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PR ARG 1287 TELOMER B ALCOHOL, CyFi;CH;CH;OH: WATER SOLUBILITY DUPONT REPORT NUMBER 12718 Test Guideline(s) OECD 105 (adopted 12 May 1981). Authors Mary A. Kaiser, Ph.D. (study director) Daryl P. Cobranchi, Ph.D. RobC Beucrk,Pth. D. Study Completion Date 16 July 2002 Report Date 27 December 2002 Test Facility DuPont Corporate Center for Analytical Sciences Experimental Station 02/5321 (and Glasgow 300) Wilmington, DE 19880-0402 Sponsor cTleoloRmaenrd RCeosrepaorrcahtiPoannel = = on ~ BS 2 35 5 ITelomer Research Program 000002 2 TABLE OF CONTENTS Title Page A -------------------------------- `TableofContents. 1 wns 2.0 GENEral Study INFOMIANON vss EE ---- NN ---------------- El 4 SATA SAN smmmmmmmmmmmmmm-- dt 3.3 Test Conduct... senmmmmmen----"5 El 35 BENE ARTIS Scmmmmmmmm------------ 7 0 VIILY CMR OL SY ommmmmmmmmmmmsmmsmmmamominss 7 3.7 Guideline] Deviations - - I 40 Resulis and Discussion. sn 8 5.0 CONCIUSIONS crv rn ssmm------ 6.0 RELOFEREDCUOOTAS.vvrsssssssssssssssed I DIR ETON mmm) BI BETAS Bssuresmmmmm-------- Tables Figures Appendices 8-2 TELOMER B ALCOHOL, CsF1;CH,CH;OH: WATER SOLUBILITY Authors Mary A. Kaiser, Ph.D. (study director) DarylP. Cobranchi, Ph.D. RoberCt Buck, Ph.D. 1.0 SumMmMARY TestSystem: `The water solubilityof8-2 Telomer B Alcohol, CyF,CH:CH;OH, was determined in aqueous solution at 12 C, 25 C, 37C and 60 C using a TelomorResearch Program 000003 variationof OECD method 105. The experimental mixture was shaken for at least three days and the test substance concentration determined at various intervals via gas chromatography mass spectrometry. Findings: "The solubility in water was 134 pg/L (+-29 ug/L) at 12C ; 137 (+/-53 pg/L) at at60C. 25 C; 318 g/Lb (+-176 pg/L) at 37 C, and 225 pg/L (+/- 51 pg/L) Conclusions: `The solubilityof 8-2 Telomer B Alcohol, CyF:CH:CH;OH, in water from 12 C1C0isv/ery6low0(134 10318 g/L). 20 GENERAL STUDY INFORMATION Study Objectives "The objectives of this study were to: Determine the water solubility between 12 C, 25 C, 37C, and 60C in pure water. Determine the effectofpH on water solubility at 12 C, 25 C, 37C and60C. TestSystem Justification "The test system was selected by the sponsor. Study Personnel Test Facility Name `DuPont Corporate Center for Analytical Sciences Building 300, Glasgow, Delaware, 197146101 USA Management Study Director Marianne Marsi, Ph.D. Mary A. Kaiser, Ph.D. DuPont Company STelomer Research Program 000004 3 Principle Investigator: Technical Personnel: Daryl P. Cobranchi, Ph.D. DuPont Company Corporate Center for Analytical Sciences Barry W. Wolstenholme Study Execution Dates `Study Initiation Date: Experimental Start Date: Experimental Completion Date: Study Completion Date: 15-Jun-2001 15-Jun-2001 28-June 2002 12-July 2002 3.0 MATERIALS AND METHODS 31 Test Guidelines `The solubility in water ofa substanceisspecified by the saturation mass concentration of the substance in water andis a functionof temperature. The sisolkugb/imli't;ygi/nl wmaatyeralissospbeeciufsieed.d in untofweight per volumeofsolution. The Sl-uit 32 Chemical System 3.21 TestSubstance `The test substance was obtained from Clariant Gmbh (Germany) and was 99.2% pure via gas chromatography. The major impurity (0.8% by area) was tentatively identified as CF sCF=CH;OH based onthemass spectral fragmentation pattem. Name: `Synonym: Active substance(s) CAS Name: CAS Number(s): 8:2 Telomer B Alcohol (Perfluorooctylethanol 8:2 Telomer B Alcohol, 9.2% 3I-3D4e,ca4n5a5l,66778899.10,10,10heptadecafluoro678397 4Telomer Research Program 4 000005 Structure: F F OH F FF F F FF F FF F F FF H Number Lot Number: EMSE Sample Number: Concentration, nominal: Concentration, analyzed: Certificateof Analysis Date: Date Received: Vapor pressure Stability: Appearanc/Calor: Storage Conditions: 24691 P0000 E93386-63 99% 992% 03-Apr. 2001 15-June 2001 3Paat2sec Stable at ambient room temperature White solid Room temperature; keep tightly closed 322 Test Vehicle "The test substance was dissolved in ultrapurewater(17.6MG-cm). 