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AR226 _ 02897 BIODEGRADATION (301E) TEST SUBSTANCE Identity: A mixture containing perfluorooctanesulfonate, which may also be referred to as PFOS, FC-95, or as a component of FC-3017. Octanesulfonic acid) (CAS # 2795-39-3). (1- RFeCm-a30r1k7s:prodTuhceed3iMn Apnrotdwuecrtpi,onBellogtinuumm.beCrurwraenst2i3n3f0o.rmaTthieonteisntdiscaamtpesleFCis3017 is a mixture of 0.67% PFOS, 20% diethylene glycol butyl ether, 55.41% 0wa.t5e%r,p2ol1y%oxeytehtyhlyelneeneglmyoconlo,oc1t.y3l3p%heHnyydlroexthyerf,oa0m.e0r4,%1s%odsioudmiulmauorcyltyslulsfualtfea,te, and 0.05% tolyltraizole. cThhaerafcotlelroiwziendg scounmcmeantrryataipoplnisoesftiompaurmiitxiteusr.e Dwaittha imnacyomnpoltetaeclcyurately reflect the biodegradation potentialofthe thetest sample. fluorochemical component of METHOD Method: Modified 1979 version OECD Screening Test, OECD 301E with DOC Analysis, Test type: Aerobic Ready Biodegradation GLP: No Year Completed: 1980 Analytical Statistical monitoring: Dissolved organic carbon methods: Results were determined by (DOC) calculationofthe % DOC removed as compared to the blank controls. TTehsetsoercgoanndairsym esfofulurecnet:waAs 5f0r:o5m0 amnixacotfivsoaitledexstlraucdtgeanadersateicoonndbaasriyneafftlutehnet. sMoeitlrforoWmasttheewtaotwenrofTrWehaittmeenBteaPlranLta,keS,t.RPaamuls,eMyNC,ouwnhtiyl,e tMhNe.soil was garden Test condition: Dilution water: Deionized water - Mineral (1979). Nutrient Initial pH Medium: 7.0. Nutrient medium per OECD 301E method Test and prepared reference solution preparation: by dissolving 208 mg in on liter of The test material was mineral nutrient medium. Trheifserseonlcuetisounbgsitvaenscea,fhinyadlrtoeqsuticnoonncee,ntwraastipornoepfa4r0edmbgy DdiOsCs/oLl.vinTgh3e0.6 mg in one liter of mineral nutrient medium. test concentration of 20 mg DOC/L This solution gives a final ~ Tsoelsuttivoensasneldsc:a5p0p0edmLwitEhrlfeonammeypleurgsf.lasks containing 250 mL test Incubation conditions: Lighting: Constant dark conditions. 002747 Temperature: 23.5-24C Agitation: Continuously sNuubmsbtaenrdo)facnodncbelanntkr,aatliloinnsd:upl1icpaltues. hydroquinone (reference Iarneocrueqluuimrecdopnedrittihoenroefnerteesntceidnimteiatthioodn):.Not given (No measurements Total suspended solids and Element Basis: Decrease in pH on dayoftesting: Not given. dissolved organic carbon compared to Ttheestblsaunkbss.tance flask conditions: Not given. | RESULTS Nanodmianta~l2c0omncgenDtOrCaItLiopnlsu:s HBglCakn,k c(ionnhtirboilt,edh)y,tdersotqumaitneorniealata~t2~04m0gmDgODCO/CLIL and at ~40 mg DOCIL plus HgCh, all in duplicate. Element values: and 94.6% DOC 28-Day removal in Degradation duplicate 2. = 96.2% DOC Mean value = removal 95%. in duplicate 1 Remarks: Testing was conducted on the mixture as described in the Test SthuebsftluaonrcoechReemmicaarlkpsrofipeoldr.tiTonhealvoanleu.es reported apply to that mixture and not CONCLUSIONS Percent biodegradation of FC-3017 value was 95 after 28 days. was based on the mean DOC removal Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 DATA QUALITY tReesltiianbgi.lityH:owKeivmeirs,cthhreasnakimnpgle= p2u.riTthyiwsasstundoyt mperoeptesrltyhechcarritaecrtiearfiozreqduaalnidtythe isntusodlyutliaocnk.s analytical confirmationofthe amountoffluorochemical proportion REFERENCES The studies were conducted by the 3M Company, EnvironmentalLaboratory, St. Paul, MN, Lab Request number 5541S, 1980. oo OTHER Last changed: 6/26/00 002748 iimmena TECHNICAL REPORT SUMMARY 3 TECHNICAL COMMUNICATIONS CENTER -- 201.208 portan--t Ifrepisporinrtedton both siodfpaepesr,send te copes to TCC.) [=oom 6/30/80 ="Environmental Laboratory ( & pC) 0535 Commercial Chemicals Division 9e97e00r12600 Biodegradation of "LIGHT WATER" Products in OECD Test-6/80 | 040 John A. Pignato - Commercial Chemicals Division - 236-24 (01) Eric A. Reiner - Environmental Lab (EE&PC) - 21-BW (63) 47816 None - See 3M ---- Environmental 0cows Lab Request No. 55418 ERS 31 meen ESwoensas:rmomas CURRENT oRIEGTIVE: a athe bvoirraotnomreyntal TpTeorsotudsucewtistthheaDrOeiCnhtiaegnrhanllayytsiibosinoadltelogyrsahrdoeawcbolgtenh.iatzed"LOIEGCHDT WSAcTrEeRe"ning E & BC) FFF aLEPOS RT ABSTCRAoCT,m200250 word) Tis snvact formations deed oytoTemi Commansioms Som oc sAT"hnoLianIslcGylHsuTsistsiWu'vAdeTyElaRynu"dsdedeBsmruoaptnnhpdeslterm"aeMtnoetdailftiheepdaerxOatlEelCneDlsiSvcserteeebrniiiolndegegcrToaendstatrboilwlsiitthcoy.DoOfC lFCe-v3e0l1s7.of FInC-21046dadyesg,rAaFdFteFhedpdrbyiodsus9co0t8lsv:eadndoFrFCgC-a-2n3003i1,c7 