Document ganOpy3Zw7xw53DyKO5KgGNRN

WATER SOLUBILITY TEST SUBSTANCE Identity:N-methylperfluorooctanseulfonamidoethanolm;ay alsobe referredtoas N-MEFOSE Alcohol,FC-790, or FM-3925. (1Octanesulfonamide,N-methyl-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8heptadecafluoro-N-(2-hydroxyethyClA)S-,# 24448-09-7) 'Remarks: Materialisan off-whitew,axy solid.Sample was taken from 3M lotnumber 505. Purityinformatiownas not recorded. METHOD: Method followed: The Veith-Comstock technique,G. D. Veithand V. M. Comstock, J.Fish Res. Board Can.,32,1849 (1975) GLP: No Year study was performed: 1979 RESULTS: Value (mg/L) at18 + 1OC: 0.82 Remarks: Initivaalluesforsaturatedsolutionsresultinfgrom circulating the system for24 hours indicateda solubiliotfyapproximately2.3 mg/L. It was suspected thatthisnumber was inaccurateas itwas considerably higherthan thesolubilitoyfthe closelyrelatedmaterial,N-ETFOSE .alcoholS.ince it'ksnown thatwater-solubleimpuritieasnd some homologues are p@eferentialsloylubilizebdy thistechnique,the saturated water was replacedwithfreshwater and was allowed torecirculatfeor5 hours. Replicatesolubilivtayluesofthe recirculatesdolutionthen indicateda solubiliotfy0.82 ppm. CONCLUSIONS: The testsubstance isrelativeliynsolubleinwater. DATA QUALITY: ReliabilityK:limischranking= 3. Thisstudy does notmeet criterifaor qualitytesting.Thisstudy lackssufficienctharacterizatioonfthe test substance purity.The propertiesofthe testwater were notnoted. Additionallyt,hesecond circulatioonffreshwaterforonly5 hours without any sampling duringthattime periodorforextended times isinadequate to definitivecloyncludethatthe solubiliitsy0.82 ppm. Although solubility -apparentlyplateauedbetween 4 and 6 hours initialilnythefirs2t4 hour cycle,itdoesn'tfollowthatthe same effectwilloccur inthe absence of impuritieosr homologues. Additionalltyh,erewas no identificatioofnthe homologues orimpuritieisnthe sample. Theirpresence isassumed, thus they are onlypossiblyinterferinwgiththesolubilizatioofnN-methylFOSE alcohol.The extractioenfficiencwyithethylacetatewas not characterized.The analyticamlethod was not validated.Electroncapture detectorisnotanalytespecifitcothetargetanalyte(FM-3925),therefore peak used forquantitatiomnay not be targetanalyte. REFERENCES: This study was conducted by the3M Company, Environmental Laboratory,1979. OTHER Submifter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St.Paul,Minnesota,55133 Last changed: 5/17/00 3m" Fbrm ST47- 11-A TO: TECHNICAL TECHNICAL REPORT COMMUNICATMS CENTER - 201-2CN SUMMARY D sio 1/8/79 (Important- If reportisprintedon both sidpsofpaper,sondt"copiesto TCC.) Division Environmental. Project Laborato ry.i(EE, & PC) Premanufacturing mepcwt ultio Notice FC-790 Solubility of FM 3925 To Dept Number 0535 FroiectNumber 9970012600 Report Number 014 V. Pothapragada Author(s) Emp-Uov"Number(s) A. N. Welter//P.@@@-A,,.,iR.e@i:nz e r@,.,. Notebook Reference NB 462 -53; NB'--441PI-113,44-; NB 42669-41; ,@9 " NB 48277-8; See Environmental Lab Request 4197 09362/47816 No. of PfteslnciudinCgovershoot SECURITY10- t' Open 1:1Closed 3M CHEMICAL io, (CompanCyonfidentia(lS)peciAaulthorization) REGISTRY Now ChemicalsReported 0 Yes 0 No KEYWORDS: (Seletcetrmfsrom3M ThesaurSuusg.psotther applicablteerms.) CURRENT OBJECTIVE: To determine the water solubility of FM 3925 (Lot 505). EE & PC Div. (Environmental Lab) Fluorochemical REPORT ABSTRACT:(200-2w5o0rdsT)hiasbsvacitnformatiisdoinstribbuyttehdeTechnicCaolmmunicatiCoennstetro Solubility 3M'ertsoCorypmyR&D.ItisCompancyonfidonmtawterial. Studiesalert (Veith Technique) The solubility of FM 3925 was determined by a method in which water was recirculated from a reservoir through a column containing glass beads coated with FM-3925. Analysis of water samples showed that the FM 3925 concentration reached a plateau of \,2.3 mg/l at 4 to 6 tiours. Since water soluble impurities and more soluble chemical homologs are preferentially solubilized by this teefinique, the saturated water was replaced with fresh water. The second sequential circulation of water gave an FM 3925 solubility of 0.82 mg/l. This solubility value is considered more realistic. nforrnationLiaison :nitiikis.