323.1 Test Units Test vesselswere 2 mL (nominal) borosilicate glass vial, 12mm outer diameter by 3ru2bmbemr sleepngttuhm. cVapisa.l caps were blue caps with Teflon fluoropolymer resin and red- STelomer Research Program 000006 3232 Test Conditions Test solutions were kept closed during the dissolution and shaking process. 33 Test Conduct `The water solubilityofthe 8-2 Telomer B Alcohol study material was determined at 12C, 25, 37C and 60C !. Excess test substance was placed in a 2-mL gas. chromatography sample vials and shaken at constant temperature for 24 hourson a shaker able. The test substance concentration was measured at various time intervals by gas chromatography with mass spectrometric detection (Electron Impact (EI) detection, m/z 463). Inthe second method used to determine water solubility, approximately 100 mgofthe 8-2 TelomeBr Alcohol was added to astandard screwcap 2-mL glass gas chromatography vial. The vial was coated with excess 8:2 `Telomer B Alcohol by placing the open vialon a warm surface to melt the test substance and condense the study substance onto the cooler upper surfacesof the vial The vial was then removed from the warm surface and allowed to come to room temperature. Ultrapure (conductivity of 17.6 MQ-cm) water was added to the vial so that no headspace was available. The silicone-rubber sideof the vial cap was turned to cover the vialbefore scaling. The vialwasplaced on a thermostated, insulated shaker tableat the temperatureofinteres. The table rotation ratewas set at approximately 100 rpm for at least four days. A sample was removed to 3 temperature-chromatographic autosampler tray and the test substance was determined by GC/MS. This method is much faster than the first method and gives the same result, Details of the GC/MS experiment Vials: Target DP (dal purpose) Vials, 1.8 ml capacity, borosilicate glass, 12mm outer dismete by 32 mem length, National Scientific Inc, 205 East Pletown Road, Quakertown, PA 13951 USA, catalog number C4000-1. Vial caps: Target DP (dual purpose) blue caps with Telon and re-rubler septum, National Scienifc Inc, 205 Eas Paltown Road, Quakertown, PA 18951 USA, catalog numberCA000-S1B. Helium: 99.999% pure, plumbed wih stainless steel and copper wbing, MG Indusris, Newark, DE USA. + Gas Chromatograph and Mass Spectrometer HP (now Agilent) Series I1 Plus as chromatograph and HP (now Agilent) 3972 mass selective detector (MSD) with 8 100-sample autosampler tray and HP. (vow Agilen) 7673 GC injector tower, Agilent Technologies, 2850 Centerill Road, Wilmington, DE 19808, USA. + Gas chromatograph's septa: MerlinMicroscal, Medlin Instrument Company, Half Bay, CA 94019 USA, part number 310. VWR cooling unit, 1310 Goshen Parkway, West Chester, PA 19380 USA, model 11604. 6Telomer Research Program 000007 6 + Nalgene polypropylene volumetric asks, rom VWR, 1310 Goshen Parkway, West Chester, PA 19380 USA. + Thermolyne Bigger Bill orbitalshakerstat 300 rpm, VWR, 1310Goshen Parkway, West Chester, PA 19380 USA, with temperature controlled able and ray. Shaker connected to a Brinkmann RM-6. cooling uit, Brinkmann Instruments, Inc., One Cantiague Road, PO Box 1019 `Westbury, NY 11590 USA GC/MS conditions: + Oven temperature: 80C for one minute, increased at 20C/minut 10 300C and held for 10 minutes. Runtime 22 mines. + Injector: spliss, 225C, purge low $0.0 mLiminute, purge time 0.70 mines, saver flow 20 mL/minute3, sample washes, no pump (quiscent), IAL injectionsize,(10 uL. Agilent syringe), three post injection washes with JTBakerultaresianalyzed ea. #9263-03) methanol, sampling depth 100 mm above the nominal positon. Solvent delay: 5.0minutes ic, deccior