c0aw-ra2bso0n6'9,45(DaOnCg) nTdeohgetradpduaeerda.ltloelcECh-es2mt0ie3craillsehoorwceodpnhtyr9so3il3csaDlOp.Cr-opdrveoegcdreastdshaeatstiostnuhcihsinaDgO2C1 dlaoysss. was maadtseorripatli.on, volatilization, or precipitation of the parent HE SRa0 002749 nls r BG am TECHNICAL . REPORT SUMMARY TO: TECHNICAL COMMUNICATIONS CENTER -- 201.20 pane sorsn bo ss ofapr nd cio 76) FL FC) = 6/30/80 "Environmental Laboratory (EE & pC) 0535 Commercial Chemicals Division 9970012600 Biodegradation of "LIGHT WATER" Products in OECD Test-6/80 040 John A. Pignato - Commercial Chemicals Division - 236-24 (01) emEoriRac A. Reiner - Environmental Lab (EE&PC) - 21-BW (63 SP47816 Ce None ecomvy - See 3M 8 oom Environmental T coma Lab Request No. 5541S mcnameALy 31 on re rs Ke eroroS : romau CURRENT GRIECTIVE: ost To To use the internationally recognized OECD Screening Environmental Tpersotducwtisth aDreOChiagnhallyysbiisodteogrsahdoawblteh.at "LIGHT WATER" L(EaEbo&ratPCo)r]y SEE Rc-203 rE REPOSRTNABESTRnACTe: (2a0s0.:250word) Tos somvectinfGoviromteadtoyioneashen Sommers Some TOC gonclusively demon TAhniaslyssitsu"dy aundsedsuptphelem"eMnotdailfiepdaraOlElCeDlScsrteeerniilneg cToensttrolwsithtoDOC strate the extensive biodegradanitity of "LIGHT WATER" Brand AFFF products: FC-3017. In 14 days, the dissolved FC-203, organic FC-206, and carbon (DOC) levels of degraded. FC-206 degraded by FC-203 showed 93% 90% DOC and FC-3017 degradation was 94% in 21 days. The not dpuaeraltloelchesmtiecraille orconphtyrsoilcsalProPrvoecdestsheast-stuhcihs DOC as loss was material. adsorption, volatilization, or precipitation of the parent ste: --Fe-2,e MFP eo Sin AplyeaShreds 0 w[ahSt Eover ST J oe 002750 . -2- 3 BIODEGRADATIONIOnF02"CLhIGTHETSWTATER" PRODUCTS INTRODUCTION hbieode3g4raEdnavbiirolnimteyntoafl "LLaIGbHoTraWtAoTrEyR"chopsreodutcotsattuesmipntg ttohedeOmEoCnDstsrcarteeenitnhge nEentvhiordonmbeenctaaulse Ltahbehatsesthadhasexwpiedreienicneterunsaintgiontahle aOcEcCeDpttaenscte,asanad the Cpaormtpilceimpeanntt thien eanxisitnitnegrnaBtOiDondaaltaritnhgattesshto.w tThheesseeprroedsuuclttss wtiollhave a high degree of biodegradability. TchaerboOnE.CD Fteosrt tihseserunwataetr-2m0i-s2c5i0bCleand"LIitGHmTeaWsATuErRe"s opnrloyducdtiss,solwvheidchoragraenic dntoeetgsrtaiendxgap,teicottneh.de OtTEohCeDvoTltOaeCtsitlainizasel,yasnipsraepcpmierptoihptoraditaete,evenomretmhbeeoadsuardfesosorrbmteehdaesudprueirrinfnglguoritnoattaeld portion of these products. METHODS AND MATERIALS FHetohodls lantodheCwSoneidpittneimogbnesr-19W,ade197A9., ScvheerislionperoffortmheedMotdhiisfietdestOiEnCgD aSctrteaecnhiendg (TAepsptenwdiixth1)D.OC Analysis{l). A copy of this method is ) Raevdauicltaibolnesshiankitnhge esqcuailpemeOnft.theFitveesthwuenrderedn-enclessEarrlyenmtoeyaedrapftlasitksto rceeppllaacceedd 920-0limtle,r aflnadsktsh,e s25a0mplmle osfizeinwoacsula2t5,ednontutr30ienmtl. solAsutiionnthe pErielstcrraitebedforproDcOeCduarnea,lystihse.analyst used only the last 10 ml of sample wAitchailnibrtaheted20c-h2a5r0tC rraencgoerdedrurimnognittohreed28-thdeaytetmespte,rateuxrceepwthifcohr sata3y-4edhr. pheerairodthwehehnighitenrdeaocfhedthe25.r5a9nCg.e (T2h3e.5-t2e4m9pCe)r.ature was most frequently Chemicals - All chemicals were reagent grade unless otherwise noted. oTfheAn3tuwe"rLpIGmHaTnuWfAaTcERt"urep.roduTchtesirusleadbelweriedenstaimfpileeds otfhemcoamsmerFcCi-a2l03maNFtPe,rial FC-3017 Lot 2303, and FC-206 (FM 3824) Lot 2330 10/79. gThreadehydhryodqruoiqnuoinneoneuse9d8.5a%s, thLeotca1l0i0b14r7a.tionFocuormpcohuenmdicawlassAulpdprliychhourseeasgent pWerreescrciobnetdactbeydthien ManodiaftiteedmptOECtDo oSbctraeiennintgheTe9s9t.,5%bupturethihsydrpouqruiitnyonies SZpepdaurceendtypurnoittyrweialdliyhaavvaeilnaoblseignifnictahentUSeAf.fecWteonexpreecsutlttsh.at Tthheis ) tfhuepiurritpireessenhcaevecnoouldappmaarkeentonliynhiabittroirviyaleffcehcatngeonimnicTrOCoormgeaansiusremmsenatnsd. 002751 oa wwaasterSt.usePdaulincittnye wparteeprarpaatsisoendofthraollughsolautciaornbso,n beexdc,epmtactrhoepoirnooucsulum, ) atnhiroonuigch ares0i.n2-ubend,filatnder.2 miTxheids wbaetderdewiaosnizaelrsso, usaendd ttohenmakfeilutpereldosses etxopeerviampeonrtatieonns.uredStcoocknssiosftenwtatewratecrolqlueacltietdy.at the start of the Itnhepprreepasrcirnigbednut3r3.i4entg OsFoluNIt,iUoInPsO,4-22161.340, g3o6f.3agnhOyfdrCoauCslyN-a3p1l1i5P00, rerpelpalcaceedd 2i7d.e5ntigcaClaCly5. tho`sheesereqrueiprleadcempeynttsheyOiEeClDdedMetshooldu.tioTnhseaonpdticoonnaclentyreaatsitons e(x1t.r6a.c1t.2(so)l)u.tion`Thweas100usemdg oifn pFlea-cceheloaftetheusevditaimninthesolturtaiceonelement sanodlut70ionmgcoEnDsTAi)s.ted of equimolar amounts of FeCl and EDTA (30 mg FeCly TSeesrtveCdoancsetnthreabtaisoinss =foDrOCadmjeuasstuirnegmeinntistioafl staemsptlecosntcoecnktrdaitliuotnisontso acpopnrcoexnitmraatteiloyn 4i0n mtgheofracngaerbornecpoemrmenlditeedr.by TthhiesOEisCDthteesth.igheUsste of this mheiagshurienmietnitasl. coTnhceentlroawtitoonxiciintcyreoafsed"LIthGeHTsWeAnTsEiRt"iviptryodoufcts& DtOoC removal microorganisms unlikely. made significant inhibition at this concentration Acdajrubsotnnepnetr olfitheyrdrwoagsuidnoonnee,bythweeicghatlibbraastediononcoimtpsouknndo,wntocar20bonmg of ) concentration of 65.4%. Tcwoorbrelcatnikoncso.ntrols, instead of 1, were utilized in making blank DOC 1I.no6c.u2l.u1nan-dTh1e.6.i2n.o2cuOlfumtwhaesOE5C0D-50temsitxtuusriengprferpeasrhedsoialccofrrdoimngE. tAo. steps Rseliundegre'saegraartdieonn banadsintheatsutpheernSta.tanPtaulofMaetrsoampPlleantf.romTahne afcitlitveartepdaper cusheldorwianse-fWrheaetmawenlkl54w,atearn.d the water for- soil extraction was aSsterilecCoosterilennttrorlosl-sRefpolriceaatceh vteessstelmsatceroinatlainainndg th4e00cmagl/ilbraigtCiloyn served choamnpdoluinndg. ofiltahnedlvinigabOlfe ctuhletsueresst.erilTeheyconhtardoltshewassameideinntnioccaullumtoantdhe s0-ampalnidng28f-rdeaqyuesnacwyp,lesb.ut the analyst only made DOC measurements on the Sample Preservation - The sample preservation method used was that dpsraromeppslceorfibtecodon<pcbieylnt2tr,haetaenTddOC HsCmtLaonruitfnoagctthtuehree1r0s(a4mm)lp.lefsiTlhtueenrdemederthsroaedmfprliiegnsev,roalvtbeirsoinngaidindnignvtgihael1s pwirtehseravlautmiinounmmet0hiold-.lineTdhecampasn.ufaTchteuremrethionddicisataens etfhfaetcttihveemethod can J pshttahbaillaitzee, caalirberaadtiiloynbsioolduetgiroandsablmeadematferroimalp,otafsosriusmevehryadlrogmeonnths. 002752 Soa in 0 Since the necessary acidification in this preservation step in the TOC analysis protocol, method was also its use was the a most dpmeorsnactcrhtiibcoeafdl thaienndptrhaeelslOeoErwCevDdatimeoeltnihmooidfn.attihoAeLnLsoafTmOplCtehsea.naglCylsyespwreerseervmaadteionwittheicnhniaque DIonnsrtmraunmenDtCs-52aAn.d per liter. eqIutsipmseenntsi-tiTvhietyorlgiamniitc iscarbbeotnweeannal1 yzaendr 2usmedg wOafs caarbon Tpthlieungesss.taonpdGpeerlssmtaonrfeodr0.2tinheudmerimeoeanmcibtzrieaodnnewfalftaieslrkt,esrsws,eerrev(ePdcalrettaonH,of.iplot6re4o8ru1s4s,)ampbploleiaslsetdifcor3 foDaOCm analysis. G(lCahsrsowmaerregeRc)leafnoilnlgoweidnvobylve6ddesiooankiinzgedinwatcehrromFiicnseasc.id cleaning solution RESULTS AND DISCUSSION Tcaobnlteain1 stuhemmaarcitzueasl function of time. dtahtearesshuelettss oafndtphlisotsstuodfy.theAdpepegnrdaidcaetsion1 aasnda 2 All 3 "LIGHT WATER" AFFF products degraded nearly completely. 3 Percent Degradation of HydroquiTnAoBnLeE 1 and "LIGHT WATER" APFF Products FC-203,ModFiCf-i2e0d6,OEanCdD FSCc-r3e0e1n7ingWitThestTime in * Degradation at Day: Product 1 14 21 27 28 FC-203 FC-206 13 23 85 90 9943 9931_ 9923 FHCy-d3r0o1-7 8397 992a 9976 996 9935 quinone ovIrenrpytrheeucniclapisiketealtyofiotnhtahectauhpsihegydhsliyctahelwatmleeorasnsssOoflsuubcslhoeluabs"lLeIaGdTHsOoTCrpWtA(iTDoEOnRC,"). pvroTolhdauitcsitlsii,sz.atiitoni,s steusbtsstaonftiattheed 3Mby EnthveirornemleanttiavlelyLabhoirgahtoorxyyge(nFCd-e20m3andBODob5s/eCrOvDed= FC-206 BOD5/COD = 0.5). 0i.n5,BOD- J "e"TvLhiIedGeHsnTtceeWrAiTltEehRa"ctonpttrhroeodluscotdlsautblaies inTnOoCtTabdlluoeess2tofprarodomsvoitrdhpeetiftouenrs,tthevsroalmapstluieblssitzacanottniitoaanli,ninogF psraemcpilpeistaetxicoenp."t tThhaetsethesyamcpolnestaiwneerde hHgaCnldpledto ipdreenvteinctalmliycrtoobitahle gtreoswtth. 002753 SoA s- ) AnttohetthiaenmieatnijdaolrofDfOaCtc.hteor,T2h8u-astdaylloesatssetstoffpoersroilnouodbn,lmeettTahObeCoylibszyteidltlhe"scLeoInGtpHhaTyisnWieAcdTaElRn"eamordleysawllas cnootmporneemnotvse. "LTIhGiHsT cWoAnTtErRo"lmdeoteasbno'ltitepsrovien tthheattpehsytsircuanls,prsoicnceessenso did mfeotrambaotlioinsmofoccluersrsedwatienr tsheosleublsetermialteericaolntsroilss,unbluitkeltyhe bceactauasbeolic* catabolic products are usually more polar and smaller. TABLE 2 DOC Loss from Sterile Controls Product % atDODCayRem2a8 ining Cc--220063 iicy-a3r0o1q7uinone 9914..32 8787..15 - Adsnalyiogf0hft-lpywrhiiobtrreowtnpoirsefhci,ilptieatsraitnwegasffotorhremeDdsOColinuatniatolheynsihisyn.drtoheqTuhiehnyodpnrreoeqcusiitpneiortinaleteescwtaoesnritlreol on ) OcatEoCntDlreoaelsxtpearfiitnemretnhte2.1prdeaTyshsei.snceaTphpoifasrelinsgtuCgLgyt,eesntdtsehnrcotyuhgahtofouhthyyddrthroeoqqucuioinunoronsneee iostfonotthest2a8b-ldea,y sipnoanptparnoeporuisaltye precipitation cfoonrtmroilnsocloumbploeundhumfuors-ltihkeeOmEaCtDertieaslt.makIetss piatrtainal with HgCly also casts some doubts about the