Document KG3KzG0NvZ1J3QjXk0jw96grw

DownloadRandom document
" I PFOS: An ActivatedSludge, RespirationInhibitioTnest Ii i L'. ACTIVATED SLUDGE RESPIRATION INHIBITION TEST TEST SUBSTANCE Identity:Perfluorooctanesulfonatmea;y alsobe referredtoas PFOS or FC-95. (1-Octanesulfoniaccid,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8heptadecafluoro-p,otassiumsalt,CAS # 2795-39-3) Remarks: The testsubstance isa white powder. Sample was taken from 3M lotnumber 217. Sample was storedunder ambient conditions priortotestingP.uritydeterminedto be 90.49% by LC/MS, 'H-HMR, 19FNMR and elementalanalyses techniques. METHOD Method: OECD 209 Test type:Staticacute GLP: Yes Year Completed: Study completed1999. Reportcompleted2000 Analyticalmonitoring:Dissolvedoxygen concentrations. Statisticamlethods: ProbitanalysisusingthecomputersoftwareofC.E. Stephan. Test organism source: Activatedsludge collectedfrom the ProspectBay Wastewater Treatment FacilityG,rasonvilleM,aryland. Test conditions Dilutionwater: NANOpure@ SyntheticSewage: 1 litemrunicipalwater 16.0g peptone 11.0g meat extract 3.0 g urea 0.7g NaCi 0.4 g CaC12 2H20 0.2g MgSO4 7H20 2.8 g K2HP04 Reference and testsolutionpreparation:A stocksolutionofthe referencesubstance,3,5-dichlorophenowla,s prepared by dissolving500 mg in10 mL of 1N NAOH, dilutedto30 mL with NANOpure@ water,then broughttothe pointofincipient precipitatiownith1N H2SO4, and dilutedto 1 L withNANOpure@ water.The pH ofthe referencesolutionwas measured tobe 7.18. PFOS was added directltyotestvesselsratherthanvolumetric additioonfa stocksolutionT.his method was deemed appropriate based on theobserved solubiliotfythetestsubstanceinwater. Test vessels:Mixtureswere preparedand aeratedin500 mL Edenmeyer flasksand thentransferreidnto300 mL Biochemical Oxygen Demand (BOD) boftles Number ofconcentrations7: plus3 referencecontrolasnd 2 Blankcontrols Temperature: 19-21*C TotalSuspended Solidsand pH forsludge on day of testing: 4380 mg/L and 7.87respectively. Element Basis: Respiratioinnhibitiaosn determinedby dissolved oxygen concentration. Method Remarks: Stocksolutionsof PFOS thatwere preparedat nominal concentratioonfapproximately500 and 1000 mg/L in NANOpure@ water containedtestmaterialthatwas notinsolutionafter 20-minutesofsonicationT.herefore,direcwteightadditiownas employed toadministerPFOS tothetestsystem. Test mixtureswere preparedat 15-minuteintervalasnd aerateduntilthe contacttimeofthetestsubstancewiththeactivatedsludgewas three hours.After3-hoursofcontacttime,dissolvedoxygen was measured over a periodof up to10-minutes. RESULTS Nominal concentrations: Two blankcontrolst,hreereference substance controls0,.90,2.7,9.0,27,90,271,905 mg/L testmaterial solutions StatisticaAlnalyses: ECso valueswere calculatefdorthereference materialby probitanalysisusingthecomputersoftwareofC.E.Stephan. An EC50 valuecouldnotbe calculatefdorthetestsubstance. AnalyticalMethodology: AnalysisofDO concentrationisnalltest solutionswere performedatWildlifIenternationLatld.usinga YSI Model 50B DissolvedOxygen Meter. Dissolvedoxygen readingswere recorded every 10 seconds for10 minutesor untitlhedissolvedoxygen dropped below 1.0mg/L RespiratiRoantesand PercentInhibitions Treatment Contml 1 Control2 3,5-dichlorophenol3 mg/L 3,5-dichlomphenol15 nig/L 3,5-dichlorophenol50 mg/L Test substance 0.90 mgtl Test substance 2.7nig/L Test substance 9.0 mg/L Test substance 27 mg/L Test substance 90 mg/L Test substance 271 ffig@L, Test substance 905 mg/L RespirationRate mg 02AJhour 39.6 41.1 31.1 14.6 5.1 38.9 35.1 33.5 37.9 32.7 28.1 24.7 Percent Inhibition NA NA 22.9 63.8 87.4 3.6 13.0 17.0 6.1 19.0 30.4 38.8 Controlresponse:satisfactory CONCLUSIONS The testsubstanceexhibiteda maximum inhibitoreyffectof38% upon respiratioanta nominaltestsubstanceconcentratioonf905 mg/L. The_ ECr,o(respiratiionhibitioins)thereforegreaterthan thesolubiliotfythe testsubstance. Submifter: 