tunoneafdtr five minutes) . Tons: 463.0, 131.0,95.310.,0(6pr9ef.er0ed,) ElaTev + Column: Restek RTX-200 tfloropropylmethy! polyslox6a0nmeete)r, 250 um diameter, 1.0 um lm thickness, catalog number 15056, Restek Corporation, 110 Benner Circle, Bellefonte, PA 16823 USA. Initial flowsetat1.4mL minut, constant low, nial inlet pressure 25.89 ps, average velosty 31 emis LimitofDetection (LOD) approximately 20 pp; limit ofquantification (LOQ) approximately 50 ppb. 34 Parameters Observed s"Tohleutpieoankatarsepaecoirfihceitgehmptewraatsurmeesa,sured for the test substance saturated in the aqueous 35 ResultAnalysis s`Tahmeepepaakrahmeeitgehrtoofraspteaankdaarreadocbatraeifunleldyfporretphaerteedstisnumbestthaanncoelw.as compared to the 3.6 Validity Criteriaofthe Study a"Tnhdeatfesetrrtehseulttesstwesrubesctoannsciedwereerde vwailtihdiinft5h%epoeftahkeapreaarsamoeftthere msteaansduarredds. run before 37 Guideline Deviations Deviation | Conceming: Deviation: Reason: Additionof the test substance to the vessel `The test substance was coated on the wall of the test vessel, The "excess" test substance formed needle like structures, which interfered with the TTelomer Research Program 000008 Deviation 2 Impact on Study: Conceming: Deviation: Reason: Impact on Study: chromatographic injection. None Choiceoftest method cThoemp"ofulansdks" hmaevtihnogdsroleucboilmimteyn>de1d0 pfoprm was umseetdhordat"hewrhtihcahn itshre e"ccoomlmuemnndeeldutfioorn `compounds having solubility < 10ppm. r"eTlhiea"blceolthuamtntheelu"tfiloanskm"emtehtohdo"difloerssvolatile compounds. None 4.0 RESULTS AND Discussion "Table | summarizes the solubility data versus temperature. TwhiethsnoolsiugnbiflaicltapinHttd3iy,ffperHen1c1eainndthae usoltuboilgityeopnrHo8(-5u2.3sT)elatom1e2rBC Awlecroehmoelaosvuerretdhe PdeHterramnignea.tioTnasb.le 2 through 7 summarize the measured water solubility versus pH `The solubility in water at 12C is 134 pg/L (+/-29 pg/L); 137 pg/L (+/-53 BEL) 25C; 318 ug/L (+-176 pg/L) at 37 C, and 225 pg/L. (+/- 51 ug/L) at60 C. Varying pH from 3 to 11 had no impact on the solubility measurement. 5.0 CONCLUSIONS o"Trhce.solubilityof 82 Telomer B Alcohol i in the 100 to 250 jg range from 12C to Telomer Research Program 000008 s 6.0 RETENTION OF RECORDS EStxupdeyridmoecnuamlenattsinodn imnactleurdiianlgs bwuitlnboetstroarevdend0t:he archivesofthe DuPont + study proto; + any protocol andor report amendmoeadndetndsa or devitions; -- + one original signed copy ofthe fina report + elafbiograotmooryrs,paenidlfocr fesozsetssrpewcdfia.rw data suas pecrsonhne les, instrument, equipment, 7.0 DisPOSAL OF TEST ITEM ADfutPeornstsGulaansegoowftihteefuinnaliriespetx,pitrhaetiroenmdaaltnaindtetsthesnubdsteancse wtibleylbbeyusmetionrdge,d aotlthees other asngements as mads between he sponsor andthe Tew Facil 8.0 REFERENCE 1. oCOhuEenCmiiDschaGlduihpdreyolip1ne9er9si5s)foTrethseNTeosti10n5g:ofWaCtheermSilcuablislSye,saidoonpt1e: dP1h3ysaiycal1981 Table 1 Water Solubility versus Temperature (C) at Autogeneous pH 2 TT 5 Ts] [2s [1p[53 [47] Cne = mamo bor ofT tests2255 [51 Tuo STelomer Research Program 000010 Table 2 `Water Solubility versus pH at 12C [pH Cs [Sou2 biiy in1 gmi)[Std bevp .(gmr)e1]] C[w avi1 og|en1s7 04ou1 |sp2 a R57=5TTos8]] n= numberof toss 0Tlomer Research Program 000011 Table 3 Water Solubility Raw Data : Autogeneous pH 5.8, 12C Slope Intercept 238.61 6555.5] ho Sample | Area | Conc. (ppb) 1 [3712] 126 C52 3|s2s,ra8r6]|5 1i1s0 [54 [aa[ssiooar] 10s0 76 [o[3I7210] 0129 8 [stim ter 9 38,660 135 10 0 0 I[nP=eankuAmrbeearuosfeddeftoerrmqiuannattiitoantsion IUCL = Upper Confidence Level (ppb) LCL = Lower Confidence Level (ppb) | Teme Research Progam 000012 Ww Table 4 Water Solubility Raw Data : Autogeneous pH 5.8, 25C [Slope Intercept Set SetZ 29948 | Sample |Peak Height|Peak Height| Conc q 1 511 {opb) 595 185 25 47.0 5433 169 [95% UCL 164 [95% LCL 709) [Average 137 ppb ET 5 | 40 67 || s4o5r9 || 8 | 10 o | 203 | 10 : "a0 405. 