maeptphroodp.riateness of using the HgCl, preservation procedure in the OECD concLusToN Tpihrneod2up1crtedsas,yesntFuC-ns2dt0eu3rd,ytchFeoCn-2cc0lo6un,sdiivtaienoldnysFdCe-om3f0o1nt7sh,teramatoredesifniteehadartlyOE"cCLoDIGmHpSTlcerWteAeeTnlEiyRn"gdegTresatd.ed REFERENCES (1) To1er97sg9ta,innigTzeastPtiroonGguriafdmoerlEiExncpeoenrotfmoirGcrotCuheop-MooopndeirDfaeitgeirdoandOaaEtnCidDon/SDAcecrveceeulnmoiupnlmgaetnitToensC,themwDiiectcah.lsDOC Analysis (Level I) (H. G. Nosler) Revision of Sept. 19, 1979. (2) Dohrnan DC-52A Operating Manual, 4th Ed., 1978, p. 3-1. . Appendices: 12 -- ODaEtCaD TSheesettsGuidelines (Sept. 19, 1979) h) 3 - Graphs * Cnoalteacbuolleiss.m is biologically facilitated breakdown to less complex 002754 3. APPENDIX 1 : | Tokyo, December 1st, 1979 D C 118/79/1nt. OECD - Chemicals Testing Programme Expert Group C, Degradation/Accumulation Modified OECD Screening Test with DOC Analysis 002755 Bes Test Guideline C 118/79/Int. Tweistth DGOuCideAlnianleysifsor the Modifid OECD Screening Test Date of last revision: Sept. 19,1979 Levl I test for ready biodegradability 1. Prerequisites sItoluhabsletoinbetheknocwonncwehnettrhaetriontherantgeestemmaptleoryieadl inisthe test (corresponding to 5 - 40 mg DOC/1). 2. Guidance Information Kpnroowpleerdtgiecsofof thtehebatcetsterimaaltertioaxliciitsymootr uinmehqiubiitvoorcyally ) creoqnudiurcctdionbutofctohnestittesutt.es useful information for the 3. Qualifying Statements Tuohrlegtaimnmeiatctheocdobmipoiosduensgdursia.tdeadbItilfioirtsyutnhoesfuiwmetaaetsdeurrfesomorelnuttbhleeo,fbiotnhdoeeng-rvaaoedlroaabtbiiiclleity cvaluation of mixtures. _ 002756 Bar Ds. Groa/s Sept. 19. 1979 Modified OECD Screening Test with DOC Analysis Preamble It has to be realized that the following procedure for the modified OECD Screening Test has to be ) regarded in some points as provisional since se- veral important features such as the calibration compound and the new test duration of 28 days are completely untried yet. However, since the test constitutes a modification the official, widely practised and well accepted OECD Screening Test for the biodegradability evaluation of surfactants there should exist a good prospect for success. J 002757 D4 D Septemder 19., 1979 OECD Chemicals Testing Programme Test Guideline for the Modified OECD Screening Test with DOC Analysis 0. The test procedure constitutes a modification of the OECD Screening Test (OECD Environment Directorate, Proposed Method for the Determination of the Biodegradadbility of Surfactants Used in Synthetic Detergents, Paris 1976, and council directive of Nov. 22, 1973, on the approximation of the laws of the member states relating to methods of testing the biodegrada- ) bility of anionic surfactagts (73/405/EEC), Offigial Journal of the European Communities No. 4 347/53 of Dec. 17, 1973) for the application of the dissolved organic carbon DOC analysis. 1. Method 1.1 Introduction: Purpose, scope, relevance, and application of test and explanation of-limits. The purpose of the method is the measurement of the ultimate biodegradability of water soluble, non = volatile organic compounds in an aerobic, aqueous medium at a starting test concentration correspondirg to 5 - 40mg DOC/1 ( In order to avoid inhibitory effects it is in the investigator's own interest - -2- 002758 oy d Re to choose as low a starting concentration as his analytical capability permits ) 1.2 Definitions and units 1.2.1 Definition of biodegradability oe | LL oom] % | 1- L c, = , |i x 100 bl, where Dy = degradation in.percent DOC-removal ) at time t Cy = starting DOC concentration of the culture medium (mg DOC/1) Cy = DOC' concentration of the culture medium at time t (mg DOC/1) Cy,= starting DOC concentration of the blank (mg DOC/1) - Cpy= DOC concentration of the blank at time t (mg DOC/1) 1.2.2 Units The degradation is stated as the percentage DOC-removal within 28 days with respect to the test material ( % DOC-removal ) 2 002759 LS @ ) -3- 1.3 Reference compounds 1.3.1 Calibration compound The calibration compound used in this test is hydroquinone at a concentration corresponding to 20 mg DOC/1. Hydroquinone has to exhibit a DOC-removal of 260 % within 28 days, otherwise the test is regarded as invalid. 1.4 The orinciple of the method . A predetermined amount of the compound is dissol- ved in an inorganic medium (mineral nutrient solu- tion, fortified with a trace element and essential ) vitamin solution), providing a concentration corres- ponding to 5 - 40 mg DOC/1. The solution is inocu= lated with a small number of microorganisms from a mixed population and aerated at 293 - 208 (20 - 25C) in the dark or at least in diffuse light only. The degradation is followed by DOC analysis over a 28 day period. The procedure is checked by means of a standard (hydroquinone). = A control with inoculation but without either test material or standard is run parallel for the deter- mination of DOC blanks. 