Document ppygKk9Bk0ag2ndk0eQO8jjjd

I TechnicalReport. SolubiliMteyasurements on FC-95 WATER SOLUBILITY TEST SUBSTANCE Identity:Perfluorooctanesulfonatmea;y alsobe referredtoas PFOS or FC-95. (1-Octanesulfbnicacid,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8heptadecafluoro-p,otassiumsalt,CAS # 2795-39-3) Remarks floid: The testsubstance isa whitepowder (3M Lot 583) of uncharacterizedpurity. The followingsummary isabbreviateddue tothe factthatthisstudy has been superceded by a more recenttest. METHOD Method: Procedure developed by M. T. Pike and E. A. Reinerof 3M Company GLP (YIN): No Year (studyperforfned):1980 Remarks field: Test was done indeionizedwater. RESULTS Value at temperature *C: 1.08 g/Lat22.50C Descriptionofsolubilit(ye.g.m,iscibleto solubleto not soluble): Slightlsyoluble. DATA QUALITY ReliabilityK:Jimischranking= 2. Thisstudysatsw criterifaorquality testingatthe time performed,but actualconcentrationswere not measured. The valuewas determined by indirecmteasurement. Additionallyt,hisstudylackssufficienctharactedzabon ofthe test substance purity. REFERENCES This studywas conducted by the 3M Company, Environmental Laboratory,1980. OTHER Submitter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St.Paul,Minnesota,55133 Last changed: 5/3/00 Comments on 'SoWilky Meawements on FC-95* E. A. Reiwr, W. A. ScheilProject9M126W CommercialChmdcals DtvWm, RepoptNo. 49,Feb 6.1981. GeneralPreface:Ithasbeenbxficatebdy 3M personnelOw thefluorachemiadproducts producedare mvanably mixturesof compoundswith somewhatvariablcehainlo4ft and positioniaslomerism.Giventhisf,t definitioofnIsolubffitoyfma pardculaprroducthaslittle meaningexceptin an operationaslense. That is,one can say (assuming*,atadequate aperimentalprocedum arefollowedand Lha appropriataenalyticatloolsareathand)thatthe totaalmount offluorocarbosnubstancdeissolvinignwaterfrom a parbculabratchn a caftm value.Thatvalueof solubiliitsyprobablynotpertinenttoanodw batchunks thechemical compositioonf dz secondbatchisidentictaolthefirstT.hisisparticularilmyportanitnte caseofdeterminingsolubiliotfysurfweactivesubstancebsecauseamome surfactantwshich may beneartheiKrrdftpomtsina parbeulasolubilietxypmmt willshow substanticahlangesin solubiliwtiyth temperaturec,hainlengthi,somericswxwm, mid counter-io(ne.g.,lithium, sodiumor potassium). 7U proceduresused in the currentreportare rally not adepate for solubility determinationI.ngenerala,number ofsolutionosfdiffering shouldbe prepared andanalyzedafteerquilibrationne. approachtoequilibriusmhouldbedone inbothdirections, i.e.f,rom lowerand highertemperaturetsothetempera=e of interesl 7he solubilirteysulftrom dib reportisinagreementwiththeresul(t 1.08gfl)forFC-95 from Env. Lab. RequestNo. 5372S of Dec. 2, 1980. However,no higher lktration mixturesofFC-95 (than0.25%) withwaterwereattempteadnd thisisa defectofthereporl 'Mereisa di=6ing suggestioinnthereporthatthe'solubilitmya'y be a fimctioonf the quantitoyfFC-95 mixedwithwater(seep. 2,Introductiotne,xtfollowin-gne Cotnm=W Chemicals.. .