Document bd1k74d6JzjkJ6nbggw25mm3

SOIL ADSORPTION TEST SUBSTANCE Identity: NN--eEtthyFlOpSeErfAllucoorhooolctoarneFMs-u3lf4o2n2a.mi(d1oe-tOhcatnaonle;sumlafoynaalmsiodeb,eNr-eeftehryrle-d to as 1.1,222,3,3.4.4,5,5,6,6,7.7,8,8 8-heptadecafluoro-N-(2-hydroxyethyl)-, CAS #1691-99-2) Remarks: Material is an off-white, waxy solid of uncharacterized purity. METHOD Method: dAedsscorripbteidonb-ydeDsaovripdtsioonn,st1u9d7ie6sadnedveHlaompaekderus,i1n9g7p5r.ocedures GLP (YIN): No Year (study performed): 1978 Statistical methods: Statistical analysis and plottingofthe data was done with the MINITAB package of the 3M TRAC computer service. Temperature: 16-19C during the 24-hours of wrist-action shaker exposure. Stock and test solution preparation: The stock solution was made by putting a few milligrams N-EtFOSE alcohol in D.1. water and stirring with a magnetic stirrer for several days.The supematant was poured into a graduated cylinder to settle fo4r days and then 50 ml portions were drawn off and centrifuged. The Rteestmasorlkustifoinesldw:ere mTahdeeBrbiylldsilauntdinyglaolaiqmuostoislowfatshecshtaorcakctseorliuzteiodna.s having 57% sand, 36% silt, 7% clay, 2.5% organic matter, 1.5% organic carbon, with pH 6.5 and cation exchange capacity of 15.3 meq.100 g. Standard solutions were prepared in deionized water at concentrations of 0.49 mg/L, 0.27 mg/L, and 0.16 mg/L. Forty-five ml of each solution was shaken with 5 gram samples of the soil in 50 ml glass centrifuge tubes for 24 hours in duplicate on a wrist shaker at room temperature (16-19C) Desorption extractions were performed with deionized water after the adsorption phase of the experiment. The samples from the adsorption and desorption experiments were centrifuged individually at 3000 rpm for 10 minutes, and 40 ml oGfC.eacThhesurpeemmaaintianngtssuolpuetmiaontawnetrewaesxtrdarcatiendedwiotfhf aenthdyl45acmeltaotfeDf.oIr. awnaatleyrsiwserbey put into the tubes. RESULTS K: Koc: 3269,21%47" 006196 Remarks field: The linear shapeofthe adsorption isotherm indicated that NEtFOSE alcohol adsorption on soil would be independentofconcentration in solution. * The study report had indicated a Kof 330. This is the coefficient of C in the regression equation, not the adsorption coefficient value. AKevalue was calculated using the formula: Ke. = 100 K/% organic carbon. However, the calculation used an organic carbon content of 2.2% while the report indicates the organic carbon to be 1.5%. This is a discrepancy. If the 1.5% value is used along with the corrected K value, the Ko. becomes 26,147. CONCLUSIONS The study substance is expected to exhibit low mobility in the kindofsoil tested. Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 DATA QUALITY Reliability: Kiimisch ranking 3. The purity of the test substance is unknown. Testing was not performed in duplicate. There was no analysisofthe soil to VBeoryidfy, aMmiochuingtarneSmtaaitneinUgn.ivAedrdsiittiyonaarlelys,ucmmoamrmieznetdsbmealdoew abnydPirnocfleusdseodrwSittehpthheen report. They also indicate the unreliable nature of this study. The batch method does not compensate for losses due to volatilization, sorption to the container, degradation, or other mechanisms. The concentrations used in the study were significantly above the solubility limit of the test substance, indicating there was crystalline N-EtFOSE alcohol in the stock solution. The number of data points and rangeoftest substance concentrations are too small to definitively determine soil sorption. Test parameters were not sufficient to establish the isotherm linearity. REFERENCES 3M Technical Report "Adsorption of FM-3422 on Soil." Stephen K. Welsh, Project 1978. 