Document aBrpQ2RR5aGkydYJyy2BQwNe9

MAatyta4,ch20m0e0:tnotEnLevtitreorntmoenCt.aAluSetruDdaietsedon Perfluorooctanesulfonates (Post-1875) IPhysicalichemical Properties Laboratoroyr Completion zy | CFeronaneohrWak Porting Farge ofPOS,Bois -- Wnior TSaine 2 [R[orSGuagoe etrheeatVapoorPrerssuroeso PFO Uiporing tayWid [FFOS. Deteromf incaatriootna PaionCaras iis---- 77% 3 [bSyatphemS acth anFala tasskk mMeate nhoadn-aANon-GSLPeFeaspibiliaty Studyir nSe International, Lig. etait Sos i Tesi Resa: Ar-Wate Parton Cogn hor POS naSmWaS1g, U Sha[vOeCsTTTorfraeoWanl Sousa ofPFOS oh Shak Fisk wViTo nemaionl i. | [Soa WE Tosser 86Fa r oe 7 ve FE Sy oan TOG A ar WE Sram] BAF] TEinevironmental Fate and Transport Laborstoryor Campion Type Ps[uamamesasruysmsoSaTaetFG:oif0SP5eo3ut3runrFcCyooo4cf5ahGennSsSsouiAtdtossonrceps.tio7hn23sS5tW0oyEroeoToS Envori63o7ur -- e Trel s a "| [sFCSEmPRntLeobdsiSduiemcsmhStiaoundrinyUaeysPsaSsurmsmaeSomdfaShantoreayiSoey UowngSSE ToT -- Flat [BopcaerstrausaartsooncSnueesssisoofanFysrocab+ons G12) per amd SWTERw 38 BTEFare Sree 73 + [B[[iooBdtOegDrvaOdnatT ioenpSotrute dsoiressFoEsfRrFEluore(ocwairbn3ooanrTseP-aKrvilee(7yn/ss18/o78)grrepyort i Fas Rea SE ners TSauemmr. C2Foers eee [rs[aaeirioasnnasr)SncewoecsmnSaeueeotnneC cdoamsdeDono Maana Thaeescts her ouer Nodwe Memtmmer es or rode BRT WE Sm 000172 ENVIRONMENTAL FATE AND TRANSPORT sTohiilsadsescotripotniopnressteundtisesi.nDfeorgmraatdiaotnioanndsttuedsitesreisnucltlsudferhoymdraobliyostiics,, and biotic degradation photolysis, and and biodegradation. Much of this work is in progress with final reports scheduled for the June to August, 2000 timeframe. As these studies progress, there are certain key findings that can be presented as preliminary results: 1. There has been no indication that perfluorooctanesulfonate undergoes any degradation from hydrolysis, photolysis, or biodegradation mechanisms. d2.etIenctaleldhaysdraoldyesgirsadaantdiopnhoptroolydsuicstsitnudaineys,cpoenrcflluusoirvoeoecxtpaenreismuelnfto.naTtheihsapsrneoltimbieneanry ffilnudoirnogchceamlliscailnstotqoupeesrtfilounortohcetaansessuumlpftoinoanteo.f expected degradation of other S3.trIuncttuhreesotfudtihees sfpoeccuisfiecd ionnduhsytdrrioallyasinsd ocfofnlsuuomreorchpermoidcuacltsp,olitymhearssbteheantdfeotremrmtihneed that these following materials are relatively half-lives are estimated stable in the environment. for various polymers: For example, the POLYMER HALF-LIFE Acrylate and ester 1-5 years Polyethylene glycol based 3-50 years Urethane >500 years For hydrolysis to occur, polymers must be subjected to an aqueous environment, `which is not expected to occur in a municipal or industrial landfill w4.ilRleplhaottiovleytzoepthootcoalrybsoisx,yltahteecsutrrruecntturdeast.aThsuegsgeessttsruacthuyrpeosthheasvies mthuacththdeisfefemraetnterials properties then sulfonates in that they are much less bioaccumulative in ecological species. Additional discussion of these results and ongoing studies will be presented in subsequent submissions and reports. 000173 EFT) SOIL ADSORPTION : TEST SUBSTANCE Identity: Perfluorooctanesulfonate; may also be referred to as PFOS or FC-95. (1-Octanesulfonic acid, 1,1,22,33.4,4,6,5,6.6,7.7.8.8,8heptadecafiuoro-, potassium salt, CAS # 2795-39-3) Remarks field: The test substance is a white powder of upnecrhcaurrarcetnetrpirzoedcepduurirteys. aTnhdisbetessttianvgaiilsabbeleinpgrarcetpiceeast.ed METHOD Method: ~~ Adsorption-Desorption study using the approach GLP (YIN): rNeocommended by the U.S. EPA for pesticide registration Year (study performed): 1978 Statistical methods: Statistical analysis and plotting of the data was done with the MINITAB package of the 3M TRAC computer service. Temperature: ~~ 16-19C Stock and test solution preparation: Test solutions were made by diluting a stock solutionof "C-labeled Perfluorooctanesulfonate. The type of solvent used to make the stock solution is not noted, nor is the activity ofthe radio-labeled test substance. Remarks field: The Brill sandy loam soil was characterized as having w5i7th%psHan6d.,53a6n%d csialtt,io7n%exclcahya,n2g.e5c%aopragcaitnyicofma1t5t.e3r,me1q..5/%10or0gganmisc.carbon, Standard solutions of the 14C-labeled compound were prepared in D.1. `waterat concentrations of 262 mg/L, 158 mg/L, 90 g/L, 51 mg/L, and 28 mg/L. Twenty-five miofeach solution was shaken with duplicate 5 gram samplesofthe sail in a 50 ml polypropylene centrifuge tubes for 24 hours on a wrist shaker at room temperature (16-19C). Desorption extraction were performed with D.1. water after the adsorption phaseofthe experiment. The samples from the adsorption and dmeisnourtpetsi,oanfteexrpwehriicmhe,ntthsrweeeraelicqeunottrsioffugeeadcihndsiuvpieduranlaltyaantt5s0o0lu0tiropnmweforre10 prepared for scintilation counting. From the raw counting data, compound concentrations were calculated for al of the supematant solutions. RESULTS 00174 Ki 099 (N=1) Koc: 66 Remarks field: The linear shapeofthe adsorption isotherms indicated that perfiuorooctanesulfonate adsorption on soil would be independent of concentration. + The study report had calculated a soil / organic carbon partitioning coefficient of 45. After review, it was determined that the value should have been 66 based on the formula (Kee = K' x 100/1.5(% organic carbon); K'= (m)/Co). CONCLUSIONS The study substance is expected to exhibit high mobility in the kind of soil tested and would move with the groundwater. Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 DATA QUALITY Reliability: Kiimisch ranking 2. This study lacks detail on the stock solution and the purityofthe radio-labeled test substance. Additionally, `some calculations have questionable reliabilty. REFERENCES 3M Technical Report "Adsorption of FC 95 and FC 143 on Soil." SK. Welsh, Project 9970612633 Fate of Fluorochemicals, Report No. 1, Feb. 27,1978 OTHER " Last changed: 5/2/00 000175 SUMMARY OF THE SOIL ADSORPTION STUDY OF THE POTASSIUM SALT OF PERFLUOROOCTANESULFONIC ACID . . Soil adsorption-desorption studies were conducted to indicate the mobility of potassium perfluorooctanesulfonate in a sandy loam soil. The approach used was that recommended by the U.S. Environmental Protection Agency for pesticide registration. The Brill sandy loam soil was characterized as 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./100gms. Standard solutionsofthe "C-labeled compound were `preparedin D.Iwateratconcentrationsof 282 mg/l, 158 mg/l, 90 mg/l, 51 mg/l, and 28 mg/l. Twenty-five mlofeach solution was shaken with duplicate 5 gram samples of the soil in a S0'ml polypropylene centrifuge tubes for 24 hours on awrist sheker at room temperature (16-19 C). ' Desorption extractions were performed with D.L. water aftr the adsorption phase ofthe experiment. The samples from the adsorption and desorption experiments were centrifuged individually at 5000 rpm for 10 minutes, after which, three aliquots of each supematant solution were prepared for scintillation counting. From the raw counting dats,compound concentrations were calculated for all ofthe supematant solutions. R _-- The linear shape ofthe adsorption isotherms ifificated that potassium perfluorooctanesulfonate adsorption on soil would be independent of concentration. A soil adsorption coefficient (K) of 0.99 indicated that this compound would be mobile in this kindofsoil and would move with the groundwater. A soil organic carbon partitioningcoefficient(K..) was calculated in this report to be 45. However, afer closer examination the K. value should be 66 (K,, = 100 * K / (1.5% organic carbon). Again, this value indicates high mobility in this kindofsoil. 000176 July 2, 1998 MICHIGAN STATE UNIVERSITY eTevvLeoea,m yay 15, 1993 roe aston 25c. cCtoomompatbneye.suaso, w2t-38-00 Hora sili eae De. Bowe ET SeaectnoinstsEITaie roemasy rFeoviTewaN TpovcoorFmtonorT .testtelreuagaahlrcicdaishn,yrg otf"ehFevlcieshasieneneeeInoredeMniv.viiTebawucnhttnhticsslbuaIddntfeRorarspioerstcnisdo,n AEdRoEEEhtahevotevceedesnoemmrmeeasnntisattdtiahoFensasttbeaaTtiosesroictciftobigoeyeotvsirpoTeonesesroaetfracrshTcoohuaperopePofesipseorln.potdssu0cvbeen3sHochioenusLdisnsssionarfcdouarnnmscaetion Jly acoLnyEsuicaSinsgEffaontEfFooxnecsheoewforakeeieirafto]araeSaadd.copOedsaecseIatiiaoRn3,o2f00r.o0p0eck(schephwossanosde JPAR Sincerely, J4 S FroetaesoAr. Boyd, Ph.] MSUisanAffmationActionsOportmityntiuion 00177 ReviewofTechnical Report Summary `AdsorptionofFC 95 and FC 143 in Sail Material and Methods Should give recoveriesofcompoundins blank (no-s0i) experiments. States that polypropylene: 501s less than glass on polyethylene, but doesn't givae numerical value. `The large headspace (25 ml in a 50 tube) is undesirable; any lossesofthe "C-label, e.g., from volatilization or sticking to the tube, will inflate the sorption coefficient since the method c`caolnccuelnattreastitohnes.amAolusnottsheor2b4edhobuyrdmiiffxeirnegncpeerbieotdweseenemtshearibniittriaarly.andWefrinealexeqpueirliimbernitusm dsoonleutifoonr different periods of time 10 establish that equilibrium was reached within 24 hours? Detailsonthestocksolutionarelacking. Whatsolventwasusedandwhatisthespecific activity and radiochemical puriyofthe "C-FC 95. `sToihle aisdewaeollf uassiwnagtaerc.ottTohnesw~a2ba0f%terofthleessdrdaeicnrienagsestineispsoluuntuesucaoln.cenHtorpaetfiuolnldyuie s igor" wowvte ashighas I'dlike osee it. A SO%orgreater decrease wobueblettder = This section generally lacks detail that would normally be required for \ NE Results and Dicscuussssion wep `The linearity of the isotherm has been shown over the concentration range us 2 cdoenmcoennsttrraattieontshatthattheapepnrtoiraechistohtehewramteirs sloilnuebai,littyhoefltihneearciotympmouusntde.xtDenodytooueqkunio a of FC95 or FC143: If not, how were the initial solution concentrations selected `The sorption coefficient (K)ofFC 95 appears to be about 1 as indicated. The organic matter normalizedsorptioncoefficient(Ka, = K/f,2isKoy = 110.025 = 40,orloKge, = 1.6. This isasoil sorption coefficient intermediate betweenbenzeneand toluene. It would 10 examine some additional soils to confirm this Kos value. Generally, the Ko convergewithin afactorof 2to 3 fordifferentsoils. This would increase my coi accuracy of the one measured value. I've spot checked the soil concentrations of FC-95 for both the sorption a ~~ experiments and 1 get essentially the same values. The calculations look good. The K values for FC 143 is lower than FC 95 indicating that it probably has a solubility. The hystersi inthedesorption isoitsshurperirsinmg, and has been ovt `The sorption isotherm is linear indicatinga single sorptive process. The conclusion regaraing c"othnrveeersdeifafterleontwebrincdoinncgenmtercathiaonniss"miss .v.e.rwyitshpescturloantgievre bbiansdeidngonatthhiegshienrglceonecxepnetrriamteinotn.s aInfdotnhee examinescolumn I "AmountDesorbed2s a PerocfAemonuntt Adsorbed" the values range from 000178 26 10.212 percent,so t's pretty inconclusive. There is afairlygood discussionofhysteresis in J. Environ. Qual. 12:325-330 by Koskinen and Cheng who observed this phenomena for the `weak acid pesticide 2,4,5-T. The causes of hysteresis are varied and complicated and may ainncdl/uodrecmhiecmriocbailalprdoepgerratdiaetsioofn tohfe tshoeilc-osomlpuotiuonndsydsutreimn.g dFeosrorepxtiaomnp,lea,nddecshoarnpgteiosniunstihneg pdhiystsiilclaeld cwoautledr n(oatsbiestohbeaciansede. hTehrei)sccaounldcaruesseulqtueinncshoiinlgdoisfpreardsiiooanctsiovittyhaitn asoclluetaironsaupnedrnoatthaenrtprsoolbulteimosn leading to error. _ `The "material balance" as presented in the report is a little misleading. To obtain a material balance you should measure the amountof "C-activity insoilat the end oftheexperiment, and add it to the measured solution concentrations. General Comments. The K,, values calculated here use an organic carbon content of 2.2% `whereas the value stated in the Materials and Methods is 1.5%? `TTahteerwavtaelruesoilsubwirliotniges. arIef ctihteedsoalsub3il0i0timesg/arLeftorrlFyCth9a5t adinfdfe>rent2,0gt/heLnfotrheFsCor1p4t3i.ve Spurropeelrytitehse should be vastly different, which they are not. If FC143 has a solubility of >20,000 mg/L, then Iwould expect no sorption. This value must be erroneous. Recommendations: 1 Obtaining K, Ke, values on additional soils. Determine if K, is relatively constant. 