3M Company, EnvironmentalLaboratoryP,.O. Box 33331, St.Paul,Minnesota,55133 DATA QUALITY ReliabilityK:limischranking1. REFERENCES Thisstudywas conductedatWildlifIenternationaLlt,d.Easton,MD atthe requestofthe3M Company. OTHER Last changed: 5/3/00 PFOS: AN ACTIVATED SLUDGE, RESPIRATION INHIBITION TEST FINAL REPORT WILDLIFE INTERNATIONAL LTD. PROJECT NUMBER: 3M LAB REQUEST NUMBER: U2723 454E-101 AUTHORS: Edward C. Schaefer R- ScottFlaggs STUDY INITIATION DATE: De=ber 11,1998 STUDY COMPLETION DATE: March 23,1999 AMENDED REPORT DATE: April28,2000 SUBMITTED TO: 3M EnvironimentaLlaboratory Bldg 2-3E-09 St.Paul,Minnesota 55133 WildlffeInternational,Ltd. 8598 Commerce Drive Easton,Maryland 21601 (410)822-8600 Page I of 49 AMENDED WILDLIFE INTERNATIONAL LTD. -2- PROJECTNO.: 454E-101 GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT SPONSOR: 3M Corporation TITLE: PFOS: An ActivatedSludge,RespirationInhibitioTnest 3M LAB REQUEST NUMBER- U2723 WILDLIFE INTERNATIONAL LTD. PROJECT NUMBER: 454E-101 STUDY COMPLETION: March 23,1999 REPORT AMENDED: April28,2000 Thisstudywas conductedincompliancewith theU.S. Environmental ProtectionAgency in40 CFR Part 160; 17 August 1989; OECD Principleosf Good LaboratoryPractices[OCDE/GD(92)32] Environment MonographNo. 45; Paris1992;and Japan MAFF 59 NohSan, NotificatioNno, 3850, AgriculturaPlroduction Bureau,with thefollowingexceptions: The referencesubstance,obtainedfrom Aldrich Chemical Company (Milwaukee,WI), was not charactmimd incompliancewithGood Laboratmy PracticSetandards.A certificatoef analysishas been supplied by Aldrich. Stabilityh,omogeneity and verificationfthe testand referencesubstancesinthemixtureswere not determined. The testsubstancewas not charactenzodin accordancewith fullGLP compliance;however,the chamctmzatlan was performedaccordingto 3M StandardOperatingProceduresand Methods, and allraw data arebeingmaintainedin the3M archives.The testsubstanceisbeingrecharacwfizedin accordancewith GLP. The stabilitoyf the testsubstanceunder conditionsof storageat thetestsitewas not determinedin accordancewith Good LaboratoryPracticeStandards. STUDY DIRECTORO Edward u. zicrmter Manager, Biodegradation DATE AMENDED WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 -3- QUALITY ASSURANCE STATEMENT Thissb* wasocmrnnefdorcomplianvcaeditheU.S.EnvirorunenPtraoltectiAognencyin40 CFR Part 160, 17 August 1989; OECD Principleosf Good LaboratoryPractices[OCDE/GD(92)32] Environment Monograph No. 45 [OCDE/GD(92)32] and Japan MAFF, 59 NohSan, NotificatioNno, 3850, Agricultural ProductionBureau;WildlifeIntmmationaLLtcLStmidardOperatingProceduresand the studyprotocol.The dates ofallinspectionasnd auditsand thedatesthatany findingswere reportedto the Study Directorand Laboratory Management were as follows: ACI=Y: TestChamber Preparation DO Measurements Raw Data andDmft Report FinalReport Amended FinalReport DATE CONDUCTED: DATE REPORTED TO: STUDYDIRECTOR: MANAGFIVEENT: December 22, 1998 December 22, 1998 December 23,1998 December 22,1998 December 22,1999 January27 and28,1999 January28,1999 December 22,1998 February3, 1999 March 23,1999 April28,2000 March 23,1999 April28,2000 March 23,1999 April28,2000 MarsVU T. Hynson Qu AssuranceProgram Sasor t DATE AMENDED WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 -4, REPORT APPROVAL SPONSOR: 3M Corporation TITLE: PFOS: An ActivatedSludge,RespirationInhibitioTnest 3M LAB REQUEST NUMBER- U2723 WILDLEFE INTERNATIONAL LTD. PROJECT NUMBEK- 454E-101 STUDY DIRECTOR: Edward C. Schaefer,B.S. r Manager, Biodegradation MANAGEMENTE Henry Okru@ger, Ph.D. DirectorA,quaticToxicologyand Non-Target Plants SOR'S REPRESENTATIVE* 2L L^- r) SusA A. Beach 3M Corporation -DATE 7.0-" DATL( DATE ANENDED WILDLIFE INTERNATIONAL LTD. -5STUDY INFORMATION StudyInitiatDiaotne: ExperimentalStartDate: ExperimentalTerminationDate: Study Completion Date: Amended FinalReport