9970612631, Fate of Fluorochemicals, Report No. 009, September 1, PRreovfieeswsoorfSTtecehpnhiecnalA.ReBpooyrdt, SMuimchmiagrayn.StAadtseopUrnitvieornsiotfy,FMMa3y42192,o1n99S3oi.l. 006197 PIERret -------------- Last changed: 5/17/00 006198 Attached are comments on the 3M Technical Report "Adsorptionof FM-3422 on Soil. Stephen K. Welsh, Project 9970612631 FateofFluorochemicals, Report No. 9, Sept. 1, 1978" made by `Professor Stephen A. Boyd, Michigan State University, dated May 19, 1993. 006199 Review of Technical Report Summary `Adsorption of FM-3422 on Soil Tshainsdyrelpooarmt dseosilc.ribFesMa3b4a2t2chhsaosrpatiroenp/odretseodrpsotliuobniliistoytihnerwmateexrpeorfim0e.n0t5 fmogr/FLM(3042p2pbo).naTshiinsglies considerably and FC 143 lower than FC-95 are both anionic. or FC-143. It would be FM very 3422 is helpful a to non-ionic compound have accurate water whereas FC 95 solubilities and porcetdaincotli-nwgatKerapvaarltuiteisonuscionegffeimcpiiernitcsalforreltahteisoenschoimpspobuentdwse.enKT.h,ealnadtteKr,w,otuhlatd hbaevemboereenurseepfourlteidn in the literature. Water solubilities of solids are more difficult to use for predicting they should be converted first to the corresponding supercooled liquid solubilities." K.., because A favorable comparison of measured Kou 10 Key predicted from K., using published empirical relationships wthoautladnystrloesnsgt(hee.ng.m, ybycovnolfaitdielnizcaetiionn,thseosreptviaolnuetso. One problem the container, with the batch degradation) is method counted used is as soil sorption which results in higher apparent K values. Material and Methods The concentrations of FM 3422 prepared in distilled water are given as .49 mg/L, 0.27 mg/L ahnadvea0.1d6ismcgr/eLp.ancHyohweerveeorf ian ftahcetoarbsotfra1c0t7thEeitwhaetrerthseol0u.b0il5itmygi/sLrespoolrubtielditays i0s.w0r5omngg/oLr. thWeree was crystalline FM 3422 in the stock solution. The number of data points (three) and the range of concentrations are both too small. The range of concentrations evaluated should be at least abne oerxdteerndoefdmtaognaitsuodluet,ewciotnhceanttlreaatsitofnivtehaotraspixprioniatcihalescointcsewntartaetriosnosl.ubiAliltsyo;, tthhies iissotthheeromnlsyhowualyd 0 establish the linearity of the isotherm. Results and Discussion . The three concentrations tested, and the narrow range of concentrations isn't sufficient to establish isotherm linearity. `fTachte,ctohneclduastiaodnothnaottbiinnddiicnagteoefleFctMros3t4a2ti2c tiontseorialcitinovnosl.vesTheilsecmtreocshtaatniicsfmorwcoesulids naoltmojusstticfeiretda.inIlny give non-linear isotherms. mechanism based on strong High (e.g., sorption coefficients can electrostatic) molecular be obtained interaction. without invoking some My opinion is that FM 3422 partitions into soil organic matter in the same sense that it would partition into a bulk tohregasnoilcubsiloiltvyenitn pthheasseoilsuocrhgaansicocmtaatntoelr. phTahsee tmoagtnhietsuodluebiolfittyheinsowraptteiro,nacnoaelfofgiociuesnttoisanaorcattainoool-f water partition coefficient. The magnitude of the sorption coefficient is determined largely by thheencweattehre ssoorlpubtiilointycooeffftihceiensotliusteh.ighT.heDwDaTteirs solguoboilditeyxoafmFplMe o3f4a22coims paopupanrdenwtiltyh qluoiwtewaltoewr, solubility (5.5 ppb) resulting in a high sorption coefficient. Certainly DDT does not sorb by an electrostatic mechanism. `The partition mechanism does manifest linear isotherms. 