*. Ifsolubiliitstyomean anythingo,neshouldgetthesamevaluewithdiffering amountsof solidphasepresent. Edwin E. Tucker,Ph.D. 1805 AladdinSt. Norman, OK 73072 March 1,1993 Form 6747-11 -8 TECHNICAL REPORT SUMMARY Date 2-6-81 TO: TECHNICALCOMMUNICATIONSCENTER - 201-2CN timporta-ntIfreporitsprinteodnbothsideosfpaperm,odr" copietsoTCCL Division Project Environmental Laboratory (EE & PC) Commercial Report TIVO Chemicals Division Solubility Measurements on FC-95 To Don Ricker Authartar 0. E. A. Rei*'her,W. A. Scheil Notebook Reference None See Env. Lakb Request No. 5372S SECURITYIP- : Open 1%;Offqnnv Confidential) 0 Closed (Special Authorization) 3m CHEMICAL REGTSTRY KEYWORDS: (Selecttermsfrom 3M Thesaurus. Suggeirt other applicable terms.) CURRENT OBJECTIVE; To measure the water solubility Dapt Numbw 0535 Project N umber 9970012600 Report fjl#mber 049 Employee Number(&' 47816 214128 No. of Pa"s IncludingCoversh"t 5 b. Nftv Chemicals Reported Yes No of Commercial FC-95. Camiercial Chemizal ErxvLroment:al Lab EE & PC Solubility REPORT ABSTRACT: (200-250 words) This abstractinformationisdistributedby theTechnical Cofnmuniations alert3M'ers to Convany R&D. Center to Replicate laboratory measurements showed.the water solubility of FC-95, Lot 583, to be 1.08-g/l at 22-SOC. The procedure for determining this solubility involves stirring 2.5 grams of-FC-95 in deionized water'for 24 hours, settling for 1 hour, and filtering through a 0.45 ul membrane filter or filtering through a 0.7 ul glass-fiber filter or centrifuging at 12,000 x G for 10 minutes. TOC measurements on the saturated solutions developed by all 3 of the above procedures varied from each other by <1%. The complete solubility of FC-95 at 0.25 g/l demonstrated that saturation and not the presence of insoluble components caused the incomplete dissolution of FC-95 with 2.5 g/l mixtures. InformationLiaison Initials: \IN\ c@ Solu. Meas. FC-95 - EAR/WAS Page 2 February 16, 1981 INTRODUCTION This project, to measure the water solubility of commercial FC-95, was undertaken because of large discrepancies that existed between measurements made by the Environmental Laboratory and by Commercial Chemicals LaboratorT. The Environmental Laboratory had used the Veith technique(I for saturating water with organic materials. The saturation procedure utilized radio-labeled FC-95 and saturated the solution by recycling water through an FC-95 coated column for 48 hours prior to determining a concentration of 286 mg/l by scintillation counting(2). The Commercial Chemicals reported solubility value for FC-95 is 1 gram per 100 grams of distilled water, which is 35 times the previous Environmental Laboratory's measured concentration. CCD's procedure, however, involved mixing very large quantities of the Commercial FC-95 with water and may have select:.ivelydissolved very soluble components of FC-95. The present study measures the water solubility of FC-95 using water-product mixture levels that are near the saturation level, and thus should eliminate the possible error in the Commercial Chemicals' technique. METHODS AND MATERIALS The measurements utilized FC-95, Lot 583. Test mixture concentrations were 2.5 grams and 0.25 grams per liter. mixing took place in a 200+10C incubator, using 1 1/2" Teflon-coated magnetic stirring bais and magnetic stirrers. Styrofoam sheeting separated and insulated the bottlei containing the test mixtures from the heat generated by the magnetic stirring boxes. At the end of the stirring period (24 hours), the temperature of the test solutions were 22.60C for the 2.5 g/l mixture and 23.20C for the 0.25 g/l mixturep indicating incomplete insulation. Following mixing, the mixtures settled for 1 hour prior to pipetting off the supernatants and their division into 3 aliquots. Three separate procedures, performed in parallel, insured complete clarification of the supernatant. These included: 1) filtration of one of the 3 aliquots from each mixture through a 0.7 um glass-fiber filter, 2) filtration through a .45 um millipore membrane filter Type HA, and 3) centrifugation at 10,000 rpm (approx. 