2. Obtain a true mass balance by measuring "C-activity in soil and solution phase. 3. Interpret desorption datamorecautiously. 4 Get correct value of water solubility of FC 143. 000179 : Hi AoE i. ` Forher1 IA TECHNICAL REPORT SUMMARY 2/27/78 ee 5 70: TECHNICAL COMMUNICATIONS CENTER -- 201-208 (Inport. port seinndonbthios ofpp, ndtwo coprso 705) Co R Faattee of Fluorochea-hemicals leew| | _ _~ | GQ Fif m &! ge ta , ory |i | TFeoe gaoc. wmmeerCe | secpten kein SEW de aii Adsorption of FC 95 and FC 143 on soil -- hou D. L. Bacon 1| (1) (9a") peii ove. Sa [5 Ging a : savs73, 47708 | PE rm sol14l ny BO cova si rereier |REED - | Eoewonrnoseaiomsa.w CunENT GRECTIVE: > To obtain an indication of FC 95'and FC 143 mobility in sandy loam soil. BE & PC - Div. DFIUOROChemical Soil Adsorption Nobility [merA on ATTCRAnCTn. (R0a2:50 ard Toeoat orator nna TeeCommnionsGrr As a part of the Fate of Fluorochemicals Project, an indication of mobility of FC 95 and FC 143 in sandy loam soil was desired. Adsorption-desorption experiments (after Davidson, 1976, and Hamaker, 1975) along with water solubility data can provide such information. The adsorption coeffi@nts for FC 95 and.FC 143 were deternined to be 0.99 and 0.38, respectively. For FC 95 adsorption and desorption could be described by a single valued function while for FC 143, they could not. Based on these data, both compounds would be judged mobile in the sandy loam soil used in this study. RE tomae SE) . 00180 PERLE 2 TEE a D CONCLUSIONS ' Adsorption coefficient for FC 95 and FC 143 were 0.99 and 0.38, respectively. For FC 95, adsorption and desorption could be described by a single valued function while for FC 143, they could not, Considering adsorption coefficients, desorption characteristics and water solubilities, both compounds would be judged mobile in the sandy loam soil used in this study. : INTRODUCTION + As a part of the Fate of Fluorochemicals Project, an indication of mobility of FC 95 and FC 143 in sandy loam soil was desired. Adsorptiondesorption experinents (after Davidson, 1976, and Hamaker, 1975) along with water solubility data can provide this indication of mobility. This approach yi usd by the Uo So EPA dn pesticide segistration requirements. - MATERIALS AND METHODS Duplicate S-g samples of air-dried Brill sandy loam soil (57% sand, 36% silt, 7% clay, 2.5% organic matter, 1.5% organic carbon, with pH 6.5 and C.E.C. of 15.3 meq./100g) were shaken with 25 ml of solution in 50 ml. poly- propylene centrifuge fubes for 24 hours on a wrist action shaker at room temp. (16-19C). Polypropylene tubes were used because they were found in separate experiments (3M Tech Notebook #470673, C. H. Schrandt) to absorb less FC 95 and FC 143 than glass or polyethylene tubes. Solutions were made by diluting a stock solution of each chemical. Concentrations of C-labeled FC 95 were 282 mg/1., 158 mg/1., 90 mg/1., $1 mg/1., 28 mg/1., (100%, 56%, 32%, 18%, 10%, 1% of stock). Concentrations J of Mc.1abeled FC 145 were 523 ng/1., 293 mg/1., 167 ng/1., 94 mg/1., 52 mg/1., and 5.2 mg/1. . 000181 TR : d After shaking the initial solutions as well as the three desorption extractions with deionized water, the samples Were centrifuged at 5000 rpm for 10 min, and three aliquots of each supernatant solution vere taken for scintillation comting. After the adsorption step, 22.5 ml of solution were recovered, Therefore, it was assumed that 2.5 ml of liquid remained with the soil in each step and this amount was accounted for in the desorption calculations (see Results and Discussion section). In the FC 95 experiment, the supernatant liquid was simply drained : Off at each step and the next 25 nl of 1iquid were put into the tubes. In the FC 143 experiment, the supernatant liquid remaining after the draining step was sbsorbed with a cotton swab before putting the next ) 25 n of liquid into the tubes. The procedures for the FC 95 and FC 143 experiments were recorded in 34 Technical Notebook #40673, p. 49 and p. S51, respectively. From the raw counting data, disintegrations per minute (DPM) and FC 95 and FC 143 concentrations were calculated for all of the supernatant solutions. Statistical analysis and plotting of the data was done with the MINITAB package of the SM TRAC computer service. RESULTS AND DISCUSSION FC 95 Adsorption data for FC 95 are presented in TABLE I and FIGURE 1. Comparing the regression equation of the adsorption isothern (FIGURE 1) ) x/B = -0,20 + 0.99C with the Freundlich equation x/m = Kc'/N, it could ve seen that the adsorption coefficient, K, equaled 0.99 and the exponent, N, equaled one. The linear shape of the adsorption isotherms (N=1) indicated 00018x% KEELE ` I that FC 95 adsorption on soil would be independent of concentration. The low adsorption coefficient (K=0.99) indicated that FC 95 would be mobile, i.e., it vould move readily with the ground water through this sandy loam soil. TABLE 1 FC 95 ADSORPTION DATA A B c Initial Fe 95 Equi. Conc. * Beaoued . Cone,. mg/l C, mg/l. (AF To 218528..20 90.0 28$1..00 ) 2.8 213303..29 1157..11 7462..90 1174..86 22..10 2271.0 o Total FC 95 (IAnxIn0i.t0i2a5l lSiotelr'sn) 7.0500 23..29550000 10..27705000 0.0700 E SoTlo'tnalatFCEqu9i5l.i,n mg _(B x 0.025 liters) 35..3845755000 11..9025205000 00..5055205000 F onFCSo9i5l,Adxs/onr,bedug/g (--8) x 10 vy/eg 12490..08 4655..73 293..58 : Desorption data for FC 95 are shown in TABLE II and FIGURE 2. For