74 2e8o2s Ca1r3s | 200 |e 180 | 64 544 182 [Peak Height usedfor quantitation "Peak too high to measure. Solid probably included in injection. In = number of determinations UCL = Upper Confidence Level (ppb) [LCL = Lower Confidence Level (ppb) 12Telomer Research Program 000013 Tabl5e Water Solubility Raw Data : Autogeneous pH, 37C Slope Intercept 10.0332] 642.42) EO -- Sample | Area Cone. (ppb) 1 4207 | 355 a32 JT4a6sa2e4s].| t3ae9s7ss TeTefsae|| ameor a meet wme 9 5870| 521 10 7366 670 Peak Area used for quaniiation In = number of determinations [UCL = Upper Confidence Level (ppb) LCL = Lower Confidence Level (ppb) I5Teomer Rosaarch Program 000014 Table 6 Water Solubility Raw Data : Autogeneous pH, 60C [Standard run before [_TSasmpelet|iA[reaS|eArreza|[C7one]. landafter each sample. [Sid Dev pIh [95% UCL les% LCL 51) 20932002 249) 201 [Average 225 ppb |1 |486500|366225| {2op9b)7 2 |289001|266224| 196 | 3 |atooes |273785| 219 | 4 [225266226886 175 | 65 [2[73535724253] |224603122717|| 232614 | "7 [206398190197| 171 _ 8 [180304|326568| 228 9 1301712 |343656| 288 10 | 285294|212058| 227 [Peak Area used for quantitation In = number of determinations UCL = Upper Confidence Level (ppb) LCL = Lower Confidence Level (ppb) 14Telomer Research Program " 000015 Table 7 Water Solubility vs. pH Raw Data at 12C Sao {a] esi aSslauctt wol s33 5ai a2hei : i io ---------- [Sa5 Te EoseoaFec oPHEomGoh wToGron) aSslauctt wl soSaoer ;:S Ha% So : * -- [ ateTHo T s oc5 e ce=o) 5 as uot EEhii :: i7 ACY oonn oonglS 1uised ------------] [Peak Area used for quantitation CIne=tenrumimnbaetrioonfs IUCL = Upper Confidence Level (ppb) LCL = Lower Confidence Level (ppb) 15Talmer Research Program 000016 is Appendix A 2-PerfluCchreomocitcyalleAtnhaalnyosli:sCSguFm1m7aCrHyzCH20H H-24691 Analysis Summary `The subject material was analyzed by gas chromatography using a standard method to assess its composition. This analysis showed that the `material comprised 99.2% of the subject material. The balance, 0.8%, was not another Telomer B alcohol, or Telomer B lodide at a limit of quantitation of w0.h0o2s%e. chFeurmtihcearlasntarluycstiusrebiys GCC7IFM1S5CsuFg=gCesHtCsHtOhaHt.the 0.8% is a single impurity, Finally, the subject material was evaluated by High Performance Liquid Chromatograpy - Tandem Mass Spectrometry (LC/MS/MS) for the presence of perfluorooctyl sulfonic acid and perfluorooctanoic acid at a detection limit of 0.1ppm. Neither material was observed to be present Based upon these analyses, we conclude that methods are in hand to determine and confirm the composition of H-24691 to be as follows: Material CgF 17CH2CH20H 2-Perfluorooctyl ethanol C7F15CF=CHCHZ0H WE. % (+03) 92 08 16Telomer Research Program 000017 Appendix B Solubility Determination Modified ASTM Procedure 1. A concentrated (~50% w/w) solutionof 8-2A in GC grade methanol was prepared. 2. Approximately 200uLwere placed into a standard screw-cap GC vial, 3. The open vial is placed in a warm location to evaporate the solvent. 4. After the methanol had evaporated, the 8-2 was observed to collect on the upper surfacesof the GC vial 5. The vial was then removed and allowed to cool to room temperature. 6. Ulirapure]8 MQ water was carefully added to the vial, filling it all the way to the top. (litle or no headspace). 7. The septum was tumed upside down so that the silicone rubber side was facing towards the solution. 8. The vials were then capped and placed in a temperature controlled shaker table operating at ~100 rpm. 9. The vials were shaken foar minimum of4 days prior to analysis. 10. The vials were then removed to the GC/MS auto-sampler tray, temperature controlled. 11. The GC/MS was calibrated against 8-2A samples prepared in methanol. 17Telomer Research Program 1" 000018