Date: December 11, 1998 December 22, 1998 December 22, 1998 March 23, 1999 April28,2000 PROJECTNO.: 454E-101 Study Director: Sponsor: Sponsor'sRepresentative: Study Personnel: Edward C. SchaeferB.S. 3M EnvironmentalLaboratory St Paul,Minnesota 55133 Susan A. Beach Edward C. Schaefer,B.S.,Manager, Biodegradation Henry 0. Krueger,Ph.D.,DirectorA,quaticToxicologyand Non-Target Plants Abul SiddiquiB,.S.,ScientisBti,odegradation SheriTnunbuR, Technologist,Biodegradation R- ScottFlaggs,B.S.,BiologistB,iodegradation AMENDED WILDLIFE INTERNATIONAL LTD. -6TABLE OF CONTENTS PROJECTNO.: 454E-101 TitlPeage......................................................P.a.g.e .I............ Good LaboratoryPracticeCompliance Statement ...............................Pa.g.e .2...... QualityAssurance Statement ...........................................Pa.g.e .3.......... ReportApproval ..................................................P.ag.e.4............ StudyInformation.................................................P.a.ge..5 ............ Table of Contents .................................................P.a.ge..6 ............ Abstract .......................................................P.a.ge..8 ............ Introduction.....................................................P.ag.e.9............ Objective ......................................................P.a.ge..9............ -ExperimentalDesign .......I......................@V..........................P.ag.e.9... Materialsand Methods ..............................................P.a.ge.9............ Test Substance ..............................................P.a.ge.9............ ReferenceSubstance ...........................................P.a.ge..10.......... Route of Exposure and Duration ....................................Pa.g.e.I.I....... I Test System .................................................P.a.ge..I I.......... Test Conditionsand Apparatus ....................................P.a.g.e .I.I....... Test Inoculum ...............................................P.ag.e.1.1........... Procedure...:**'',****...*'****''****'*'*''''.'.'.** '..*.** ....***''*.*..* Page 12 Sample Analysis .............................................P.a.g.e .1.2 .......... Calculations................................................Pa.g.e.1.2........... StatisticAanlalyses ...........................................P.ag.e..13.......... Resultsand Discussion ..............................................P.a.ge..13........... Conclusion ......................................................Pa.g.e .1.4........... References ......................................................Pa.g.e.1.5........... WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 -7- TABLE OF CONTENTS - Continued- TABLE Table1. RespiratiRoantesandPercenItnhibitio.n.s...........................P.ag.e..16..... FIGURES Figure 1. Figure2. Figure3. Figure4. Figure5. Figure6. Figure7. -.Figure8. Figure9. Figure 10. Figure11. Figure 12. DissolvedOxygen ConcentrationOver Time, ControlI ...................P.a.ge..1.7 . DissolvedOxygen ConcentrationOver Time, Control2 ...................P.a.ge..1.8 . DissolvedOxygen ConcentrationOver Time, 3,5-Dichlorophenol3,mg/L ........P.a.ge 19 DissolvedOxygen ConcentrationOver Time, 3,5-Dichlorophenol1,5 mg/L .......P.a.ge 20 DissolvedOxygen ConcentrationOver Time, 3,5-Dichlorophenol5,0 mg/L .......P.a.ge 21 DissolvedOxygen ConcentrationOver Time, PerfluorooctanSeulfonicAcid, PotassiumSalt(PFOS), 0.90mg a.i./.L .............................Pa.g.e.2.2 ..... DissolvedOxygen ConcentrationOver Time, PerfluorooctanSeulfonicAcid, Potassium Salt(PFOS), 2.7mg a.i./L...............................Pa.g.e .2.3 ..... DissolvedOxygen ConcentrationOver Time, PerfluorooctaneSulfonicAcid, PotassiumSalt(PFOS), 9.0mg a.i./L.................................Pa.g.e .2.4 .. DissolvedOxygen ConcentrationOver