comparison, desorption isotherns for the pesticide fluoneturon are given in FIGURE 3. For clarity FC 95 desorption isotherns are not drawn in FIGURE 2. However, all of the data points lie very close to the adsorption isotherms ) indicating that adsorption and desorption could be described by a single-valued function with desorption coefficients, K', equaling the adsorption coefficient, * 00183 Ed SpE 3 Y 240 3g 180 Rr & 120 Lo 3 b i 60 0 o A : A , A Regression Eqn.: R-Squared = Y = -0,29 0,985 + 0,99 X A = Actual Data Points B = Predicted Y Values @ 120 180 210 300 Equil, Cenc., C, mg/l FIGURE 1 FC 95 Adsorption Isotherm - This, along with the observation that approximately all of the adsorbed FC 95 was subsequently desorbed (TABLE II, Column H) indicated that of FG 55. binding forces were weak and would be another indication of high mobility Material balance data for FC 95 are presented in TABLE III and these data indicate experiment, that all of the chemical was accounted for throughout the * 000184 D TABLE 11 ' ShPoei, T253i5ok.ri930000 a RT 2.000 FC s95 DESORPTION ISOTHERM cDATA* Fives LBeeosoepeion sF2Lr.a7o000 2aS000 secondoDoesorpiion 1x o03F.-a350d0000 0.6000 0.2000 e Amouna t Adsorbed v Ji OA (C`rmuy a IEEE Desorption, ug/s ANneovuenrt.sooncosmoit EE Desorption, Thi fBosroention b$52e00it0]0 psoeoo]0n 0.10000 Asopunrt uon soit bests Desorption, ug/, ) esio0 3.3000 Z16.7000 "23.9500 3rio 29.500 Yon 11.4000 too4.7000 bd 2.2500 ith corsaction for whe smoons oF FC.BS bo the 2s mh of semation momsining *Columns F, G, and H were calculated in the same way as Column F, TABLE I from the previous step in each case (See Materials and Methods Section.) : : ot . Sak "~ Adsorption Isotherm GETTER 95 DEfSFOiIRGPtUTRIEON2 NTA POINTS Tiay 180TiERy 3J % vas Pr fre HA Ca SOTION CONC (wphm) 000185 ABSORPTION AD BDESFEOIRGPUaRTnEIO:N3 11S3O0T0I.ERaSo,FOsRhore LINES ARE BEST FIT FOR ADSORPTION AND ET REIT psp. on Cn , 4 y TABLE TIT FC 95 Material Balance* Total AInitial (FCColu95mniDn,SToAluBtLiEonT,) mg. 73..0955000000 21..2257050000 00..07700000 FC 95 in8Solution (CaotluEmqnuilE.,,"TmAgB.LE I) 35..3854570500 1.1.909520500 00..0555020500 FC 95 con soil "ataE-quBil., ng. 10..2509255000 00..322275500 00..0124070500 Amount Reomoved by Amount ReEmoved by Amount RFemoved by First Desorption, mg. Second Desorption, mg.. Third Desorption, mg. 00..489674755000 00..217781070500 00..100554755000 00..311519000000 00..015050705000 00..002306225500 ) 00..001910550000 00..000343050000 00..000122225500 Total GAmount DDeessoorrpbteidonbsy,Thnrgee (DEF) 10..27428430 00..24345703 00..10316738 Amount RemHaining on Stoiiolns,Aftmge.r 3 (DCes-or6)p- --00..4152795000 -0-0..0111090705 00..01012225500 Amount1Desorbed as P(e6r/cCenxt1o00f)Amount Adsorbed 112015..688015 110346..454645 9828..377530 "Columns D, E, and F were obtained by first calculating the amount (ag) ooff FsCo-l9u5tioinn 2i7n.5eamclh r(e25spmelctaidvdeedstpelpusand2.5thmeln rseumbatirnaicntginfgrotmhepraemvoiuonuts(nsgt)ep) in the 2.5 nl of solution remaining from the previous step. : 000186 Te 2 : S=U LR 8 in ig FC 143 ) Data for FC 143 are presented in TABLE IV and TABLE V and in FIGURE 4. The adsorption isothern indicated FC 143 mobility similar to that of FC 95 with K=0.38 and Nel. Regression analyses were not perforned on the desorp- tion isotherns, however, the graphed data (FIGURE 4) indicated that adsorption and desorption could not be described by a single-valued function. That is, the K' and N' values for desorption would not be the same as K and N for adsorption. Subjective evaluation would indicate that the desorption coefficient X', would be mich smaller than the adsorption coefficient, K, at solution concentrations greater than about 25 mg/1, since the slope of the adsorption isothern was much greater than the slopes of the desorption isotherns in this Tange. At solution concentrations less than 25 mg/l., the desorption coefficients would appear to be much greater than the adsorption coefficient. ) Fron this it would appear that two or three different binding mechanisas Were involved with stronger binding occuring at the higher concentrations and the converse at lower concentrations. While this may indicate a tendency for FC 143 to be immobile at high concentrations, it would be quite mobile in any situations involving low concentrations. . Material balance data for FC 143 are presented in TABLE VI. While the two concentrations resulting in 212%and 201% desorption (last column in TABLE VI) were erratic, in general, the data indicated that all of the FC 143 vas accounted for throughout the experiment. 2 00187 Brkt 3 FEES TLE Tv FC 143 Adsorption Data L A 5 c Initial FC 143 Conc., mg/l. Equil. Conme., Cc, mg/l. X Removed By Soil - - s22922..56 428759..81 (4x2x4 1000) C1406 1695742...213 14699020..932 4u2..s10 5.2 51 13 . E Ti5ongtaIlniFtCia1l43Sol'n, STonoltg'anl aFtC E1q4u3ili.n, FG 143 Adsorbed o0n-5S)oixl',10x/n, ug/g . (Ax 0.035 liters) (Bx 0.025 liters) ) 71.3.30165205 162..91747550 18637..55 42.1..133850072055 124...230400757505 93142...550 0.1300 0.1275 0.5 3 . 