12,000 x G) at 200C for 10 minutes. Solub. Meas. FC-95 - EAR/WAS Page 3 February 16, 1981 TOC measurement provided the data for the calculation of the FC-95 concentrations in the filtrates and supernatants. Boiling the millipore filters 3 times for 1 hour and washing the glass-fiber filters thoroughly with distilled water before filtering insured that the filters did not add organic material (TOC) to the filtrate. The calculation of the FC-95 concentrations assumed a TOC of 17.8%. This is the theoretical TOC and is also the TOC we have measured in our laboratory analysis of FC-95. RESULTS AND DISCUSSION Table 1 shows the results of the dissolved TOC (DOC) measurements and the corresponding FC-95 concentrations. The data shows that at .25 g/l, FC-95 is completed dissolved. This indicates that there are no very insoluble components of FC-95.. At 2.5 g/l, only approximately 1 g/l is dissolved. This idp-ntical result was obtained using all three clarification procedur4s. In addition, as a quality assurance test, TOC measurements were made on potassium hydrogen phthalate solutions of known concentration (Table 2). These controls demonstrated the accuracy of our TOC procedure. REFERENCES (1) G. D. Veith and V. M. Comstock, J. Fish. Res. Board Can. 32, 1848 (1975). (2)Art Mendel, Analytical Methodology and Support, Dept. 0535, Project 9970612643, Report 008, 1/17/79. EAR/cel Attachments: Table I and 2 TABEZ 1 DISSOLVM TOTAL OFGMIC CARBON (DOC) AND CALCEXATED SOLTM[Z CONCENTRATION OF FC-95 Initial Concentration of FC-95 Water Mixture 250 mg/l 2,500 mg/l SOLIM F040M PROCEMM Fi.ltration (0.45 m M/F)l' DOC Conc. mg/i ng/i 43.2 243 Filtration (0.7 um GF/F)2 DOC Conc. mg/i m/l 43.6 245 Centrifugation (10 min. @ 1200 x G DOC conc. ng/i mg/1- 45.2 45.43 44.53 2534 192.0 192.63 1,0804 191.6 192.63 1,0804 193.4 193.23 1,0904 Footnotes: 1 0.45 m mwbrane filter 2 0.7 um glass-fiber filter 3 Replicate analysis 4 Solubility is calculated from average DOC. TAJRE 2 DOC MEASURDENTS AND CMLULATED CCNCDM@ATICNS OF STANDARD SOLUTIa4S Concentration of PotasSim Hydrogen Phthalate (KHP) Standard 382.5 rg/l Tkieoretical DOC 180.0 150 mg/i 70.6 Measured - DOC 181.2 179.51 178.9-1 72.0 71-11 70.61 KEIP Concentration Calculated from DOC 382.32 1512 Fbotnotes: -1 Replicate analysis 2 Solubility is calculated fran average DOC. Form 10620-0 PWO Reques@torLaboratoWroyrk EnvironmentalLab-EE & PC Bldg.2-3E (9) Lab Request No. - -C'37 2 S Page-I of Requemr 1. .14 C-IeP-,A;EIAIE7A Dept. Charge [--)0012 [:30222 Description Ft&q@l@rR,OU (3 7-ionround 0 Other 'Razardaus Precautions 0535 Project No. ptoq~ Data I/-31-.TiD rfadlem No. W71Vl?-t-001 S-S3 Purpose of Dou I C3Agency Cl intemal OR" Received Analyst EirtirnateLdab Hours (EL) Dow Camp @2-02 Hra. -040 Comments K4 - F-piv;& I Lab rip Contract Lab ExP*@tod Completion onto tC L) Sample No. 1 2 3 4 5 6 code Date Dowdption Yg 3 Da b SOMPWS vwtlbe dbarded 30 davs aftercompletion ofanel"!sunim otherwise.noted to Approved ev I CIEC.-O05-35 C reECUESI TOP LABORAIGEY UORK FINAL REPCRT LAB REQUEST MOo 5372S --RECUESICR-ISPE: EIR FSCJECI MCo 991001;EOO &ESE: FC 55 LOT 5R3 --LAB PERSONNEL-- DAIE RECEIVID.0 2101/1980 ANALYST: WAS DAIE COMPLE?ED: 12JD2/1980 HRS SPENT. 