Time, PerfluorooctaneSulfonicAcid, PotassiumSalt(PFOS), 27 mg a.i./L...............................Pa.g.e .2.5 ..... DissolvedOxygen ConcentrationOver Time, PmfluorooctaneSulfonicAcid, PotassimnSalt(PFOS), 90 mg a.i./L...............................Pa.g.e .2.6 ..... DissolvedOxygen ConcentrationOver Time, PerfluorooetanSeulfonicAcid, PotassiumSalt(PFOS), 271 mg a.i./L..............................Pa.g.e.2.7..... DissolvedOxygen ConcentrationOver Time, PerfluorooctanSeulfonicAcid, Potassium Salt(PFOS), 905 mg a.i./L....................................... Page 28 APPENDICES Appendix 1. Measured DissolvedOxygen (DO) Concentration(smg 0,/L) .............P.a.ge..29 Appendix 11. GraphicalPresentatioonf PercentInhibitioannd PerfluorooctanSeulfonicAcid, Potassium Salt(PFOS) Concentration...........................P.a.ge..31..... Appendix M. Protocol,Amendment and Deviation ............................P.a.ge..33..... Appendix IV. Report Amendment ......................................P.ag.e.4.8........ AMENDED WILDLIFE INTERNATIONAL LTD. -8- PROJECTNO.: 454E-101 ABSTRACF The effectof thetestsubstanceon activatedsludgenucroorgamsms was assessedby theActivatedSludge RespiratioInnhibitioTnestMethod (OECD Gwdehne 209). The testcontaineda control,referenceand treatment groups.The controlgroupwas used todeterminethebackgroundrespiratiornateof the sludgeand was not dosed withthetestorreferencseubstance.T'hereferencegroup was dosed with 3,5-(Echlorophenola,known inhibitor of respirationa,tconcentrationosf 3, 15 and 50 mg/L. The testsubstancewas dosed at0.90,2.7,9.0,27, 90, 271 and 905 mg a.i./LA.fteran exposureperiodof 3 hours,therespiratiornatesof thetestsolutionswere measured usinga dissolvedoxygen meter. The respiratiornatesinthetwo controlswere 39.8 and 41.1mg O)L/hr,oradifferencoef3.2%. The differenciencontrolrespiratiornateswas withinthe 15% differencleimit establishefdorthetest.The validitoyfthetestwas fiuthersupportedby theresultsfrom the 3,5-dichlorophenol referencegroup,which resultedin an EC50 of 9.0 mg/L. The EC50 was withinthe 5 to 30 mg/L range consideredacceptableforthe test. Dffmm= in02 respiratiornatesbetween thecontrolgroup aladtestsubstancetreatmentswere observed at alltestsubstanceconcentrationsF.ollowingisa summary of theresults. Treatment Control1 Control2 3,54chlorophenol 3 mg/L 3,5-&chlorophenot15 mgtl 3,54chlorophenol50 mgtl PerfluorooctanSeulfonicAcid, Potassium Salt(PFOS) PerfluorooctanSeulfonicAcid,PotassiumSalt(PFOS) PerfluorooctanSeulfonicAcid,PotassiumSalt(PFOS) PerfluorooctanSeulfonicAcid,PotassiumSalt(PFOS) PerfluorooctanSeulfonicAcid,PotassiumSalt(PFOS) PerfluorooetanSeulfonicAcid, Potassium Salt(PFOS) PerfluorooctanSeulfonicAcid, Potassium Salt(PFOS) 0.90mg a.i./L 2.7mg a.i./L 9.0mg a.i./L 27 mg a.i./L 90 mg a.i./L 271 mg a.i./L 905 mg a.i./L RespirationRate Percent mg 02IMour Inhibition 39.6 41.1 31.3 14.6 5.1 38.9 35.1 33.5 37.9 32.7 28.1 24.7 NA NA 22.9 63.8 97.4 3.6 13.0 17.0 6.1 19.0 30.4 38.8 AMENDED WILDLIFE INTERNATIONAL LTD. -9- PROJECTNO.: 454E-101 INTRODUCRION Thisstudywas conductedby WildlifeInternationaLltd.for3M Corporation attheWildlifeInternational LtcLbiodegradatiofnacilitiynEaston,Maryland. Originalraw datageneratedby WildlifeInternationaLltd. and a copy of theonpw finalreportarefileudnderProjectNumber 454E- 10 1 inthe arcluveslocatedon theWildlife InternationaLltcLsite. OBJECTIVE The objectiveof thisstudy was to assessthe effectsof the testsubstanceon activatedsludge microorganisms by measuring therespiratiornate. EXPERIMENTAL DESIGN 'Me testcontainedcontrolreferencea,nd treatmentgroups. The controlgroup was used to determinethe backgroundrespiratiornateofthesludgeand was not exposed to thetestor referencesubstances.The reference group was dosed with 3,5-dichlorophenoal,known inhibitoorf respirationa,tconcentrationosf 3, 15,and 50 mg/L. The testsubstancewas testedat 0.90,2.7,9.0,27, 90, 271 