1.5 Quality criteria 1.5.1 Reproducibility The reproducibility of the method is appropriate oo for a screening test which has solely an accep- ) tance but no rejective function. . 002760 97, 5 4- 1.5.2 Sensitivity The sensitivity of the method is largely deter- mined by the sensitivity limit of the organic carbon analysis which is 0.5 mg C/1 at the present state of the art. - 1.5.3 SAppepcliifciacbiltey,forapptlheicabbiioldietgyradability evaluation of water soluble, non - volatile organic compounds. 1.5.4 Possibility of standardization ) The test version with specific analyses for anionic and nonionic surfactants is standardized as "OECD Screening Test". 1.5.5 Possibility of automation Parts of the test, e.g., the analysis,can be automated, although hardly the total procedure. The procedure is, though, well suited for being operated with whole series of test materials. 1.5.6 Costs ( in 1978 Swiss Francs ) 1.5.6.1 Equipment Glassware 2000,- shaking machine 6000 = 20000,-. _ Carbon analyzer 42000,- Miscellaneous (PH meter, balance, J provision for air conditioning) 5000,~ "gw ! 002761 @r ) -5- 1.5.6.2 Person - hours 10 1.5.6.3 A(pipnrvoexsitmmaetnets taostaslumceodsttopebre test 750, = 1000,amortized) 1.6 Description of the method 1.6.1 Reagents and materials - 1.6.1.1 Deionized water Deionized or distilled water free of substances (copper in particular), for use as a solvent. Water which has been zed by distillation or ion exchange is toxic general ceionisuitable. ) A high purity of this test water is necessary in view of the DOC analyses in the concentra- tion range of 0 - 40 mg/l. The contaminations result from inherent impurities but also from the ion exchange resins and microbial devel- opments (bacteria, algae under the influence of light ete). Only one water charge must be used for one test series which is to be controlled beforehand by DOC analysis. If necessary, suitable water may be gained by UV irradiation or other means. 1.6.1.2 Nutrient solution Mix 1 ml each of the following solutions (a) o (f) and make up to a volume of 1 1 with water 1.6.1.1 J -6- 002762 3 -6- (a) KH, PO, AR. 8.58 K HPO, AR. 21.758 NaHPO, . 2 HO AR. 33.4 NH C1 AR. 2040 & in 1000 ml of water 1.6.1.1 the pi value should be 7.2 (5) 22.5 g of MgSOy . 7 H0 A.R. dissolved in 1000 ml of water (3.3.1) (3.3.1) ) (e) 27.5 g of CaCl, A.R. dissolved in 1000 ml of water (d) 0.25 g of FeCl, . 6H,0 AJR. dissolved in 10CO ml of water (3.3.1) This solution is prepared freshly immediately before use. (e) Trace element solution MnSO, . 4 H0 H380, nS0, . 7 H0 (NE) ghog0,, 39.9 mg (30.23.mg MnSO, . Hy0) 57,2 mg 42.8 mg 34.7 mg (36.85 mg (NgioK0,,,.4) 0) Fe = chelate (FeCly,EDTA) 100 mg water 1.6.1.1 1000 ml B Sterilisation of the trace element stock solution J a3 393 (X) (220C), 2 atm., 20 min. tT 002763 `a . @n ) -7- (f) Vitamin solution Biotin 0.2 mg Nicotinic acid Thiamine p-Aminobenzoic acid Pantothenic acid Pyridoxamine 2.0 mg 1.0 mg 1.0 mg 1.0 ng 5.0 mg Cyanocobalamine Folic acid 2.0 mg 5.0 mg water 1.6.1.1 100 ml The solution is filtered sterile (0.2 um). Instead ) of solution 1.6.1.2 (f) 15 mg of yeast extraxt may be used per 100 ml of water 1.6.1.1. 1.6.1.3 Biodegradability standard Hydroquinone 99,5 DAB Erg. B. 6 1.6.1.4 Mercuric chloride solution 1 per cent ofHell, in water : 1.6.1.5 Shaking machine accomodating 2 ltr. Erlenmeyer flasks either with automatic temperature control or used in a conrtant temperature room at 293 - 298(K) (20 - 25%) 1.6.1.6 Narrow neck - 2 ltr. Erlenmeyer flasks. (Creased fluted _ flasks are recommended) The flasks must be carefully cleaned with, e.g., alcoholic hydrochloric 2 -8- 002764 y -a- poe -e use, rinsed and dried in order to avoid 1 .nation with residues from previous tests. ~t .lasks ist use also since have they mtaoybebeclceoannteadminbaetfeodr.e their 1.6.1.7 Membrane filtration apparatus 1.6.1.8 Membrane filters 0,2 um - 1.6.1.9 Carbon analyzer 1.6.2 Incculation EIther of the following three alternatives may be used as inoculum or a composite sample thereof. J 1.6.2.1 Ino:ulum from secondary effluent The inoculum is gained preferentially from a secondary effluent of good quality collected from adortersetaitcmenstewapglea.ntThdeealeifnfgluewnitthmuastprebedomkienptantulnyder aerobic 21d use. conditions