000188 LER Vaart T on LET : 10 Tn iE 5 TABLE V FC 143 Desorption Isotherm Data A B SEqouliult.ionC,oncC., fn iEnquFiilr.atCoDnecs.orp- as/1 tion Solution, mg/l. (CoB,lTaublmeInV) 485.800 126709..310000 92.200 49.900 5.100 47.6000 1728..28000000 10.7000 6.1000 0.6000 c D EiqnuiSle.conCodneD.esorp- EiqnuiTlh.irdConDce.sorption tion Solution, mg/l. solution, mg/l. 6.80000 34..4800000000 2.00000 0.80000 0.10000 3.50000 22..9000000000 0.50000 0.20000 0.01000 E o u ) Amount Adsorbed aonsSoil, x/m, Amount on Soil Aafltser First Desioonrp- Amount on Soil Adount on Soil Afstlesr SectoinodnDesorp- Afgt/ger ThtiirodnDesorp- / (Colum , TABLE Tv) 183.500 67.500 34.500 9.500 12.000 0.500 164.600 50.850 20.050 =3.250 3.400 =0.250 151.000 38.650 9.950 ~8.900 2.050 ~0.500 135.150 25.100 0.650 ~10.650 1.350 ~0.505 #Columns 7, G, and H vere calculated in the same vay'ks Column , TABLE IV wfirtohm tchoerrpercetviioonusforstetpheianmoeuancth cofasFeC(1S4e3e Miantetrhieal2s.5amndl MoefthsoodlsutSieocntiroenm)a.ining 000189 SEE un 200 D 1504pa-- -- TT 8 -- A $ 100 zX A ---- = Zc 2 so { 8c -- --x B 1 ol YF E c% 2% Y= 16.5 + 0.38 X R-SQUARED = 0.936 2 : -s0 0 100 200 300 400 500 Y Equil. Conc., C, mg/l FIGURE 4 FC 143 ADSORPTION AND DESORPTION ISOTHERMS dSeosloirdptliionne iissotbheesrtmsf.it aA'dssoarprteioandsoirsoptthieornm,isoDtohtetreaddaltianesposinrtes.estBi,maCt,edD; E, and F are desorption data points for the respective concentrations. GENERAL COMMENTS The FC 95 and FC 143 adsorption coefficientsfromthese experiments my be converted to the analogous constants based on soil organic carbon content K, with the equation K,. = 100 K/(% organic carbon) giving a Ky of 45 for FC 95 and 17 for FC 143 (2.2% organic carbon for this soil). Comparing these values to those in TABLE VII, it can be seen that FC 95 and FC 143 are at the low end of the spectrum, again indicating high mobility of these compounds. 2 000190 R SREETRRE SA TTT ET TTT TE 12 TEE s D TABLE VI FC 143 WATERIAL BALANCES A c Total FC 143 Initially in Solution (Comlgl.mn D, Table 1v) FC 143 in Solution at Equil., mg. (Column E, TABLE IV) FC 143 on Soil at Equil., mg. W - B) 13.0625 12.1450 0.0175 7.3150 6.9775 0.3375 42..13582080 4.2.03007550 00..10742755 10.13300705 10.22747s5 00.000620s0 e v FAmiorusntt.DeRseomropvteidonb,y ng. ASmeocuonntd RDeesmoorvpetdiobny, mg. TAhsiorudntDeRseomropvteidonb,y ag. -D 00..0088432550 0.omazs 00..0066180000 0.05050 00..007686275500 0.046500 + 000016337050 00..002086275 00..000083755000 0.00375 olon2s 0.000025 c i 1 Total Amount De- Gee) DseosrobrepdtiboynsT,hrmege Amount Remaining on : 55 tSoiiolns,Afmtge.r 3 Desorp- Amount Desorbed as pseorrcbeendt (oGf/CAmxou1n00t) Ad- 0.2418 000...211016020808 - 00.l00503s0 0.676750 0-0.0..100250533522055000 -00..000026572580 $ 26.349 2651622...181110658 25081..705000 F*CCol1u4m3nsinD,27.E,5 malnd (F25wmelreadodbetdainpeldusby2.5fimrlst rceamlaciunliantginfgromthepreavmioouunst s(tmegp))of of solution in each respective step and then subtracting the amount (mg) in the 2.5 ml of solution remaining from the previous step. 000191 te C R LUR E R TABLE VIY CofmopraraisSoenleocftedAdGsroorupptioonf CPoeesftfiicciideensts N (Hamaker and Thompson, 1972) Chemical Koo (pobile) (ChFloCraSmbe=n= = ===2= 1712).8 2,C49-05 - vm m on = a352) PrBoropmhaacnil n51 SMionnauzrionne 1385 . DPircohplaozbienneil 116542 ACthlroarzoipnreophan 21752 APrnoemtcrtyonne 330800 PDrioumrcotnryne a51s3 PCahrlaoqruoaxturon 240,,908060 (imaobile) DOT 243,000 EAPRLORER - The small amounts adsorbed and ease of desorption is consistent with the relatively high vater solubility of FC 95 (300 mg/1) and Re 143 (520 g/1.) and with the. chemical nature of the molecules - organic salts which ionize in aqueous solution: CgF 505K 5Fy 500,M, FC 95 FC 143 000192 RET rm GR ah EE ee jo : !' 1 pr Cait E Terns DPM - Disintegrations per minute C - Concentration of chemical in solution at equilibrium x/a - Concentration of chemical adsorbed on soil at equilibrium R? - Coefficient of deternination : kK - Adsorption coefficient K' - Desorption coefficient : N - Exponential term in Freundlich Equation : N' - Exponential term for desorption equation Koc - Adsoiption coefficient based on soil organic carbon content References DavidPseosnt,iciJ.deM.M,oveemt.entalT.,hro1u97g5h,SoEUislePs,oAfU-.SoGilS. GEPP0aRr,a7meZte-rs7fo5r -De0sc0rib0in.g DavidisnonS,oiJl.s,M".,pre1s9e76n,ted"VeatrtiScyamlpoMsoivuemmeonntNoannbdioDliosgtirciablutTiroannsporotf Orgaanndics OG TfranSastafnodrlanradtst i,on hof e Pollr utanstsWDh o.n,MuLaand yrand g 1-13, ,Wa1te9r7,6.at National Bureau Hanakienr,thJe. SWo.i)anEdnvJi.roMm.enTth.ompsCo.n,A. 19I.72.Gor"iAndgsorapntdioJn." Wi.n HOarsgaakneicr C(hoedmsicalJrs farcel Dekker,Tnc., N. Y. HamakCehrem,icJa.lsW,.,Hu1n9a75n,He"aIlnttherapnrdetatthieonEnovifroSnomielntL,eAachiCnogllEexcpteiroinmeonftsD,o"w Sicnienti- fic Papers,VoT. 1, DowChemical USA, Midlan, Wich. 8640 -- : 000193 he LHR it ~o I Attachedarecommentsonthe3M TechnicalReport "AdsorptionofFC 95and FC143onSoil. SX. Welsh, Project 9970612633 FateofFluorochemicals, Report No. 1, Feb. 27, 1978"`madeby ProfessorStephenA. Boyd,MichiganStateUniversity, datedMay19, 1993. : 000194 Lf : Reviewof Technical Report Summary Adsorption of FC 95 and FC 143 in Soil Material and Methods sSohrobusldlegsisvtehraencogvlaesrsieosonfpocloymetphoyulnendes,ibnubtldaoneks(nn'ot-sgoiivle) aexnpuemreirmiecnatls.vaSltuaet.es that polypropylene "voTlhaetillairzgaetihoenadosrpascteic(ki2n5gmtlointhae 5t0ubteu,bew)iils uinndfelsaiterabtlhee;saonryptlioosnsecsooeffftihceien"tC-slianbceel,thee.g.m,etfhroodm ccaolnccuelnattreastitohnes.amAolusnot tshoer2b4edhobuyrdmiiffxeirnegncpeerbieotdweseenemtshearibniittriaarly.andWefrinealeexqpueirliimbernitusm dsoonleutifoonr differentperiods of time to establish that equilibrium was reached within 24 hours? Details on the stock solution are lacking. What solvent was used and What is the specific activity and radiochemical purity of the "C-FC 95. `The idea of using acotton swab aftethe draining step is unusual Hopefully this didn't remove asosilhiagshwaesllI'ads lwiakteetro. sTeeheit.