and 905 mg a.i./L. MATERIALS AND METHODS This study was conductedaccordingto the proceduresoutlinedin the protocol "PFOS: An Activated Sludge,RespiratioInnhibitioTnest:'(AppendixIV). The protocolwas based on theproceduresspecifiedinthe OECD GuidelineforTestingofammicaiMse,thod 209 (1)and CounciloftheEuropean Communities, Guideline C.11,ActivatedSludge,RespirationInhibitioTnest (2). Test Substan The testsubstance,PerfluorooetanSeulfonicAcid, Potassium Salt(PFOS), was receivedatWildlife InternationLatl& on October29, 1998 and was assignedWildlifeInternationaLltd.identificatinounmber 4675. ANffiNDED WILDLIFE INTERNATIONAL LTD. -10- PROJECTNO.: 454E-101 The testsubstancewas swred under ambient conditionsF.ollowing isa descriptionof thetestsubstanceused in thisstudy: Name: PerfluorooctanSeulfonicAcid,PotassiumSalt(PFOS) I.otNumber: 217 PhysicalDescription: White powder ExpirationDate: Purity: Water Solubility: StorageConditions: 2008 90.49% Slight Ambient Room temperature On theday of administratiotnh,etestsubstancewas added to the appropriatetestflasksviadirectweight ackhtion.The testsubstancewas reanalyzedby theSponsor and the Certificatoef AnalysisdatedMarch 9, 2000 indicateda purityof 90.49%. Reference Substance A stocksolutionof thereferencesubstance,3,5-&chlorophenolwas preparedby dissolving500 mg in 10 mL of IN NAOH and 0= dilutintgo30 mL withNANOpure water. While sfining,enough IN H2SO, was added toreachthepointof incipienptrecipitationT.he solutionof3,5-(HchlorophenoOlm was dilutedto 1 L with NANOpurd* water. The pH of an aliquotof the referencesubstancestock solutionwas measured (pH 7.18).Followingisa descriptioonfreferencesubstanceused inthissU*. Name: Manufacturer: 3,5-&chlorophenol AldrichChemical Co.,Milwaukee, Wl Lot Number: 00410KZ PhysicalDescriptionHandling Precautions: White crystal Standardlaboratoryprecautions ExpirationDate: March 13,2000 Purity: 97% Water Solubility: 7.39 g/L StorageConditions: Ambient CAS Number: 591-35-5 AMENDED WILDLIFE INTERNATIONAL LTD. -11- PROJECTNO.: 454E-101 Routeof E=osure and Duration The referencesubstancewas administerebdy volumetricaddition.Volumetricadditionisthemost appropriatreouteofadministrationfa substanceinan aqueous solution.The testsubstancewas administered by direcwteightaddition.Directweightadditiownas selecteadsthemost appropriatreouteofadministration based on theobservedsolubilitoyfthetestsubstanceinwater.Stocksolutiontshatwere preparedatnominal concmtzfionsoflg/Land 0.5g/L inNANOpure(t waterand sonicatedforapproximately20 n-dnutecsontained testmaterialthatwas not insolution.The durationoftheexposurewas 3 hours. Test System The biologicatlestsystemwas aconsortiumofmicroorganismscommon totheactivatedsludgetreatment process.The organismsresponsiblfeorthedecompositionof organicmaterialsareprincipallayerobica,nd facultativbeacteria.The testsystemwas chosenbecauseitisrepresentatiovfea treatmentprocessthatmay receivethetestsubstance. TestConditionsand Apparatus ControLreferencea,nd treaunentestmixtureswere incubatedat20 20C and aeratedfor3 hours atarate sufficientto provideaerobicconditionasnd maintainsolidsinsuspension.The mixtureswere preparedand aeratedin500 mL Erlenmeyerflasksand thentransferreidnto300 mL BiochemicalOxygen Demand (BOD) bottletsoconductthedissolvedoxygen (DO) measurements.Testmixtureswere identifiebdy projectnumber, testsubstanceID,testconcentratioannd bottlenumber,when appropriate. Testinoculum Activatedsludgewas collectefdrom the ProspectBay Wastewater TreatmentFacilityG,rasonviue, Maryland on December 21, 1998. The ProspectBay facilitryeceiveswastes from predominateldyomestic sources.The sludgewas sievedusinga 2 mm scretmand thensettlefdorapproximately30 minutes.The supernatanatbovethesettlesdolidwsas dmmed and thetotalsuspendedsolids(TSS) concentratioonfthesettled sludgewas determined.Based on theresul@theconcentratioonf thesludgewas