To prepare in the period the inoculum between sampling the sample is filtered through being ciscarded. a coarse filter, the The filtrate is kept first 200 ml aerobic until ised. The inoculum must be used on the day of collec= tion. 1.6.2.2 Inoculum from soil 100 g of soil (fertile, not sterile) are suspended _ in 1000 ml of chlorine-free drinking water (soils with an extremely large content of clay, sand or " 7 soursgpaneincsiocnarbisonalarleoweudnsutiotesde)t.tleAftfoerr stirring the 30 minutes. -9- 002765 . @r 9. D The supernatant is filtered through a coarse filter paper, the first 200 ml being discarded. The The filtrate inoculum is aerated immediately and must be used on the day of until use. collection. 1.6.2.3 Inoculum from a surface water An The inoculum sample is is drawn from a suitable surface water. filtered through a coarse paper, the first 200 ml being discarded. The filtrate is kept aerobic until used. The on the day of collection. inoculum must be used 1.6.2.4 Composite inoculum Equal volumes of the 3 inoculum samples are united, mixed well, and the final inoculum drawn ffom this mixture. tT ) Tohfe thseuitsatbanidlairtdy ohfydrtohqeuiinnoonceu.lum is checked by mears 1.6.3 Conduction of the test 1.6.3.1 Procedure The test materials are evaluated simultaneously in cuplicates together with the standard (1.6.1.3) and a control test with inoculation but without either test or standard material for the determination of DOC blanks. The standard moval within material has 28 days at a to attain 60 % DOC re- starting concentration corresponding to 20 mg DOC/1. If (60 % DOC removal 7TRISTIRIt1sbased on preventexperienceWTR are achieved the whole series has to be discarded +) tthheis 19lidniaty ovrerseivoenn ooff tthhee stetsatn.darAdrmeivgihstionhavoef D) to be considered after the accumulation of experience with the new 28 day version of the test. -10- 002766 on. . : ) -10 - A stock solution of the test material in water (1.6.1.1) is prepared. So much of this stock solution is added to the nutrient solution (1.6.1.2) that a carbon concentration of 5 = 40 mg DOC/1 is attained. The starting concentration Doc/1. of the standard hydroquinone is, though, 20 mg Two reaction vessels (1.6.1.5) are each filled with 900 ml of the nutrient solution and inocula= ted with 0,5 ml/1 of the inoculum (1.6.2). The opening of the vessel is covered with, e.g., alumi- ) num foil in such a way that the exchange of dir between the flask and the surrounding atmosphere is not unduly impeded (Cotton wool is unsuited because of the DOC analysis). The vessels are then inserted in the shaking machine. The tempe- rature of 293 -298K ( 20 -25C) must be maintained unchanged during the test, and the vessels should be shielded from light. The air should be free of pollutants and vents ete). toxic materials (chlorinated sol- In the course of the biodegradation test the DOC concentrations are determined in duplicate (1.6.4.2) at the beginning (day 0), and on the 27. and 28. day. Three additional analyses have to be performed or J a1 - 002767 . = ) -11- in rather regular time intervals (~7., ~21. day) ~1i., and The and analyses are evaluated. registered in the attached form sheet Only the necessary volumes of culture medium may be drawn for each determination; however, they have to be large fugation enough for preceeding the the mcaermbbornandeetfeirlmtirnaattiioonn.orThceentlrait-ter requires differing volumes for the different instruments. Evaporation losses up by adding water o(f1.6t.h1e.1c)ultiunrethemedrieuqmuiraerde to be made amounts. ) The culture medium is to be mixed well before withdrawing 2 sample. Material adhering to the wall of the vessel has ftoiltberatdiisosnolovredcenortrisfuusgpaetnidoend before has to bseamdpolnieng.imTmheediamteemlbyr.ane The filtered or centrifuged samples.have to be analyzed on the same day, otherwise they must be preserved with 0,05 ml of of nutrient the me HgCly dium or solution (1.6.1.4) by storing them at for 2 = each 4C; 10ml The bexihoidbeigtrsadaabdielgirtaydatteisotn isratvealiwdithpirnovitdheed sptheecifsiteadndraarndge. Tmhienertaelstizactainonbe isfiancicsohmepdlibsehfeodr.e the 28. day if complete All steps require pipettes etc. but great care and not sterility. cleanliness of the vessels, - J -12- 002768 Ds J -12 - 1.6.3.2 Calculation of results The degradation at the time t is calculated from the determinations of the DOC concentrations at the beginning (Cy) and the time t (C,) according to Dr |I 1m em Co = C2oyM, | lxi100 . | % "Ca, | where D, = , = Cy = Cpy = degradation in per cent at time tT measured