONS CENTER - 201-2CN SUMMARY aEr ch= 23, 197C- (importan-t Ifreportisprintedon bo& sidesofp4w, sendtm Capin toTCC.) Division Environmental Project Laboratory.(EE Fate of Fluorochemicals Report Title Final Comprehensive To R. A. Prokop Authorl .A- Welter Notebook Reference Report: & PC) FC 143 m 0535 OProject Number 9970612643 wept-wtmumow 012 Empt3@e-aNum-@rs@@@ 09362 No. at POWs IncludingC3;ershoe't SECURITY 10- Open Closed KEYWORDS: IS*Ioct torrm from 3M Thesaurus. Sugpst other applicablteerms.) CURRENT OBJECTIVE: Final Report: 3@ CHEMICAL REGISTRY I 11 Now Chemkols Reporfad (3 Yes 19 No Encompasses all work performed during the period; 1977-1979. EE&PC - Div. Fluorochemical (Analytical) (Aquatic) (Degradation) (soil) Toxicity REPORT ABSTRACT: (200-250words)Thisabstracitnformatioinscostributboyd theTechnicalCommunicationsCenterto slart3M*orstoCorr4mw R&D. Ic: D.L. Bacon R.L. Bohon Y.Pothapragada informationLiaison Initials: -@ L INTRODUCTION The rationale for performing environmental effectl25tudies on fluorochemicais has been discussed previously The subject fluorochemical of this report is FC 143, a anionic surfactant, which has the potential for widespread distribution in the environment as this material is used by the Teflon(R) coating industry, both domestically and internationally. FC 143 chemically is the ammonium salt of perfluoro-octanoic acid. This material is a white granular powder having a molecular weight of 431 and the chemical structure shown below. C7 F,S POO-NII4 -PC 143 This report consolidates all available information in the areas of water solubility, partition coefficients,degradation, soil sorption and aquatic toxicity. The probable environmental risk of PC 143 is defined. METHODS Water solubility, biodegradation and soi1t t?Egiion methodology's have been the subject of technical repor s A) Aquatic Toxicity Testing The testing protocols utilized for t@41 study were modeled after that described by TJSEPA (1975) 1. Bluegill Sunfish The bluegill sunfish (Lepomia macrochirue) used in this study were obtained from a private hatchery.4 Stock fish were held in fiberglass holding tanks filled with carbon-filtered well water maintained at 14-150C. A daily photoperiod of 16 hours light and 8 hours dark, with a 30-minute transition period, was maintained throughout the acclimation and testing period. ',"he fish were fed Tetra-Min daily, food being withheld 48 hours prior to and throughout the test period. Fish were acclimated for 14 days prior to testing. Acute short-term (96-hour) static aquatic bioassays were performed on FC 143, lot 340. Carbon-filtered well water of known composition was used as the diluent. All glass aquaria, 35 x 20 x 90 em, containing 16 liters of water or water plus FC 143 comprised a study chamber. adale Fattig Fish Farm, Brady, Nebraska b Commercial fish food of known composition. 2 Twenty bluegill sunfish, (Lepomia macrochirua), uniform in size and weight, were tested at each concentration of FC 143. Test fish were randomly' assigned to various test chambers within 30 minutes fol@@wigg FC 143 addition. Test temperatures were maintained at-19 - I 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 or erratic swimming patterns were similarly recorded when appropriate. Organisms used in this study were considered to be generally healthy and free of disease. 2. Aquatic Invertebrates - 48 hour Static LC50 Daphnia magna, twenty organisms per test chamber, were exposed to FC 143, lot 340 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. Invertebrate test concentrations were 7.5, 10, 18, 32 and 56 mg/l while vertebrate test concentrations were 420, 560, 750, 1000, and 1350 mg/l. LcgoUvalues with 95% confidence limits were calculated using th SEPA (Duluth) Probit computer program on the 3M Trac system. RESULTS Table 1 lists water solubility and partition coefficient data obtained using FC 143, lot 340. '-rhismaterial is extremely water soluble, :"20g/l. FC 143 where added to water appeared