adjustedto4000 mg/L (:L10*/o) by dilutinwgithmunicipalwater. Approximately50 mL ofsynthetiscewage (ProtocolA,ppendix IV) was addedto eachhterofactivated sludgeand the sludgewas aeratedovernightat20 2*C. Beforeuse,thepH and totalsuspendedsolids concentratioonftheactivatesdludgewere determined. WILDLIFE INTERNATIONAL LTD. -12- PROJECTNO.: 454E-101 Procedure Testnuxtureswere preparedat 15 mmute intervalsstartinwgith the firstcontrol.The controlcontained 9.6mL of syntheticsewage, 120 mL of inoculum,and enough municipalwaterto bringthetotalvolmne up to 300 mL. The mbd= was promptlyaeratedata ratesufficienttoprovide aerobicconditionsand keep thesolids insuspcnsiorlSubsequentmixum contained9.6mL of syntheticsewage, 120 mL of inoculum,theappropriate amount oftestsubstanceor volume of referencesubstancestocksolutiona,nd enough municipalwaterto bring thetotalvolume up to 300 mL. Finallya, second controlwas prepared.Allmixtureswere aeratedforthree hours. Sai=le An&sis After threehoursof aerationt,hecontentsofthefirsvtesselwere transferretdoa BOD bottleand the respiratiornatewas measured overa periodof up to 10 minutes. Dissolvedoxygen readingswere recordedevery 10 secondsfor10 minutesorunffltheDO droppedbelow 1.0mg/L, whichevercame firstusinga YSI Model 50B DissolvedOxygen Meter. The respiratiornatein subsequentvesselswas determinedin an identicamlarmer at 15 minute intervalso thatthe contacttime of thetestsubstancewith ffieactivatedsludgewas tin= hours. Calculations A respiratiornatewas calculatefdoreach testmixture and expressedinmg OAAour. The ratewas calculateudsingDO valuesbetween approximately6.5mg 02/L and 2.5mg OA, or overa 10 minuteperiod ifthe DO did notreachapproximately2.5mg 02/L.The respiratiornatewas calculateudsingthefollowing equation: Respiratiornate(mg OAAour) = Oxygen uptakeoverthecalculatiopneriod/durationfcalculatiopneriod The percentinhibitiofnoreach testsubstanceconcentratiownas calculateudsingthefollowingequation and plottedagainstthelogarithmoftestsubstanceconcentratio(nAppendix M): WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 -13- Percent Inhibition 2R = 1- ---5 x 100 RC, + RC2 where: 1'.. RC, RC2 oxygen consumption rate at a given concentration of the testsubstance oxygen consumption rate,Control I oxygen consumption rate,Control 2 StatisticaAln*ses VA= the dose response patternallows forthe calculationof an EC50 value,the data are analyzed using thecomputer program of C.E. Stephan (3).The program was designed to calculatethe EC50 value and the 95% confidenceidaval by probitanalysis,the moving average,or binomial probabilitywith nonlinear interpolation (4, 5, 6). In thisstudy,probitanalysiswas used to evaluate inhibitioninthe referencegroup. An EC50 value could not be calculatedfor the testsubstance. RESULTS AND DISCUSSION The pH of the reference stock solutionwas 7.18. Respiration ratesand percent inhibitionsare presented in Table 1. Dissolved oxygen readings recorded during the testare presented in tabularand graphicalforms in Appendices I and 11,respectively.The temperature range recorded the day of the testwas 19-21'C and was within the limitsspecifiedin the testguideline.The measured totalsuspended solids(TSS) concentrationand pH of the sludge on the day of testingwas 4380 mgtl and 7.87, respectively. The respirationratesin the two controlswere 39.6 and 41.1 mg OAJhr, or a differenceof 3.7%. The validityof the testwas furd= supported by the resultsfrom the 3,54chlorophenol referencegroup, which resultedin an EC50 of 9.0 mg/L. The EC50 was withinthe5 to 30 mg/L range considered acceptable forthe test. The 95% confidence limitsforthe EC50 were 6.9 and 11.4 mg/L. WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 -14- The inhibitoreyffectsupon respiratioanttestsubstanceconcentrationasnalyzed(0.90,2.7,9.0,27, 90, 271 and 905 mg a.i./Lr)anged from 3.6% to 38.8%. Respirationratesof thetestsubstanceconcentrations evaluatedrangedfrom 24.7 mg 0,/LJhr(at905 mg a.i./Lt)o38.9mg OA.Ihr (atImg/L). CONCLUSION The maximum inhibitoreyffectupon respiratiofnrom PerfluorooctanSeulfonicAcid,Potassium Salt (PFOS) was observedata testsubstanceconcentratioonf 905 mg a.i./Lb,ut only reached38.8%. The EC50 is thereforegreaterthan 905 mg a.i./L. AMENDED WILDLIFE INTERNATIONAL LTD. -15REFERENCES PROJECTNO.: 454E-101 1. Organisation for Economic Cooperation and Development. Inhibition Test. OECD Guideline 209. 