006200 As far as an electrostatic interaction, this would require protonation of the nitrogen. It would be usefultoknow the pKaofthe compound; then the likelihood of electrostatic interactions with soil organic matter or soil clays could be evaluated. Again the K,, calculation uses an organic carbon content of 2.2%. The value given in the materials and methods is 1.5%, so there is a discrepancy here. The K,, calculation is appropriate for nonionic compounds that partition into soil organic matter. For compounds that sorb by electrostatic interactions, the K., value is not applicable. In that case the degree of sorption would probably be related more directly to the cation exchange capacity of the soil. The K., value does appear to be quite high, and if correct, would indicate low mobility. Recommendations 1. Getan accurate water solubility (S.) and Koy values for FM 3422. 2. Measure the pKa of FM 3422 if this is not known. 3. Measure additional soil sorption isotherms using a wider range of solute (FM 3422) c`yoonucrenitsroatthieornms twhheircehshsohuoludldbaep2prdoaatcahptohientwawtheerresolCub=ility, oofrt0h.e5cSo,m..pound. That is, in 006201 Fania TECHNICAL REPORT SUMMARY Os 1/T8 TO: TECHNICAL COMMUNICATIONS CENTER ~ 201.20 portant = eportis rineon both sodfpapser,sd to opis9 TCC.) QE ee Environmental Engineering Pollution Control mga Fate of Fluorochentcals ws Adsorption of FM-3422 on Soil ALN. Welter Tm e -- St2 ep-- hen K. Welsh 0535 a57f06t12631 009 75r 8 -- s #40673 8 secomtvh B00 oars) [opinion | "AEENSE Jreniss egored AevEanSs:na Cr BEET | TToomobtsaoiiln.an indication of F-3422 mobility in a sandy PC Div. Fluorochemical soit 5 "disotreptsion E REEPOeRa T ABSTC RACT:e (R20R0-250CwToreds)nThis abstract Sninfeormation eis disStera ributed|Tee SoC m ar To obtain an indication of mobility of FM-3422 in a sandy loam sDVaoasiv.li,dJsuodangd,esdor1pt9ot76iobnaen/ddiensmooforbpitlliieaonnbaakseeerx,dpeor1ni9m75eanntwseardessiomcroipnltdaiurocntteosdo.tshfoFsFiet-i5eo4nf2t2 3 oanfd3w30a;terlesssoluthbainlit5y% doefsoornpltyio0n.05wimtgh/lt.wo desorption extractions; E: [ere--sti 006202 ] IP concuustons ( The adsorption coefficient for Fi 3422 was 330. Considering the adsorption coefficient, desorption characteristics, and water solubility, FM 3422 would be judged immobile in the sandy loam soil used in this study. INTRODUCTION As a part of the Fate of Fluorochenicals Project, an indication Of mobility of FM 3422 in sandy loam soil was desired. Adsorption- desorption experiments (after Davidson, 1976 and Hamaker, 1975) along with water solubility data can provide this indication of mobility. This approach is used by the U.S.E.P.A. in pesticide registration requirements. MATERIALS AND METHODS ~ . Duplicate 5-g samples of air-dried Brill sandy loam soil (57% and, 36% salt, 7% clay, 2.5% organic matter, 1.5% organic carbon, with pi 6.5 and C.E.C. of 15.3 meg/100g) were shaken with 45 ml of solution in 50 ml glass centrifuge tubes for 24 hours on a wrist action shaker at room temp. (16-19C). Glass tubes were used because they ere found in separate experiments to adsorb less FN-3422 than polypropylene or polyethylene tubes. Solutions were made by diluting a stock solution of the chemical. . ` The stock solution was made by putting a few