to form a gel although further additions of PC 143 were similarly absorbed. This material is slightly lipophilic as evidenced by a partition coefficient of 5. Based on these data it can be concluded that FC 14@ would not bioc entrate to an appreciable extent in the environment. Chiou et al?e@ have described an empirical relationship between the water solubility of a chemical and.its bioconcentration factor. In their system, the ascribed error is considered to be approximately one order of magnitude. When applying data generated for FC 143 to this proposed relationship, this material would be projected to possess a bioconcentration factor of approximately 10. .TABLE 1 Water Solubility and Partition Coefficient of FC 143 Parameter Test Results Solubility Coarse method >20 g/l o@S Partition Coefficient n-octanol/water 5 3 PC 143 was found to be completely istant to biodegradation under the test conditions employedf2l. The 2 1/2 month shake culture biodegradation study utilized microbial test cultures derived from activated sludge inocula obtained from the Chemolite, Decatur and Twin Cities Metro Plan waste treatment system. During the time course of this study a strain of microbes which could degrade PC 143 did not develop, hence this material would be expected to persist in the environment for extended periods of time unaltered by microbial catabolism. . Soil sorption studies have shown that approximate ly 5%, (range 2-7%), of the PC 143 present in a wa solution was adsorbed to Brill sandy loam soil (Table 2) Conversely, approximately 80% of the amount of PC 143 adsorbed to this soil would be desorbed after three (3) desorption trials (Table 2). Mobility.2@FC 143 was calculated using the scheme described by Hamaker""' whereby adsorption coefficients are converted to a constant K which reflects the organic content of the soil. Th"is 0 cinvestigator has shown that the relative mobility of a group of pesticides could be determined in this fashion and that the K Jvalue could be correlated with pesticide mobility. In a? ying this test, PC 143 had a K value of 17, being slightly less mobile than chloramben, K 08f 12-8, wt@5h was the most mobile pesticide,based on HUaker 's work Table 2 Soil Sorption Tests on PC 143 Parameter Soil Sorption Test Adsorption Desorption K oc Solution Water Water Results - 5%, range 2-7% 80% of amount adsorbe 17 Results of the acute static aquatic tests are tabulated (Table 3). Based on the aquatic toxicity criteria established by NIOSH, PC 143 would be considered practically non-t?fic to the vertebrates and invertebrates used in this test . it is to be noted that the invertebrate data correlate well with those data obtained when testing fresh warm wfA!Tolpecies. This correlation has been observed repeatedly% Egg-fry studies were contracted to EG&G Bionomics Laboratory and their results comprise Tables 4 and 5. These studies were undertaken to assess the effect of PC 143 at sublethal levels on hatchability, survival, weight and length changes (Table 4). It is generally accepted that the immature or young stages of an aquatiespecies are quite sensitive indicators 4 Table 3 PC 143, Results of 96 Hour Acute Static Testing Test Organisms c)6 HR,LC mg/l 50 Limits Lower, mg/l Upper mg/l Bluegill Sunfish 569 500 636 Daphnia magna 63P 570 699 632 570 698 Table 4 Percentage Egg Hatch, Percentage Survival, Total 'Length artd Wet Weight of Pathead Minnow Pry (PimephaZes promezaa) duri?g Exposure to varying concentrations of,FC 143 30 Days Post Hatch .Concentration Hatch % Survival % Length mm Weight mg mg/l 100 96 8.Ci 20.5 59.5 50 92.5 94 20 62.5 25 Qq 92.5 21 72 12.5 90.5 97.5 21 71 6..2 94.5 93 Pi 6q Control qc-.5 93.5 20.5 68.5 a Work performed by EG&G Bionomics Laboratory, Inc. .b Summary table submitted to Environmental Laboratory, 3M, St. Paul, as part of final report. of chemically induced toxicity. In the parameters under investigation no statistically significant differences were obtained. At the highest PC 143 concentration tested, 100 mg/l, reductions were recorded in survival percent and weight 30 days post hatch. Although these data are suggestive of a latent onset in the development of cumulative toxicity, the dose levels of PC 143 at which these phenomina were observed far exceed, (several orders of magnitude), the environmental concentrations*of PC 143. 