1989. Activated Sludge Respiration 2. Council ofthe European Communities. Directive67/548/EEC. AnnexV. Guideline C.11,Activated Sludge Respiration InhibitionTest. 3. Stephan, C.E. 1978. U.S. EPA, EnvironmentalResearch Laboratory,Duluth,Minnesota. Personal communication. 4. Finney, D.J. 197 1. StatisticaMlethods in BiologicalAssay, second edition.GTiffm Press,London. 5. Thompson, W.k 1947. BacteriologicalReviews, Vol. U, No. 2: 115-145. 6. Stephan, CY,. 1977. "Methods forCalculatingan LC50," Aquatic Toxicology and Hazard Evaluations. American Society for Testing and Materials. PublicationNumber STP 634, pp 65-84. WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 -16- Table I ReViafion Ratesand PercentInMbifiom Treatment Control1 Control2 3,5-dichloropheno3lmg/L 3,5-dichloropheno1l5 mg/L 3,5-dichlorophen5o0l mg/L PerfluorooctanSeulfonicAcid,PotassiumSalt(PFOS) PerfluorooctanSeulfonicAcid,PotassiumSalt(PFOS) PerfluorooctanSeulfor@cAcid,PotassiumSalt(PFOS) PerfluorooctanSeulfonicAcid,PotassiumSalt(PFOS) PerfluorooetanSeulfoniAccid,PotassiumSalt(PFOS) PerfluorooctanSeulfonicAcid,PotassiumSalt(PFOS) 0.90mg a.i./L 2.7mg a.i./L 9.0mg a.i./L 27 mg a.i./L 90 mg ai./L 271 mg a.i./L PerfluorooetaSnuelfoniAccid,PotassiumSalt(PFg)_905 mg a.i./L RespirationRate mg OdAour 39.6 41.1 31.1 14.6 5.1 38.9 35.1 33.5 37.9 32.7 28.1 24.7 Percent Inhibition NA NA 22.9% 63.8% 87.4% 3.60/o 13.6% 17.0% 6.1% 19.0% 30.4% 38.8% AMENDED p -17- 9.0 8.0 E 7.0 O.o x 5.0 0 4.0 > 3.0 0 fA 2.0 i.o 0.0 0 Control 1 100 200 300 400 Soo Time (seconds) Figure1. DissolvedOxygen ConcentratioOnver Time,Control1. Affows indicatmeeasureddissolveodxygenconcenb respiratiroante. AMENDED p 18- E 8.0 c 6.0 x 0 4.0 > 2.0 0.0 0 Control 2 100 200 300 400 500 Time (seconds) Figure2. DissolvedOxygen ConcentratioOnver Time,Control2. Arrows indicatmeeasured dissolvedoxygen conceni respiratiornate. AMENDED p -19- %EMO 8.0 c 6.0 x 0 4.0 > 2.0 0.0 0 3,5-Dichlorophenol3mg/L 100 200 300 400 500 Time (seconds) Figure3. DissolvedOxygm ConcentratioOnver Time,3,5-Dichloropheno3Lmg/L. Arrows indicatmeeasured dissolved to calculatreespiratiornate. AMENDED PRI -20- E 8.0 c 6.0 x 0 4.0 > 2.0 0.0 0 3,5-Dichlorophenol15mg/L 100 200 300 400 500 Time (seconds) Figure4. DissolveOdxygen ConcentratioOnver Time, 3,5-Dichlorophcno1l5, mg/L. Arrows indicatmeeasureddissolved used to calculatreespiratiornate. AMENDED p -21- 9.0 8.0 E%IWO 7.0 6.0 >x% 5.0 0 4.0 > 3.0 0 fA 2.0 F3 1.0 0.0 0 3.,5-Dichlorophonol 50mg/L 100 200 300 400 500 Time (seconds) Figure5. DissolvedOxygen ConcmtrationOver Time,3,5-Dichloropheno5l0,mg/L. Affows indicatmeeasured dissolve used tocalculatreespiratiornate. AMIENDED p -22- a 9.0 8.0 7.0 6.0 >x, 5.0 0 4.0 3.0 0 2.0 i.o 0.0 0 PFOS 0.90 mg a.i./L 100 200 300 400 500 Time (seconds) Figure6. DissolvedOxygen ConcentratioOnver Time,PeffluorooctanSeulfonicAcid,PotassiumSalt(PFOS),0.90 mg measured dissolvedoxygen concentrationussed tocalculatreespiratiornate. AMENDED p -23- 9.0 8.0 7.0 %Iwo 6.0 im >x% 5.0 0 4.0 0 3.0 2.0 1.0 0.0 0 PFOS 2.7 mg a.i./L 100 200 300 400 500 Time (seconds) Figure7. DissolvedOxygen ConcmtrationOver Time,PerfluoromtaneSulfonicAcid,PotassiumSalt(PFO@),2.7in measured dissolvedoxygen concentrationussed tocalculatreespiratiornate. AMENDED PR -24- E 8.0 G.o x 0 4.0 > 73 2.0 0.0 0 PFOS 9.0 mg a.i./L 100 200 300 400 500 Time (seconds) FigureS. DissolvedOxygen