milligrans FM 3422 in D.T. ; water on 1/25/78 and stirring with magnetic stirrer for several days. (06203 On 2/6/78 the supernatant was poured into a graduated cylinder to settle until 2/10/78 when SO ml portions were drawn off and centrifuged in ( glass tubes at 3000 rpm for 10 min. The centrifuged solution was put in a glass jar for storage. Concentrations of FM 3422 wow 0.27 mg/1., and 0.16 mg/1 (100%, S63, 32% Of stock). After shaking the initial solutions as well as the two desorption extractions with deionized water, the samples were centrifuged at 3000 rpm for 10 min. and 40 ml of each supernatant solution were extracted with ethyl accetate (See APPENDIX I for procedure) for analysis by GC. After removing the 40 ml for extraction, the remaining supernatant 1iquid was drained off and 45 ml of D.I. water were put into the tubes. Statistical analysis and plotting of the data was done with the MINITAB package of the SM TRAC computer service. { RESULTS AND DISCUSSION Adsorption data for FM 3422 are given in TABLE I. The amount of to FM 3422 removed from solution by the soil (Column C) was 98% at all " three starting (initial) concentrations. Equilibrium concentrations in solution(C) in mg/l. are shown in Column 8 and amounts adsorbed on the soil(x/m) in pg FM 3422 per gram soil are shown in Colunn F. The regression equation of the adsorption isothern shown in FIGURE 1 was x/m = 0.33 + 330C, so that the adsorption coefficient, K, was 330. The linear shape of the adsorption isothern indicated that FM 3422 adsorption on soil would be independent of concentration in solution. The high percentage adsorbed and the relatively high adsorption i coefficient indicated that FM 3422 would be imobile in this sandy loam soil. 006204 an ' TABLE I Fi-3422 Adsorption Data IniciatAP3422 Cone. mg/l. 00..4297 ((5160%0)%) 0.16 G29) Do rarer I A x 0.045altieterrs 0.02 S0.00007 Eat: .BConc. ) mg/l. 0.0120 pote ++ 2 ou 0.00 0.0032 = 0.000 Sotal oartEEFai-u3i42ln2.,Tnm8 (BBx000.0..0004400550025l84Tiitteerrs) . :0.00014 4 Rtemncoeved oo fl =98 onF-S53o4t2s2 FAxdisaorbedile D-EA +13; 00/5 A 1.41 ;! 4.0 a _-- Ep -- 3 Na/ m = 0.33 + 330 67 >. di rd R-Squared = 0.999 - Zg 3 at| y --88 --a . i ih. 5 1.6 0s ois 0.00 ao.om oz o.ois Bui librium Concentration, C, ng/L ` G2$uO1tL2,iddatLainTefoowreixsthiagdFnhsMieocsr3itp4at2li2ionniAcdisiaoslropchtceioronsncF,eInaGtbnUrrdRaoEtkDiee1onsno,rlpitn81ei3sonafroIersodmtiehasedortrmhpstibomrnciisssothheermmmse.re0ri0Ae'6iso2n,05 furchest FIGHE 3 shawncoSonceinndtrcaattieo.n.SharSctahnidsaravaldoervimtaiyonn:efcorreesrheeatmniyi. cement "5. Desorption data are given in TABLE II and the desorption isotherms are shown in FIGURE 1. OF the anounts initially adsorbed on the soil, less than S% was removed by the two desorption extractions with water (TABLE 11, Column G). This small acount of desorption is also shown by the almost horizontal slopes of the desorption isotherns. This very small amount of desorption was another indication of the immobility of FM 3422. TABLE 11 FM 3422 DESORPTION ISOTHERM DATA A EqSuoillu.tioCno,nc.C, in ` mg/l. ' 0.0120 + 0.002 00..00003623 3 00..0000505 B EFqiurislt. DCeosnocr.ptiionn mg/1. 00..000144 + 00..000014 0.002 0 c SEeqcuoinld. DCeosnocr.ptiionn ng/1 00..000022 3+ 00 0.002% 0 Amount 0Adsorbed Amount&on Soil AmountFon Soil PercentcDesorbed . 5 on Soil, x/m ug/g After First Desorption, ug/g DesAofrtpetrioSne,conpdg/g -5 F) ! 