5 Based on the results of the histopathological examination, a 30-day exposure to 100 mg/l FC 143 did not contribute to abnormal histopathology (Table 5). Both groups of organisms exhibited fatty liver changes, 6/10 controls and 5/10 treated-organisms. Similarly, gill hyperplasia was seen in both groups, 3/10 controls and 2/10 treated fry. Table 5 Histopathological Examination of Pathead Minnow Fry (Pimephalea apgomezaa) exposed 30-days to 100 mg/l PC 143 Test Material Control .100 mg/l FC 143 Numbet of Observations 10 10 Histopathological Findings 6/10 fatty liver changes 3/10 normal 3/10 gill hyperplasia 5/10 normal 5/10 fatty liver changes 2/10 gill hyperplasia DISCUSSION Th p primary purpose of this report is to provide a single source for all environmental data generated relating to FC 143 and to provide an analysis of potential environmental risk. In developing this analysis two model types will be discussed: (1) a schematized closed system environment and 2) a practical model based on use of FC 143 at a manufacturing site and consumer product usage. 1. Closed System The environment can be considered to be a closed system, schematically represented as: Air ----%--- Soil Water Chemicals entering this system might establish an equilibrium between two or all tbree.compartments, remain confined within a single compartment or pertubate all phases of the depicted cycle. 6 Specifically we can represent the impact of PC 143 in the following manner: No PhotodegradatioTL_ Air -.evolatility Soil ___,,..Nodegradation Volatility Rate? rain 80% ater? of adsorb S% adsorbed Water >20 g/l (gel) Sediment, No biodegradation sorption phenomena as seen in soil As illustrated, PC 143 enters the environment primarily by means of the waterways and secondarily via the terrestrial ecosystem and atmosphere. Thii-material does not adsorb permanently to either soil and/or sediment, remaining however in the water compartment. It'is not known whether PC 143 is volatile, a fact which assumes importance in light ofllle finding that PC 143 does not undergo photolysis. - Based on the foregoing, :the waterways apparently are the environmental sink for PC 143. Intermediate receptors have not been identified. 2. Manufacturing and Consumer Model The following construct illustrates various pathways wherein PC 143 may enter the environment at the processing site. FC 143 Anionic Surfactant Manufacturer Photographic Indust@- Process TeflonR Coating ODnswier wastes Liquid Solid Waste Treatment ..................................................................................... Effluent Outfall Sludge .!'%.Incinerate L Ash I So. Volatil Riyer Volatility Air Sediment Fish I - Birds Ian ill leach Volatile I ii2o Air/ I s\oii H 20 soil inCID7 tion Air k\ H 20 leach Volatility Ai @o Food Chain H 20 8 The above figure depicts projected pathways wherein PC 143 might enter ttf)environment. In discussing use of PC 143 by the Teflon coating and photographic industries with Dr. U. Pike, Commercial Chemical Division, I was informed that to their(hiowledge no PC 143 wastes would be generated by the Teflon coating process. Based on this information, I have depicted this no waste situation by the following sign; *. In discussing the manufacture of PC 143 with Jerry Hoffer Chemolite,. a similar observation to that outlined above was made. in view of the above we can project the environmental co,ncentration under conditions wherein all FC 143 manufactured is lost to the environment. Since waterways are the environmental sink for PC 143, a simplistic model utilizing a single point source,for PC 143 and a river would enable one to project an estimated environmental .concentration for PC 143 under 'a worst case situation. We have made several assumptions which are considered basic to this simplistic model: 1) Total production is at Chemolite and all PC 143 produced is discharged. NO.FC 143 is removed by the treatment facility. 