- -2- Introduction FM 3925, based on its structural similarity to FM 3422, may reasonably be expected to possess similar physicochemical characteristics. -The latter compound is minimally water soluble (0.05 ppm) and lipophilic. Techniques have been developed for determining the solubilities of so-called hydrophobic materials while at the same time providing saturated solutions for exposure to aquatic organisms. The data in this report reflects the results of studies; wherein, a modification of the Veith-Comstook technique has been used in determining the water solubility of FM 3925 (1). Methods The method and apparatus used in determining water solubility was modeled after that of Veith and Comstock (1). In brief, water in a reservoir is continuously saturated with the chemical by circulating the water through a bed of an iner't substrate impregnated with the chemical under investigation. Water solubility studies were carried out at 18+ 10 C. in a dark temperature-controlled chamber. 200 mg FM 3925 was dissolved in reagent-grade acetone. This solution was then added to 2 mm solid glass beads and allowed to evaporate off in room air. The coated glass beads were then packed into a glass column fitted on each end with rubber stoppers containing suitable glass-@to-tubing connectors (2). (Attachment 1, Environmental Laboratory Protocol.) One hundred (100) ml water samples were withdrawn at 1, 2,.4, 6, 8, and 24 hours after beginning the experiment. At 24 hours fresh water was added to the system and following 5 hours recirculation, replicate samples were withdrawn for analysis. All water flowed were retrograde: from bottom to top of column. Samples were analyzed using the following methodology: HewlettPgckard Model 5713 gas chromatograph with electron capture using 6 Ni as the source. Columns 61 x 1/81'O.D. SS, packed with 10% Carbowax 20M 0 on Chromosorb W-AW 60/80 mesh. 0 Temperatures -0 Detector 300 C., Injection temperature 200 C., Oven - 180 c Isothermal; flow: 40 cc/min. 95% Argon/5% Methane. Absolute lower detection limit - 0.5 nanograms. Results and Discussion Water solubilities of FM 3925 as a function of exposure time com prise TABLE 1. Chromatographic traces, 10 ppm std., 6, 8, and 24 hours, of these results are appended as Attachment 2. The replicated values are in good agreement,, -3- WATER SOLUBILITY TABLE 1 OF FM 3925 - VEITH TECHNIQUE Sample Time, Hrs. 1 2 4 6 8 24 ppm FM 3925 1.72, 1.90, 2.10, 2.33, 2.34, 2.17, 1.82 1.87 2.17 2.30 2.35 2.14 When fresh water was added to the system and allowed to recirculate for five hours, replicate solubility values of 0.82, 0.82 ppm were obtained (Attachment 3). The variability in solubilities obtained during the 24-hour run versus that obtained after the addition of fresh water may be'explained by the presence of trace impurities in the 24-hour run samples. It is known that when testing materials of,inherently low solubilities, it is possible that the trace impurities may be more soluble than the material under study. The recirculated water will then tend to solubilize the impurities, hence higher analytical values. Upon the addition of fresh water to the system and in the probable absence of trace impurities, a more realistic water solubility value of 0.82 ppm FM 3925 was recorded. all References: (1) Veith, G. D. and V. M. Comstock. Apparatus for Continuously Saturating Water with Hydrophobic Organic Chemicals. J. Fish Res. Board Can.-32:1849-1851, 1975. (2) Environmental"Laboratory Water Solubility Protocol. A ANW/EAR/cen Attachments: 1, 2, 3 Attacliment 1 AM 1/8/79 3M ENVIftONMENTAL LABORATORY PETOTOCOL FOR THE DETERMINATION OF WATER SOLUBILITY Discussion: A true solution may be defined as a "physically homogeneous mixture of two or more substances" (1). In a true solution (particle dia ter of less than 1 um), no heterogeneity can be detected and solutes cannot be separated from each other by mechanical means. In general, most organic compounds are not soluble in water and many tend to form colloids. In colloidal dispersions (particle diameters between 1 nm and lum),the particles may not be readily discernible, but they will scatter light (Tyndall effect) and can be separated by physical means. A saturated solution in water is defined as one in which no more solute will dissolve at a given temperkture, or the chemical potential of the undissolved solute equals the chemical potential of the dissolved solute. 