~2A05%0%orolresgsredaetcerreadseecrienassoeluwtoeuclodncbeentbreatteiro.n due to sorption isn't `This section generally lacks detail that would normally be required for publication. Results and Discussion dTehmeonlsinteraartietytohafttthheeiesnottihreerimsohtahsebremeins slihnoewarn, otvheerlitnheearciotnycemnutsrtateixotnenrdantgoeeuqsueidl.ibrHiouwmesvoelru,tiotno coofnFceCn9t5ratoiroFnsC1t4ha3t:apIpfrnooatc,hhtohewwwaetrere tsohleubiiniltiitaylosfoltuhteiocnomcponocuenndt.ratDioonsyosuelkecntoedw?the solubility `Thesorptioncoefficient(K) ofFC 95appearstobeabout 1asindicated. Theorganicmatter ins asooilrsorpsmtoiropantciooelnfcfoiiecfifeinzctiiennette(rdKmeedia=teKbe/twfeies,nKbo)ennz=ene1/a0n.d0t2o5lu=er4i0e,,oIrtw 10g Koobyeu =wo1r.l t6h.whTdihlies `to ecxaominwneitshvoinmeaefaadrcdtitogiroonfea2l stooils3ftoorcdoinfffierremnttshoiislKs.osTvhailsuwe.ouGlednienrcarlelay,sethmeyKc.uo,nvafliuedseishnnotcuhled accuracyofthe one measured value. : TexvpeersipmoetntcshaencdkeIdgettheesssoeinltiaclolnycetnhterastaimoensvaolfuesF.C-T9h5efcoarlcbuolatthiotnhselosoorkptgiooond.and desorption `soTlhuebiKlitvya.luTehs efohrysFteCrsi1s43in itshelodweesorrptthiaonnFiCsot9h5erimndiiscsautripnrgistihnagt,itanpdrohbaasblbyeehnasoaver-hiingtheerrprweattede.r `"Tthhereseordpitfifoenrenitsobtihnedrimngismleicnheaarniisndmisca.t.i.ngwiathsisntgrloengsoerrpbtiinvdeipnrgocaetshsi.ghTehrecocnocnecnltursaitoinonrsegaanrdditnhge ceoxnavmeirnsees actolluowmenrIc*oAncmeonutnrattDieonsso"rbiesdvaesryasPpeerccuelnattiovfeAbmaosuendtoAndsthoerbseindgletheexvpaelruiemsenrta.ngIeffornoem. 060195 26 10212 percent, so it's pretty inconclusive. There is a fairly good discussionof hysteresis in J. Environ, Qual, 12:325-330 by Koskinen and Cheng who observed this phenomena for the weak acid pesticide 2,4,5-T. The causes of hysteresis are varied and complicated and may include microbial degradation ofthecompound during desorption, and changes in the physical `and/or chemical properties of the soil-solution system. For example, desorption using distilled `water(asisthecasehere)couldresultinsoil dispersionsothat aclearsupernastolautniotn `could notbeobtained. This can cause quenchingofradioactivity in solution and other problems leading to error. `The "material balance as presented in the report is a little misleading. To obtain a material `abdadlaintcteoytohue smheoausludrmeedassoulruetitohne caomnoceunnttroatfio"nCs-.activity in soil at the endofthe .experiment, and GeneralComments. TheK,,valuescalculated hereuseanorganiccarbon contofe2n.2t% whereasthevaluestatedintheMaterialsandMethodis 1.5%? `Thewatersolubilitiesarecitedas 300 mg/L for FC 95 and > 20g/LforFC 143. Surely the Iatter value is wrong. Ifthe solubilities are truly that different, then the sorptive properties should be vastly different, which they are not. If FC143 has a solubility of >20,000 mg/L, then I would expect no sorption. This value must be erroneous. Recommendations: 1. Obtaining K, K., values on additional soils. DetermineifK., is relatively constant. 2. Obtain a true mass balance by measuring "C-activity in soil and solution phase. 3. Interpret desorption data more cautiously. - 4. Get correct valueofwater solubility of FC 143. 00196 "Pomerar 11a TECHNICAL REPORT SUMMARY TO: TECHNICAL COMMUNICATIONS CENTER -- 201.2CN {important Ifreport ispinotnbeodt siodfpaepesr,sand twocopiets0 TCC.) EE PC Fate of Fluorochemicals Adsorption of FC 95 and FC 143 on soil 2/21/78 0222 9970612633 1 Stephen x. nes SEW 73583 140673, #47708 14 ssonmvp LO0conier tosiaRunoriaton) |HEGRE aE werwaonmos:rom am CURRENT GRsECTIVE: " = pe To obtain an indication of FC 95 Co and FC 143 mobility in sandy loam soil. EE BC - Div. FluorochemicaC l [a meron ABSTCRoACmTe. (R080705.0wore Tris sovract informationsdaburedby he Techical Commrications Contr 1 Soil As a part of the Fate of Fluorochemicals Project, an indication Adsorption of mobility of FC 95 and FC 143 in sandy loam soil was desired. Nobility AMdsorption-desorption experiments (after Davidsoxn, 1976, and Hamaker, 1675) along with water solubility data can provide such' information. The adsorption coeffifnts for FC 95 anFdC 143 were determined to be 0.99 and 0.38, respectively. For FC 95 adsorption and desorption could be described by a' single valued function while for FC 143, they could not. Based on these data, both compounds would be Judged mobile in the sandy loam soil used in this study. rmation ton 00197 " 2 concLUSTONS Adsorption coefficient for FC 95 and FC 143 were 0.99 and 0.38, respectively. For FC 95, adsorption and desorption could be described by a single valued function while for FC 143, they could not, Considering adsorption coefficients, desorption characteristics and water solubilities, both conpounds would be judged mobile in the sandy loam soil used in this study. INTRODUCTION As a part of the Fate of Fluorochenicals Project, an indication of mobility of FC 95 and FC 143 in sandy loam soil vas desired. AMdsorptiondesorption 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. EPA in pesticide registration requirements. MATERIALS AND METHODS Duplicate S-g samples of air-dried Brill sandy low soil (S7% sand, 364 silt, 7% clay, 2.5% organic matter, 1.5% organic carbon, with pH 6.5 and C.E.C. of 15.3 meq./100g) were shaken with 25 ml of solution in 50 ml.' poly- Propylene centrifuge tubes for 24 hours on a wrist action shaker at room temp. (16-15C). Polypropylene tubes were used because they were found in separate experiments (3M Tech Notebook #470673, `C. H. Schrandt) to sbsorb less FC 95 and FC 143 than glass or polyethylene tubes. Solutions were made by diluting a stock solution of each chemical. Concentrations of '4C-labeled FC 95 were 282 mg/1., 158 mg/1., 90 mg/1., S1mg/l., 28 mg/l., (100%, S6%, 323, 18%, 10%, 1% of stock). Concentrations of 14C-1abeled FC 165 were 525 ng/1., 295 mg/L, 167 ng/l., % mg/l., 52 ng/l., and 5.2 ng/1. 