starting DOC concentration of the inoculated culture medium (mg DOC/1) DOC concentration of the culture medium at time t (mg DCC/1) starting DOC blank of the mineral nutrient solution with inoculation but without test material (mg DOC/1) SY = DOC blank of the mineral nutrient solution with inoculation but without test material at the time t (mg DOC/1) The degradation rates are calculated to the nearest 0,1 %. The means of theDy values are calculated ard J reported to the nearest full per cent. Results tis. 002769 @-1 ) "13 - ending in 0,5 are rounded up to the nearest whole nfuomlbleorw.edThgerapchouircsaellyof inthea degradation test diagram as shown is in the attached example. The results are reported on the attached data sheet. The results of the degradation test are valid condition is met that in the same test series standard yields = 60 % DOC-removal. if the the 1.6.4 Analytical means 1.6.4.1 Membrane paration filter of the 0f:i2ltpemrs,: 25 mm (1.6.1.6). membrane filters Pre- are impregnated with surfactants for hydrophilization. ) Thus each filter contains up to several mg of soluble carbon which would interfere in the biode= gradability determinations. Therefore the filters aorreganpiucrifiinetderfferroemncseusrfbayctabnotislinagnd thoethmer3 soluble times 1 hr each in deionized water. These filters may be stored in water (1.6.1.1) for at least one week. Other membrane filters are suitable if it is assured that they neither release carbon nor adsorb the compound in the filtration step. If at the samples are centrifuged, 40 000 m sec ( 4000 g) for t15hisminhuatsest,o bperedfoenreably in a refrigerated centrifuge, in any case <40C. (Remark: the tion at very dliofwfceornecnetnitartaitoinonTsOC:dDoOeCs by centrifuga=- not seem to = ) work well or carbon assincpearteitofherthenotbacatlelribaalcteprliaasmaareisrermeodviesdsolved. Astmalhlighienrocutlesattiocnontcheentrcaetnitornisf ug( a)t1i0o n mg e r C/1) ror and seems the to same be comparatively small ). 002770 . Form Sheet for the Modified OECD Screening Test @- - oo A: Controls: Tot 2 00 renal ueriens finociton ) Te : 7 - =het - TT Ei T1 Pie nye 2 Flask of hae.|] Fr = omen for day x HERE 00 @r . d -a 1.6.4.2 The The DOC measurement sample withdrawn frem the culture medium i(mamboeudtiat3e0lmyl)in isthecefnitlritfruagteidonoarppmaermabtruasne (f1i.6l.t1e.r6e)d using the "The first membrane 20 ml of filters prepared the filtrate are acc. to 1.6.4.1, discarded, : `The DOC concentration is determined twice in the remaining filtrate (about 10 ml) by means of the TOC/DOC instrument (1.6.1.8). If the filtrate cannot be analyzed on the same day it has to be y c(omEnCs/e1r)vedobatcaci.nedtoar1e.6r.e3.g1i,steTrheed DOoCn measurements the `attached data sheet and the DOC concentrations of the culture medium and of each sampling time. the blanks calculated for J 002772 * : APPENDIX 2 te - or t resul3tHsEnovfirtonnemeMnotdailfieLdabOor6a2torSyirDeastnainSghTeeetst : LsAonbealyRsootfg:ueSnuatrdtweo.o:T_ASsenHorST ] ES pHIranieaooscruuarlMtauetimdoc:reTT0al0l!:s(o0lAo)Nf:STTaned sTnseosRtmmacPRthaeltrFaioraerTlFe:2le:0s(CATAL,AFoTcLN0on0ECd0sPrUy LASF sTluyentESTats SteTnrodneard Material: sunt hydroquinone, o 98.5%, Lot 100147, Aldrich en Te So SEE ora Draeneimalcloslwestensier Cross slant A. Determination of voc! of Yost Material; WA hstocdkatonsiozleudtiwoanteorfs the test material was prepared by diluting _ 1170 mg to a final volume of 500 mi TRI TT TE) This esi was ved co calculate che seconsary on | re iin SF Saget! to prepare cular 5. cordon veterminations; % BEST COPY AVAILABLE nCFeloatnsockr.,iaonmfe/tftne"at||Co{TFonteFSuelatatastmeadteomrauital O90C)~ conTc. aW fter x ders E Incubagtion, mal] ) onan mtestet Inoculum MSToiosnTtearcamtloanrnsuethrrioeenTut|] but with 282 40.0 F pT eet eee aT mm alefooe [on fee 282 40.0 | Fare r RR ppnAmT ePTRr oLee fSreSsxET rs Fe A TE fumeo [e77 []7 os [eerHi e Se rTorr eTee s oTeTra 11sg |-02 |04 [12 0.5| 00 [orm froculm signe TT ve C. gesluotioofn fev vata: To Jo [isJoe Len ra rr > Herertertreteary =o.T Cones |14 |-00 [od |Z [06] 6 Fro redatio=n%DOCgesoval after xdeyy Tresbetion FRI UA. L' [esTenefens[Mf3a0ns| talmoienvesreoviiemd mInsthme csal.eutastioon,s. [=[rz Jos[esJai[as] J Pave ~ --p---- 1. 2. The test material 13 completely soluble In water. 00 anslyses performed more then tice on the sam sTahmeprleefowreer,e trhuenTfOoCr=qu0s0lKl.ty assurance purposes. 