10 ACIICX DATE 21/24/1980 12102/1980 CECE Cill JEC.CF-C. itsi c.ELtEIIIII llc icc TEC 0.0215% 0.4500 N/F 01 43*2 YC/L CECE CAIF ALE.DECO IESI SCL'UB I 117 1 IEC l(c IEC Oo25% 0.45UP Y/F 05 1060 NCIL 19@.0 VG/L 192.6 PC/L 0.025% C.'7UI4 CFIF 02 43.6 NG/L 6.25% Go7UN CF/F 06 ICSO MG/L IS1.6 MG/L iS2o6 14G/L 0.0252 CL4791FUGE 03 .45.2 MG/L 45.4 MC/L 44o5 MG/L 0.251 CENTRIFUGE 01 1090 MG/L 193.4 NG/L 193*2-PGJL GA- -rV- STD #35 04 ?2oO 71.1 70.6 14G/L MG/L MG/L Ch Irv2 STD 1431- 0 13 181.2 L79.5 11go9 PG/L MG/L IOD PG/Li. SAPPLE IDISCAND DATE 1101/1981 lntwnaClormapandenm CC*. D. R. Ricker.- 53-4 0. L. Bacon/R, L.,Bohon -..'21-nW(63). TO: M. T. PIKC COt4MERCIAL CI[Et4lCALS DIVISION 236-2AO1 Fiom: E. A. REINER - ENVIRONMENTAL LABORATORY (EE&PC) 21-BW &Oecl: SOLUBILITY DETERMINATION ON FC-9L5 (63). D8(e* JANUARY 30, 1980 The following is*rtechnlque we agreed to in our phone conversation of 1/30/80 to measure the solubility in water of FC-95: 1. Prepare 0.25% and 0.025% mixturesof FC-95 in deionized. water* GP 4;1* 2. Mix foC 24 hours,4usin2,A ma?netic stirrer. S..e %zrs,,r- rL- S--r" &..r 3. Lot settle for approximately 1 hour. 4. Pipette off the supernatants and divide the supernatants into 3 aliquots. S. Filter one of the aliquots from each initial concgntration through a .7 um glass fiber filter*. :;,@.4%.(F;(/-.- 6. Filter the second aliquots through a .45)um millipore Me@V.^n-filter*f-rt- ;#,4 7. L@6t the remaining (third) aliquots4 le fwt. 24 izocrg-*a6- 0,( remove a sample of the supern&t&nts-by';ipette. 8. Do a TOC analysis of the filtrates from Steps 5 and 6, and the supernatants from step 7o 9. Calculate the concentration of FC-95 by assuming a -&OC of' 17.8%. This is the theoretical TOC and also the TOC we have measured in our laboratory analysis of Fc-gS. The filters used will be boiled 3 times for 1 hour using fresh Dr water to prevent filters from adding TOC to the filtrate. 2 We estimate-that this procedure, modified per our phone call, will take approximately 12 hours of technician time. It will take longer than the 8 hrs. estimated in our original proposal because 6 rather than 3 samplis will have to be prepared and analyzed. our current recharge rate will cost approximately $375.00. If you have any further questions or commentsp please feel free to contact me on .778-5079. Ewcel IL SAMPLE DESCRIPTION PA-1 z 7,pd u ENVIRONMENTAL '372 5 i: Pop No. ENOR. LAB -.WORK SHEET' Daw: Ansivit: HrL: 4- 2-q 0-2-S t7, ,44- 09&2Y.-c h&gz4L&-:6 be, V d A&e,-U 2U Coll L7- 2.6 A,,,O (0. 0 2 SV. Reviewedby: -c eA- PORN I eta*.0-rW* SAMPLE DESCRIPTION ENVIRONMENTAL File: Pop 14o. ENDR. LAS -WORK SHEET oat.: Analyst: Hrs.: 2,/PV -WLXV@ q44 dazza MZ2@.6liol AA@. 244 dWi, ol 'Are d462@nA72rP L/ A IV dad A.9 Ile Reviewed by: to- u 101-1 tV room I"as-4.vwo SAMPLE DESCRIPTION ENVIRONMEN HXO file: -ft p No. E GR. LAB* 'WORK SHEET Dots: Analyst: !V.- MF--A..:J@7 dgm - v'-oet jo ar- 40 "A 4r"4x AA"@@ *e. A, o. 2 oror o 3.z A: 0,7 e; .7 3 22-5 go, Toc r 41Ate..c.@26en,& 4,1,eLW@,-t@Z rf &42.& "" 44$aA _-@ ./ - 41 -Z@ @roc Review4d by: ANALY313FoRm '37Z S 4 5 to it 12 ki. 2 131 A-A-0- - A- Ll -4 171 2D 21 n 23 .M- m 25 Z>j 25 271 20 1 291 30 1 311 321 331 34 3S 36 37 3839 421 43.L yr.2 -qS-4 Ri M7)C C^ie r imL LEZ@L 1?2.,g/062 191-(o@07(p 19Z.6 ion fig fooe /090 A&W-A