'The principal method for determining the solubility of a chemical at saturation is to analyze the solution by some suitable physical or chemical method. No single method is available to cover the entire range of solubilities in water from relatively soluble organic chemicals to very insoluble chemicals. Therefore, several methods can be used to cover the range of solubilities. The method and apparatus chosen was modeled after that of Veith and Comstock (2). Briefly, water in a reservoir is continuously saturated with the chemical by circulating the water through a bed of an inert substrate impregnated with the chemical under investigation. Experiments are carried out in duplicate. For very hydrophobic chemicals which form colloids, concentration time studies are conducted to ensure that true saturated equilibrium solubility has been reached as evidenced by a plateau in such studies. The apparatus for these solubility determinations is housed in a temperature-controlled walk-ino environmental room whose constant temperature (usually 18 C)is kept below that of room temperature to prevent hydrophobic compounds from precipitating, congealing, or otherwise coming out of solution once it is transferred from this environmental room to the laboratory for further analyses. The possibility of such an event happening would be more likely if the room temperature is below that of the environmental chamber. 7 r pj Attachinent 2 REJECT T iD-P 4 Lj 5. E 4 91 f, E44 A EA '@PE h-R E Fi 41 T M, -I-E@4 ':^ TM 13@6 TM 65929- 123 1 5 7-,@ 4. 2 4 12. 64 Fi T0 P REJECT 1000 FiT N 1'718 t 5. 6 E,7i 4 .777 p M, m S 'LIP 'A.T T.'.4 2.8 TECT gf '04 RT e 2., 6 4, T Y P E. -@,TM m IT@ Hp C,L Y.. 2. S T 0 P:.,I'S.@ 'RT TN 48 '4' @r@1-6,4. 4() STOP: :RT 0 42 -4 99 '6. 40- T. TK, m TM "'RE R: 6 71:14-igi HP 3 80R DLY 2. mv./m . 5 ,TO P'@.I" :L2S 3 4,2 4 5:-.-4 F- Attachment 3 ER % F @i 4L 5 4 -4 P L C, F' R E i E C T 1000 t-vI rl T T N S T9!@bp69 F.'T 3. Ci2 4.2 T F'E T TM TM TM I.TM 3. 4;--0 2 4. 99 FtP E A 77--,--77 7 (-6 52 24 51 5 6 -@-9.,3 FIREA % 2m 2 9. 9 32. 64 2. 024 32. 94 2. 472 STOP jo .9T T N 126 FE -YE C T loo@ !r4 '37 Avt 180" i A. I -1 7 @i.L -.821 '3m0mm I F orrn 6747 11 -A . -; TECHNICAL TECHNICAL REPORT COMMUNICATIONS CENTER - 201-2CN SUMMARY (important- Ifreportisprintedon bodt sidesofpaper,SMndtoocopi*Sto TCC.) C)ivision Environmental Lab4,ratory (T.',&E PC) Project Report Title Pate of Fluorochemicals Analytical Methodology and Support To D. L. Author(si Arthur Not&Dook Hotwence Bacon Mendel 41947, 4419:1, 462(;93 47703, 48277, 49400 SECURITY lo 0 open (Company Confidential) I .. Closed (Special Authorization) 3M CHEMICAL RE09STRY KEYWORDS: I.Weet twns from 3M Thesnurus. Sugwt other .496boac,aut.I.- tits.) CURRENT OOJECTIVE: Progrt,::.,4 EE & PC-Div. L-'Iuorochemicals Dow 1/17/79 Dept. Nurnbw 0535 Project Numbw 9970612643 Report Nunrmr 008 ernpiov@ r4umber(s) 043939 No. of Pug" Ineludsng C overshoot 22 Now Chomwals Yes Reported KI No REPORT ABSTNACT:(200-2w5o0rdsTthis abstract information isdistributed by the Technical Communications akwi 3M'ers to Cisinpany R&D. It is Company confidential material. Center to ilk lnformatinn Liaison TI,C OF Biodegrada .it)n Studic-s on P-.:tdioteitve r-C-95. and FM 3422 (47703; 6-14, 21, 25-27, -35; 39-43, 46) Details of the bic)degradation studies on labeled FC-95, FC-143, FNI3422, and controls are described in E. A. Reiner's report (14). In the present woi,k, the nineteen samples each fi-om sludge, water, and ethyl acetate extracts generated from biodegradation studies were applied directly to plates (20x2O cm, E. Herclt GF 254 silica g(al). The plates were developed in ethyl acetate then examined first by ultraviolet light (long and short wavelength) and then by autoradiography. The plates were exposed to Kodak x-ray film for one week, and the film was then developed and examined. Comparison with control sampl(@s indicated no significant di.frerences. In a second part or this experiment, a portion of the ethyl acetate extract from the v;irious samples was methylated wi.th diazometh.