002773 Lob hosuenc vo, S541 8 rest30stoGuFtrhoemarnacee)16L8aboBreaestoreyraGsatiengSheTeotse$SaCataetyaoatf:SStVA aardsoao.E FTcnn EFrS y or 235 m/77_Standard Materlals_bydrogulnons, 98.5%, Lot 100147, Atdricn pCTehhcsrcoournreidMm:aTTycsseorrotfSaTnoedsnntoramatetarBaElSTsEASVRoratraonicrCatcanuas glgfon rilosLenientte.rSromemnt slant A. Determination of oe! of Test Material; A1tshtocGkatonstoileudtiwoanteorfs the test material wes prepared by Logo diluting 4060 mg to a final voluse of So 500 ml TSStoocThk sSolutTion I|stTocnkaTslelutiIon |TtestnEamaltes]rial | ihd miesni rtooosffusounmnm easlatvainepdteiseelsos oco0aclPocsruelPitreetnheenat!oceensss 2,120 93,900 BEST COPY AVAILABLE 0. Carbon Doterminstions:? `StMoibnueecrialornnwuatirnient na ) erm leeter sa for or Inoculum or | mTeiteesr,ian ngtt | [iSnF fSaratemsaecoroion ig) TS Eg 20 Yo.0 [er1923130 E5156159 1350 B 5 Pp T t r ca eS cer -------------------- Y2 Yop BE [CefrrsEPHEer ErT IEs EAe a ATy SR rTsoe rd 1 = lle oa eo HSionheorratlonnuwthrslhaanntt]] CeI PA TTCa haa [w | Too = oui[eel C. Evalustion of Rev date; Er r r erTe ey 5 II = Colne = 10Taer e re e oe ET 14 [=o v2 [oe | PE |i eo ewaela [] m |97 | gmmpeseme [a ro[os[353 [92 | EAT vere aad In th cateut Tons J lave" 22 1. 2. The 00K atneasltysmeasteprairaflorImsadcosmoprleettehliyn stoullucbeleoninthweatsearm.s STaheeprleefovreer,e trhuen TfooCr =qu0aXl.ity assurance purposes. 002774 } co en BE 3M Environmental Laboratory Data Sheet Date of StartofTest: S-1-B0 pr AERARR eie m eye A. Determination of voc! of Test Material; FEITE Ny: TEoe | Di Ea ne cso A stock solution of the test material was prepared by diluting L245mg to a final volume of S00 m1 tite . 5 [EE Mineral nutrient. ton movertat and with St [ers 20% _ 40,0 208 | geo or _ BEST COPY AVAILABLE Te coe shes dv amg ;_--Fede Bree Ter 7] Zo po Isp Ae TET eT rr EA tree Re Lt tEo ELS BE ees r---------- EE arms [ell[eie s forle mmr Miners! nutrient] | _ 1emer le 177ToTTos[7s169| t6eres7 -- EEE a [[ oct W[o ou[0a]ec] C. Evaluation of fer vata: Cliawe= | 19 [00] 0 | 72 | 06 | o [Th oTpiRn E1mfte i T Om T |ss snea s. J [[ = [s2oJ [Jaoasae[Joosa ss[aenfa]oa aesweesa|||toC TmEs=eSay 2rd1CsmT (0o1amwsiaessim [==157 [04 Jae[2| ar] eT ere weere t5 meetets aetde vere r Toretoresr m2s,y sr . to os 3805 TE roR s SE enayTYE t Dateof StartoE fTerr TB BEST COPY AVAILABLE ER a eT heoretical JOTTen etre TAITE ee BATACTA CARBON ASSUMED 1D a a BC coSOLUBLE anORGANIC CARBON, 1 Asisetmctksstttuosnioan1o0f!toht sunssstaartrasassrsbyaa1aaitns ot Fovt of a1 Ty eheT [orn veton| conrae|| Tei nt cctut cn econtry [TT evacuarion or causramoy 8. Carbon Determinations? COMPOUND-- SEE STANDARD MATERIAL ABOVE . St eranTom | coe onan rei wr Mineral nutrient J mnrn groia 306 | 200 PlFeoT eEZ fEZ ey3sT l--e2 E1r0 R--1 t1 T1i1e7y5 Tr3 [77 | 306ac r1|2m27en00 |Pm [ r Ema Ee se EEfRe ar E[eE2E7e rtTieetEe[ie mmr |mers bTut wo ith,e] ani [or foo fos foe foes C. Galuosfthoiecourre; -- EEer LEregloz| 04 | 12 |os [0.4 1 HEIelLe Tard =o Con=e Sc [1g |01 | 04 | 12 [06| 0 [TR] opens1 ontSyoyvee | sent seit in [ses [= [907 Joa Jono oon yar gro | lerc|laonwa| IsemmTtorevtmAedossLwwom seoe Jf Tea fez[orfou[95 | 21. oTron nesatmsevarritalom1escnmpaeicetyatseetne28voeere, sTreteorn e1 +e5a.ti EES FE 002776 EEE re SSgE EsmT ns hptelreen irT oanr nn SH Eimna ds . Ee ee A Ee E er EE ecwLab Request NouA: m55e41n'ss peas wee a Soin oo) -- = -- ET -- E --_-- TE T e = ges " Eee ees A = mre a = iE a 70x heed hm EET Eos Foe] Mf epee a =} Al I e ge re e eee e e e ee e e EE ry e Led a- fy E Cme mf e ee sr epe aee e e | ---- Ep e Ee e e e p eeoTe h ee &g iirs 6 ORYS IICUBATED sasLhl 3 a ` ween $ = Eek == EESTI S ay cty rl ba oSrea--te--------------S teEmL stjt ws ET re A`OnEaClDysHto:diVfaldeed AS.crSecehneiln|g Test with 0OC Analysls FS Fe =oj-moy + ry Date of Start of Test: 4-11-1980 iAra hh e F e eEe ES eLasbtRevqueerstteNA o.L:o5r5e41a'aSseT fesoozjeagpR o3gae S S+sote o ]| ys - Er owTE E a ---- F = -- SyST Se e y e H ee e 7 = eea ee soy -- w= Re = EE nLi - = EEE ee -He er e m ee Ee S p a pe JJ 7 Wirst of BAYS CATED EE PWdS > . Co wp E NTT N TTT shimaTl = E a e C: r = e T icohA aatu fiey d SL cm reening U Tebt ith 00C Analysts h Ha Ea Eas = eee eee ey ee jn FESeEEre =S =S = E S t s : Se i SE Ba Tani Ee = SEE i aE i Te E See =e SHe EE y ER m E EE e e = e e e e S f e ee e ee ge = >3 NUFSER OF DAYS INCUBATED mmemele ee i wiashie Ee SE em em m e eee Mopaivete aScreesnineg n Test wi ols Eee hal = ss SN Lab Request No: 5541'S E Ee ee . (ca.panvion_compounin) = -_ ---- ---- ---- ---- ---- -- ee -- E RSEE IETsE ani ES EEem E Ee E . ---- :~ ed = Er "l-- s ny A 8 -- = = = = fs--_------ 5 af ee = n =r eee TS re | w Ef Ee ee ee ee e ee e ee wel ef e e e e e e 33Ro T7 iNtUFSER OF DAYS 13CUBATED. ie = ---- ) par ey Prwb hd