000198 Ba 3 After shaking the initial solutions as well as the three desorption extractions with deionized water, the samples ere centrifuged at 5000 pm for 10 min., and three aliquots of each supernatant solution were taken for scintillation comnting. After the adsorption step, 22.5 ml of solution were Tecovered, Therefore, it was assumed that 2.5 ml of liquid remsined with the soil in each step and this amount was accounted for in the desorption calculations (see Results and Discussion section). In the FC 95 experiment, the supernatant 1iquid was simply drained Off at each step and the next 25 ml of liquid were put into the tubes. In the FC 143 experinent, the supernatant liquid remaining after the draining step was absorbed with a cotton swab before putting the next 25 m1 of liquid into the tubes. "The procedures for the FC 95 and FC 143 experiments were recorded in 3 Technical Notebook #40673, p. 49 and p. 51, respectively. From the raw counting data, disintegrations per minute (DPM) and FC 95 and FC 143 concentrations were calculated for all of the supernatant solutions, Statistical analysis and plotting of the dats vas done with the MINITAB package of the 3M TRAC computer service. ) RESULTS AND DISCUSSION FC 95 Adsorption data for FC 95 are presented in TABLE I and FIGURE 1. Comparing the regression equation of the adsorption isotherm (FIGURE 1) X/m = 0,29 + 0,99C with the Freundlich equation x/m = Kc/N, it could be seen that the adsorption coefficient, K, equaled 0.99 and the exponent, N,00091! equaled one, The linear shape of the adsorption isotherms (N=1) indicated P 4 that FC 95 adsorption on soil would be independent of concentration. The low adsorption coefficient (K=0.99) indicated that FC 95 would be mobile, i.e., it would move readily with the ground water through this sandy loam soll. TABLE FC 95 ADSORPTION DATA . A 5 c ) IniCtoinael., F5C8/915 -- 21528..20 s0i.l0o 2820.08 : > EqC,uilm.g/lC.onc., --_-- 213334..92 a7z6..09 221010 E A*Ehere E10 1175.11 1176.68 2271.10, wd PY In TIontiatlialFCSo9l5'n (Ax 0.025 liters) - 3.7.90550000 21..22570500 00..07700000 SoTlo'tnalatFECqu9i5l.i,n mg (Bx 0.028 liters) 55..8348755000 11..0952020500 0.00555020500 onFCSo9i5l,Adxs/oar,bedba/g (0-E) x 10 C um oil 2109..80 a653.7 23s8 Desorption data for FC 95 are shown in TABLE II and FIGURE 2. For comparison, desorption isotherns for the pesticide fluometuron are given in FIGURE 3. For clarity FC 95 desorption isotherms are not drawn in FIGURE 2. However, all of the data points lie very close to the adsorption isotherms . indicating that adsorption and desorption could be described by a single-valued function with desorption coefficients, K', equaling the adsorption coefficient, 000200 DU s 240 BE A - i 180 . . 3 120 E i3o DZ X EE Regression Eqn.: Y = -0.29 + 0,99 X R-Squared = 0,985 oC A) 5 [I] 120 180 240 300 Equil. Conc., C, mg/l FIGURE 1 FC 95 Adsorption Isothern . This, along with the observation that approximately all of the adsorbed FC 95 was subsequently desorbed (TABLE IT, Column H) indilated that binding forces were weak and would be another indication of high mobility of EC 95. tL Material balance data for FC 95 are presented in TABLE III and these data indicate that all of the chemical was accounted for throughout the experiment. 000201 iy o . A Equil. Conc. in Solution, C, mg/l. 213334..920000 427.6.090000 22.100 2.000 TABLE 11 FC 95 DESORPTION 5 Equil. Conc. in First Desorption mg/l. 3502..73000000 189..36000000 5.3000 0.6000 ISOTHERM DATA* c Equil, Conc. in Second Desorption mg/l. 194..05000000 25..33000000 1.7000 0.2000 } 0 Equil. Conc. in Third Desorption mg/l. 52..2800000000 | 11..8000000000 0.60000 0.10000 : E \mount Adsorbed on Soil, x/m ug/g Col1u12m94n0..03F0,000TABLE I) 462595...357000000 3.800 F Amount on Soil - After First Desorption, ug/g 6179..64050000 11313...243000000000 1.7000 [I Amount on Soil After Second Desorption, ug/g -1412..50000000 126..07500000 4.0.79000000 H Amount on Soil After Third Desorption, ug/g -2-59..81050000 2"32..90500000 02..42550000 *Columns F, G, and H with correction for wtehreeacmaolucntulaotfedFCin95thine tshaeme2w.a5ymlasoCfolsuomlnutiF,onTATBeLmEainIing from the previous step in each case (See Materials and Methods Section.) el : : : ne " oi<3 3 "~ Adsorption Isothern TR . " FIGURE 2 FCC 9955DEDESSOORRPPTTIIONDATAPPOoInNtTs 3 aon % ase ce Pe som ean PY oF sean TM ony 5 0 2, soumon conc ream 000202 ADSORPTION AND Frou 3 DESORPTION ISOTHERYS FOR OE a chy, "SOANLDBIROKDEN PR 7 TABLE 111 FC 95 Material Balance* Total AInitial' (FCCol9u5mniDn;SToAluBtLiEon1,) mg. 37..9055000000 12..2257050000 00..70070000: FC 95 in8Solution (aCtolEuqmunilE.,,"TmAgB.LE I) 35..3854570500 11..909520500 00..5055020500 FC 95 con soil aAt-EBqu)il., mg. 01..5290520500 00..232257050 0.14750 0.02000 Amount ReDmoved by First Desorption, mg. 00..489674755000 00..311519000000 00.001910550000 TotalGAnount DDeessoorrpbteidonbsy, Tnhgree (DEF) 01..27428430 0.0.24345703 00..10316738 Anount REemoved by Second Desorption, mg.. 00..127718705000 00..015050705000 00..003034500000 Amount RemHaining on tSoiiolns,Aftmge.r 3 (DCes-o6r)p- AmountFRemoved by Third Desorption, mg. 00..015045570500 0.036250 00..001220225500 0.002250 Amount1Desorbed as P(e6r/cCenxt1o0f0)Amount Adsorbed --00..1425970500 --00..1011807050 00..01012225500 112013..688015 113064..454645 8982..755703 o*fColFuCa-n9s5 Di,n 2E,7.5anmdlF (w2e5rneloabdtadiendedplubsy 2f.ir5stmlcarlecmualiantiinnggfrtohme parmeovuinotus(mgs)tep) oinf tshoelut2i.o5nmlinofeacsholurteisopnecrtievmeainsitnegp farnodmtthheen psruebvtiroaucstinsgtept.he amount (mg) 000203 IE . * FC 143 Data for FC 143 are presented in TABLE IV and TABLE V and in FIGURE 4. The adsorption isothern indicated FC 143 mobility similar to that of FC 95 "With K=0.38 and Nel. Regression analyses were not perforned on the desorp- tion isotherms, however, the graphed data (FIGURE 4) indicated that adsorption and desorption could not be described by a single-valued function. That is, the K' and N' values for desorption would not be the same as K and N for adsorption. Subjective evaluation would indicate that the desorption coefficients x', would be much smaller than the adsorption coefficient, K, at solution concentrations greater than about 25 mg/l, since the slope of the adsorption - isothern was mich greater than the slopes of the desorption isotherns in this range. At solution concentrations less than 25 mg/l., the desorption coefficients would appear to be much greater than the adsorption coefficient. From this it would appear that two or three different binding mechanisms were involved with stronger binding occuring at the higher concentrations and the converse at lower concentrations. While this may indicate a tendency for FC 143 to be imnobile at high concentrations, it would be quite. mobile in any situations involving low concentrations. : Material balance data for FC 143 are presented in TABLE VI. While the two concentrations resulting in 212%and 201% dsorption (last column in TABLE VI) were erratic, in general, the data indicated that all of the FC 143 was accounted for throughout the experiment. 