-Ine to convert any nonvolatile components to GC volatile species. Both the unmethylated ind methylated samples were then analyzed by gas chromatography. No differences were noted between these and control samples. GC conditions are detailed in Notebook 47703-43. Determination of tiieSolubility of iZ-Methyl FOSE Alcohol FM 3925 -8; 4626 - - -1 4 About 20 g of FM 3925 Lot 505 was melted (steam bitth) to obtain a homogeneous sampl(,. The cooled, solid material, 200 mg, was dis- solved in about 20U ml of reagent grade acetone, and this solution was added to pre(tl(,,iii2c-mdm diamc,t:(--r,olid glass head.,@c,ontaine(i in a beaker. BeU(i.-WiL'L*Cpi*t--e.lt@asnutt--d.ecssivt!.wLiytli llci)Lane, chloroform, acetoil(@,water, methanol, and then a4@r dried. The FM 3925 coated gl;iss beads were placed in a glass coluwn (350xl8 mm) and supported by wool (preti-eated with Gla-;Lz-eat The end rubber -,toppers wt-i*(c?onnected to li(?v-],iiViR(@tul)iiigtiid L peristaltic pump was used to t-ircu.Latedeionizt!d water thrc)ugliLlic (;c)lumn. The entire setup was (-t)nductedin thg dark in t temperature-controlled wLLik-in environm@iilttl i-uuii(i18+1( Lt) Llic.-,,L:Li*oLl* Lhi:.-i experiment, water was pumped for 5 hours through the setup, and this water was di.-icarded. The purpose of this was to remove any impurities that wt)uld be as soluble as, or more soluble than, FM 3925. Fresh w:iler was ther.plteed into the system and at intervals (see Table 3), 100 ml (volumetric pipel) t)rwater was withdrawn from the main 2-liter storage chaml-er. Each or the 100 ml samples was quantitatively tr;tiisferredto '.tsl-liaratoryfunnel, and 10 ml of saturated aqueous sodium chlo;-ide was added followed by 15 ml or ethyl acetate. Tli(@mixture wt--;extracted and the separated organic pliase was quantit:tlively tran.,-@rerretdu a 10-ml volumetric flask. TtiL@aqueous phase wis reextra(-.Ledwith 4 ml of ethyl acetate, ,tnd the organic phase was added tc, thL@ 10-ml volumetric flask whose volume was finall.@-brought to the mark with ethyl acetate. An aliquot was used it)r gas chrc.)mLLtographyusing an electron clpture detector and a six-rt)ot (1-8 nictei'-,c)olumn of Carbowax CW20M run at 180-. The i-L,,.iulitrse rep(irted in Table 3. -21- Table 3 Su'lubility of FM 3925 in Water Time of Watc-r Circulation (hrs.) 1 2 4 6 8 24 FM 3925 (ppm) 1.72; 1.90; 2.10; 2.33; 2.34; 2.17; 1.82 1.87 2.17 2.30 2.35 2.14 Avg. (Hrs. 4-24) 2.3 ppm The solubility of I'M3925 is forty-six times that of FM 3422. Ttic r(!tention tiitw-()I'I-M3925 is (-.Iosct)o Lli:totl' I-M3122, tncl the gas chromatogi,,Lphicpattei-ns (see Figure 2 in reference 1) are essentially tlit@same. REFERENCES (1) "AnalyticaMl(,LhodoloognyFM 3422,1A1. kfendel'psrogress report to D. 1,.Bacon, dated 11/15/77, p. 8. (2)D. B. Easty an(.1B. A. Wabers, Analytical Letters, 10. 857 (1977). (3) Interofficce()i-i-(!sl)ofndCe,n.Ac.e Vraspirto D. L. Bacon, March 26, 197(i. entitled "Gas ChruiiiatographicAnalyses of FM 3422.11 Th(@ distribution coefficient is defined as the ratio of the i-,)ncL@ntratioonf t-ompt)tjnsdolubl(@ in n-octano I phase to the (-,)tieentratioonf ;tll-ipecies in the aqueous phase at a givi@iipll (usti,.Lll7y). (4) A. Otsuki and l@. Fuwa, Taltnt:i, 24, 584 (1977). (5) G. T. Wallace, Jr., I. S. 1,'IeLcher,and R. A. Duce, J. Environ. Sci. 11(@altliA,12 493 (1977). (6) G. D. Veitlaiii(Vi. M. CorrL,;tJo.ckF,isliR.es.Bc)ardC:xn., 321 1849 (1975). (7)It.F. Heineaiiiiit.R. Buz*furdC,. (I.Klaus,J. D. LaZerte, J. W. Sargent. (Unpubli.,itied) (8) A. Mendel rep(ii-ton FaLe or Fluurochemicals to D. L. Bacon, Nov. 15, 1977. (9) C. T. Cliiau, %'.11. Freed, D. W. Sclinieddingan(i It. L. KohneriL, EtivironniL,nta:l,t-iciieetnd Technology, Ll, 475 (1977).