24..337032 1.411 24..313776 1.393 24.135189 | 32.333 1.375 26 The large amount adsorbed and the small amount desorbed suggests strong binding of FM 3422 to soil particles by intermolecular interactions involving electrostatic forces. { 006206 : The adsorption coefficient based on soil organic carbon, K _, for ` FM 3422 would be 15,000 (100 K/% organic carbon = 100x330/2.2). Compared with Koc values for a selected group of pesticides and other fluorochenicals (Table 111), 15,000 is quite high and is another indication of low mobility of FM 3422. : TABLE TTL CofmopraraisSoenlecotfedAdGsroorupptioonf CPoeesftfiicciideensts (Hamaker and Thompson, 1972) Chemical Xo (mobile) Ch(iFoCr-1a4n3be~n = == 2o 1D1)2.8 2,J4-0I)32 BPrroompahcainl 7s1 : MSiomnauzrionne 13853 PDircohplaozbienneil 116542 AChtlroarzoipnreophan 127025 "x v APnreotnertyonne 330800 3> DPrioumreotnryne 1581s3 C(hFiMo-r3o4x2u2ron 154,,090806) 3 (immobile) PaDrOaTquat 24230,,000000 These adsorption and desorption data along with the low water solubility of FM 3422 (0.05 mg/1.) provide good evidence that FM-3422 would have very low mobility in the sandy loam soil used in this study. 006207 ; Terns C - Concentration of chemical in solution at equilibriun Xin - Concentration of `chemical adsorbed on soil at equilibriva &? - Coefficient of determination K ~ Adsorption coefficient X,, - Adsorption coefficient based on soil organic carbon content References Davidson, J. M., et. al., 1975, Use of Soil Parameters for Describing Pesticide Movement Through Soils, U. S. EPA, EPA-660/2-75-009. DavidisnonS,oiJl.s,M.,Pre1s97e6n,ted"VeatrtiScyamlpoMsoivuemmeonntNeamnbdioDliosgtirciablutiTornansopfoOrtrgaannidcs GTOFanSaatfaonrdiaaartdt is.onhof ePol urtasrte#0bo.n uLWoanydru1n1d-g13W,a,te1r9s76.+i Natioral Berea # HamakCehrea,icJa.ls,W., Hu1m9a75n, HeManlttehrparnedtatthieonEnvoifroSnomielntL,eacAhiCnoglleEcxtpieornicoafentDso,w"Sciinenti- Fie Papers; Voi. 1, Dow Chemical USA, Midland, Wich. 48630 HamakWteanrr,ctehlJe. sDoeW.iktkearnE,dnviJT.znoenM,m.enTNt.h.omYp.sCo.n,A. 191.72.Gori"nAgdsoarngptiJ.on"W. iHnaOmrsgtaenri(cadChse3msicals ~~ . * 3. i 006208 . APPENDIX I , FM-3422 Analytical Procedure Reference: N.B. #46269-50 - Results obtained from this method. 2Th/e2/7480 wmelreH",0asnaamlpylzeesd tihnatthweerfeolsluobwminigttemadnnbeyr.S. K. Welsh on wTihteh40temfllonH',s0tospacmopclke. was10pmllaceodf sinatuara1t2e5dmlNaCslep.H,0fuwnanesl,addfeidtted bsyep.pipfeutn.nel.7 mlTheoffeutnhnyell waacsetaitnev*ertaeddded50bytimpeispetaZndtotsheampplheasein tarlalnoswfeedrtopipseetparaantde.placTehde itnopaEdtrAyc p1h0amsle vwaoslumdertarwincoffflawsikt.h Naote: Oifn Ht,h0e. 7 AmllsoE,tAcifadedmeudl,sio3nmlisisa prercoobvleermedtheduefoatmoy10l%ayeErtAcofsEotlAucbility wraptme?forcan10bmeinp.lacteodbrienaka eglmauslssiocno.ntrTihfeugeEtAtcubeisatndhensputnranatsfe5r0r00ed . atondthtehirvdolutmimeet,ricasflaabsokv.e, uThseingex3trmalctiEotAnc iseaccharrtiimeed. outAlla EsteAccond teoxtrtahcetslinceomwbiintehdEtiAnc.10 ml volumetric flask which is then diluted w5imtihcrtohelitfeorlloiwnijnegcticoonnsditoifontsh.e saSmtpalnedsardwerFeM-m3a4d2e2 siontloutiEo.nCs.G.iCn. p EtAc are injected for comparison. Inst: Heelwelcetrtotn-PaccakpatrudreModdeetlectSo7r1.3 equip: ped with Ni 63 Column: C6'hroxmg1s/o8"rb0.WD-.AWS.S. 10% CH-20M on 60/80 Mesh Oven Temp - 180C Isgthermal : . DIentj.. TPeomrpt. Te-mp300-2C00C 3 Flow 40 C.C./min - Argon: Methane 95:5 *Analytical Reagent - Mallinckrodt (R) - Ethyl Acetate G. A. Vraspir : 006209