000204 RE. El TABLE TV : FC 143 Adsorption Data a 3 c . | CInointci,.almg/Cl.143 Ec,qumigl/.1.Conc. By2 SRoeimloved . (452x100 To2s92s.6 247859..81 E4Y.)6 1697.1.2 16902..32 42.10 . 52s.a3z 495.19 a19s : > E . iTnotIalniFtCial143Sol'n, TSootla'ln aFtC E1q4u3ili.n, oFnG S1o4i3l,Adsxfomr,beudg/g u(Agx 0.025 11ters) (Bngx 0.025 liters) ( ) X10 1 : 173..30165205 162..91747550 183.5 67.5 4.1800 2.3525 4.0075 2.3050 "3o.l5s . 01..13300750 01..12247755 12:0 0.5 060205 ZF. We 10 `TABLE V : FC 143 Desorption Isotherm Data* A ESqouliult.ionC,oncC., in =e/1 5 iEnqufiilr.etCoDnecs.orp- tion Solution, mg/l. (Column3,Table IV) + 485.800 279.100 160.300 92.200 495..910000 47.6000 28.8000 17.2000 10.7000 06..61000000 c iEqnuiSle.coCnodncD.esorp- tion Solution, mg/l. E{iqnuiTlh.irdConDce.sorption _solution, mg/l. 6.80000 4.80000 3.40000 2.00000 00..8100000000 . 3.50000 2.90000 2.00000 0.50000 00..2001000000 E Amount Adsorbed Amount on Soil on Soil, x/m, After First Desorp- u(eC/oglum 7, TABLE IVu)g/g tion 183.500 67.500 349..550000 12.000 0.500 164.600 50.850 -320..205500 3.400 ~0.250 c u Azount on Sol Asount_on Soil After Second Desorp- After Third Desorp- ng/g tion ug/g tion 151.000 38.650 89..990500 2.050 =0.500 135.150 25.100 100..665500 - 1.350 =0.505 *Colums F, G, and H vere calculated in the same way as Colum , TABLE IV with from correction for the amount the previous step in each of FC 143 case (See in the 2.5 ml Materials and of solution remaining Methods Section). 000206 co u 200 . 150k 57 _-- -- 8 J-- A ' > 100 22 A Zc 1 efx g3 so La A s -- --% B : E 5 2K 2 YR-=SQU1A6R.E3D += 00..93368 .ca - -s0 o 100 200 300 400 EN Equil. Conc., C, mg/l FIGURE 4 FC 143 ADSORPTION AND DESORPTION ISOTHERMS : Sdeosloirdptliionne iissobtheesrtmsf,it Aa'dssoraprteioandsoirsoptthieornm,isoDtohtetremddaltianepsoianrtes.estBi,maCt,edD, E, and F are desorption data points for the respective concentrations. GENERAL COMMENTS The FC'95 and FC 143 adsorption coefficients from these experiments may be converted to the analogous constants based on soil organic carbon content K,., with the equation K,. = 100 K/(% organic carbon) giving a Ky. of 45 for FC 95 and 17 for FC 145 (2.2% organic carbon for this soil); Comparing these values to those in TABLE VII, it can be seen that FC 95 and FC 143 are at the low end of the spectrum, again indicating high mobility of these compounds. : 000207 Co 12 TABLE VI FC 143 MATERTAL BALANCE* A 5 c InTiottiaalllyFCin143Solution (Cmoglu.mn D, Table 1v) FCat 1E4q3uiiln.,Somlgu.tion (Column E, TABLE IV) FatC 1E4q3uilo.n,Somgi.l (A .- B) 13.7.03612550 162..91747550 0.o33o75 : - 2.4.31582050 42..03007550 00..10742755 1.031037050 1.0.21027755 00..00062050 E or AFmiorusntt.DeRseomropvteidonb,y mg. ASmeocuonntd RDeesmoorvpetdiobny, mg. ATmhoiurndtDeRseomropvteidon,by mg. 00..0083342550 0.00:067327255 00..004037050 00..0066810000 00..0052085205 00..0000617255 00..007696275500 00..004068570500 00..000030500205 . G sToortbaeld AbmyouTnhtieDee(DDe+sEoSrFp)tions, ng 0.0.22142108 00..11609038 00..00503550 H SoAimlounAtftRerema3iDneisnogrpo-n'. tions:, 6ng). 00..617265755000 00..000533225500 -00..000062572550 1 : ApmeorucnenttDoefsoArmboeudntasAd- sorbied (6/C x 100) 2626..831459 . 29128..110186 28081..705000 "FCCol2u4m3nsinD,27E.,5 amlnd(F25wmelreadodbetdaipneldusby2.5fimrlstrceamlaciunliantginfgrotmhepraevoiuonuts s(taeg)p)of oifn tshoelut2i.o5nmlinofeacsholruetsipoenctrievmeainsitnegp afnrdomthtehne psruebvtiroauctsinsgtept.he amount (mg) 000208 . oF : = - gr s TABLE VIT CofmorpaariSseolnecotfedAdsGorroputpioofn PCeosetfifciicdieesnts (Hamaker andThompson]1872) Chemical Koo (mobile) (immobile) C(hFlCo1r4a3mbon = 2(,C495 -- ooo PBrroompahcainl SWiomnauzrionne DPircohplaozbienneil ChAltroarzoipnreophan APnreotmreytonne DPrioumreotnryne CPhalroarqouxautron DOT oo2. 1712).8 voogn3s2) 7s1 13835 152 116742 234050 34880s ou- 513 4,986 i 24230,,000000 71 . e. n The small amounts adsorbed and ease of desorption is consistent with the Telatively high water solubility of FC 95 (300 mg/1) and Kc 143 (>20 g/1.) end with the chemical nature of the molecules - organic salts which ionize in aqueous solution: . N CaF,3505 K CF 50, NH, k FC 95 FC 143 : C0209 i 14 / Terns DPM - Disintegrations per minute - - Concentration of chemical in solution at equilibrium x/m - Concentration of chemical adsorbed on soil at equilibrium RZ - Coefficient of deternination . KX - Msorption coefficient K' - Desorption coefficient N - Exponential term in Freundlich Equation % N' - Exponential term for desorption equation i Koc - Adsorption coefficient based on soil organic carbon content References . DavidPseosnt,icJi.deM.M,oveetm.entalT.,hro1u97g5h,SUosielosfU,.ESoPiS.lA-PaGErPAa,Gme0te7rs2-foTr 8De-sc0r0ib0i =, +DavidTisrnoannS,sofioJl.rsm,aM".tp,iroen1s9e7o6nf,tPeod"lVlaeutrttaiSncytamlspooMsionuvmemLindeonntNsndoamnbdioWDlaiotsgetirrciabalurtTiroorantnosoipfooTrOtrgaaPnndiocus C Of Sa tandlardst, hersWDb.,Muayr 11-g 13,,1976. Hamaker, J. in the 'SWo.ilaEnndvJi.roMm.enTth.ompsC.on,A. 191.72.Gor"iAndgsoarrpdtiJo.n Wi.nHOarmgaakneicr C(heemfiscagls FarceT Dekker, Tnc., N. Y. HanakCehre,micJa.lsW,.,Hu1m9a75n,He"aIlnttherapnrdettathieonEnvoifroSnomielntL,eacAhiCnoglleEcxtpieornimoenftDso,w" SicnientiFic Papers, Vol. 1, Dow Chemical USA, Midland, Wich. 48640 00210