3) All effluent is discharged into the Mississippi River. 4) PC 143 is discharged uniformly. 5) River flow and all other parameters are constanti hence not subject to seasonal and/or climatic perturbations. The formulae used in these projections include: 1) MG/min 2) MG/min x 3) Lbs/day (River Flow, CFM)(Conversion,gal/ft 3 )(Time,min) Production, per annum 1440 = MG/Day (mg/l x wt. lbs. H2 0 per gal)(MG/Day) Mississippi River flow at Hastings, MN, based on a 10 year low flow record is 10,000 CPS. The total 5 year production figures were provided by D.R. Ricker, Commercial Chemicals Division. In utilizing these figures an estimated environmental concentration of PC 143 in the Misg'issippi RTver below Che-molite was calculated. During the period 1973-1978, the EEC for PC 143 was calculated to be 1.6 pg/l at Hastings, ?In., while the EEC projected for the period 1978-1983 is projected at 2.4f g/l. Since the water compartment is the environmental a nk for FC 1439 it is determined that at the present and projected levels of production FC 143 will not present an unreasonable environmental risk under worst case situations. CONCLUSIONS Under the test conditions employed in characterizing selected physicochemical and environmental properties' of PC 143 it has been determined that this material 1) is extremely water soluble, forming a gel at 20 g/l. 2) has an n-octanol/water partition coefficient of-,5 13) is resistant to microbial degradation 4) is extremely-mobile in Brill sandy loam soil 5) in an egg-fry siudy did not affect hatchability, survival, length or weight following a 30 day exposure to PC 143 at sublethal levels to a statistically significant degree. Similarly, no adverse effect was noted on tissues examined for evidence of chemical induced pathology. 6) is to be found primarily in the water compartment, hence its environmental sink. No specific intermediate receptors have been identified. 7) would have an estimated environmental concentration of approximat4@1-y 1.6-2.4Tg/l, under con7ditions wherein all FC 143 were manufactured at Chemolite and discharged into the Mississippi River. 8) will not present an unreasonable environmental risk .based on present and projected production levels, usage patterns etc. 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, 1978. 3. Welsh, S.K., Technical Report: "Adsorption of FC 95 and FC 143 on Soil", February 27, 1978. 4. US/EPA - Methods for Acute Toxicity Test with Fish, Macro-ihvertebrates and Amphibians, Ecological Research Series 660/3-75-009, 1975. 5. Chiou, Cary T., Virgil H. Freed, David W. Schmedding, and Rodger L. Kohnert: Partition Coefficient and Bioaccumulation of Selected Organic Chemicals, Environmental Science and Technology, 11(5): 475-478, 1977. 10 6. Hamaker, i.W., "Interpretation of Soil Leaching Experiments" in Chemicals, Human Health and the Environmeni, A Collection of Dow Scientific Papers, Vol. 1, Dow Chemical USA Midland, Michigan 48640. 7. Registry of Toxic Effects of Chemical Substances, '76 Edition, Christensen, H.E., and E.J. Fairchild, Eds. p.xv and Ci, US Department of Health, Education, and Welfare; National Institute for Occupational Safety and Health, Washington, D.C., June, 1976. 8. Welteri A.N., Technical Report: Aquatic Toxicity Studies FC 214-30 lot 566, February.16, 1979. 9. Welter, A.N., Technical Report: Aquatic Toxicity Studies, FC*232 lot 610, January 17, 1979., 10. Welter, A.N., Technical Report: Final Comprehensive Report, FC 95 March, 1979. 11. Todd, J.W., Technical Report: FC 143 Photolysis Study using Simulated Sunlight, February 2, 1979. 12. Welter, A.M. Technical Report: Final Comprehensive Report on FM 3422, February 2, 1979.