ConcentratioOnver Time,PerfluorooctanSeulfonicAcid,PotassiumSalt(PFOS), 9.0mg measured dissolvedoxygen concentrationused tocalculatreespiratiornate. AMENDED p -25- 9.0 B.o co 7.0 6 .0 im >x% 5.0 0 4.0 > 3.0 0 ta 2.0 $A i.o 0.0 - 0 PFOS 27 mg a.i./L 100 200 300 400 500 Time (seconds) Figure9. DissolvedOxygen ConcentratioOnver Time, PerfluorooetanSeulfonicAcid,PotassiumSalt(PFOS), 27 mg measured dissolvedoxygen concentrationussedtocalculatreespiratiornate. AMENDED PR -26- E 8.0 6.0 x 0 4.0 > 2.0 0.0 0 PFOS 90mg a.l./L 100 200 300 400 500 Time (seconds) Figure10. DissolvedOxygen ConcentratioOnver Time, PerfluorooctanSeulfonicAcid,PotassiumSalt(PFOS),90 mg measured dissolvedoxygen concentrationussed tocalculatreespiratiornate. ANENDED PR( -27- 9.0 im --'.E--7.0 6.0 x 5.0 0 4.0 10 0 3.0 to 2.0 14 F3 1.0 0.0 0 PFOS 271 mg/ a.I.L 100 200 300 400 500 Time (seconds) Figure 11. Dissolved Oxygen ConcentrationOver Time, PerfluorooctanSeulfonicAcid,Potassium Salt(PFOS), 271 mg measured dissolvedoxygen concentrationussed to calculatreespiratiornate. AMENDED p -28- 9.0 8.0 E-1 7.0 c 6.0 x s.o 0 4.0 > 3.0 0 2.0 1.0 0.0 0 PFOS 905 mg a.l./L 100 200 300 400 500 Time (seconds) Fipre 12. DissolvedOxytm ConcentratioOnver Time,PerfluorooctaSnuelfoniAccid,PotassiumSalt(PFOS),905 mg measured dissolvedoxygen concentrationussed tocalculatreespiration. AMENDED WILDLIFE INTERNATIONAL LTD. PROJFCTNO.: 454E-101 -29- APPENDIX I Measured DissolvedOxygen (DO) Concentration(smg 02/L) Time (min.) Control1 00:10 7.3 00:20 6.5 00:30 6.0 00:40 5.8 00:50 5.6 01:00 5.5 01:10 5.4 01:20 5.3 01:30 5.2 01:40 5.1 01:50 5.0 02:00 4.9 02:10 5.0 02:20 4.8 02:30 4.8 02:40 4.5 02:50 4.3 03:00 4.2 03:10 4.1 03:20 3.9 03:30 3.8 03:40 3.7 03:50 3.6 04:00 3.5 04:10 3.4 04:20 3.3 04.30 3.2 04.40 3.1 04.50 3.0 05:00 2.9 05:10 2.8 05:20 2.7 05:30 2.6 05:40 2.5 05:50 2.4 06:00 2.3 06:10 2.2 06:20 2.1 06:30 2.0 06.40 1.9 06:50 1.8 07:00 1.7 07:10 1.5 07:20 1.5 07:30 1.3 07:40 1.3 07:50 1.2 08:00 1.1 08:10 0.9 08:20 - 08:30 - 08-40 - 08:50 - 09:00 - 09:10 - 09:20 - 09:30 - 09:40 - 09:50 - 10:00 - TreatmentDissolveOdxygen (mg/L) 3,5-Dichlorophenol3,5-Dichlo enol 3,5-Dichl,ophrconol 3 mg/E 15 m@e 50 MGIL 8.0 8-3 8.2 7.8 8.2 8.4 7.6 8.1 8A 7.5 8.0 8.5 7.4 8.0 8.5 7.3 7.9 8.5 7.3 7.9 8.5 7.2 7.9 8.5 7.1 7.8 8.5 7.0 7.8 8.5 6.9 7.8 8.5 6.9 7.7 8.4 6.7 7.7 8.4 6.7 7.7 8.4 6.6 7.6 8.4 6.5 7.6 8.4 6.4 7.5 8.4 6.3 7.5 8.4 6.2 7.5 8.4 6.1 7.4 8.3 6.1 7.4 8.3 6.0 7.3 8.3 5.9 7.3 8.3 5.8 7.3 8.3 5.7 7.2 8.3 5.6 7.2 8.2 5.5 7.1 8.2 5.4 7.1 9.2 5.4 7.1 8.2 5.3 7.0 8.2 5.2 7.0 8.1 5.1 6.9 &1 5.0 6.9 8.1 4.9 6.9 8.1 4.8 6.8 8.1 4.8 6.8 8.1 4.7 6.7 8.0 4.6 6.7 8.0 4.5 6.7 8.0 4.4 6.6 8.0 4.3 6.6 8.0 4.2 6.6 9.0 4.1 6.5 8.0 4.1 6.5 7.9 4.0 6.4 7.9 3.9 6.4 7.9 3.8 6.4 7.9 3.7 6.3 7.9 3.6 6.3 7.9 3.5 6.3 7.8 3.4 6.2 7.8 3.4 6.2 7.8 3.3 6.1 7.8 3.2 6.1 7.8 3.1 6.1 7.7 3.0 6.0 7.7 2.9 6.0 7.7 2.8 6.0 7.7 2.7 5.9 7.7 2.7 5.9 7.7 Bold numbers indicatedissolvedoxygen concentrationsused to calculaterespirationrates. PFOS 0.90 mg a.i./L- 7.6 6.9 6.6 6.5 6.3 6.2 6.1 5.9 5.8 5.7 5.6 5.5 5.4 53 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.6 2.5 2.4 2.3 22 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 12 1.1 1.0 0.9 - PFOS 2.7mg a.i./L 7.3 7.0 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.1 2.9 2.8 2.7 2.7 2.6 2.5 2.4 2.3 22 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 AMENDED WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 -30- APPENDIX I (Continued) Measured DissolvedOxygen (DO) Concentration(smg 02/L) Time (min.) PFOS 9.0mg a.i./L PFOS 27 mg a.i./L TreatmentDissolveOdxygen (mgtl) PFOS 90 mg a.ijl PFOS 271 mg a.i./L 00:10 7.3 7.4 7.5 7.6 00:20 6.8 6.7 7.0 7.3 00:30 6.5 6.4 6.9 7.1 00:40 6.3 6.2 6.8 7.0 00:50 6.2 6.1 6.7 6.9 011)0 6.1 6.0 6.6 6.8 01:10 6.0 5.8 6.5 6.7 01:20 5.9 5.7 6.4 6.7 01:30 5.8 5.6 6.3 6.6 01:40 5.7 5.5 6.2 6.5 01:50 5.6 5.4 6.1 6.4 02:00 5.5 5.3 6.0 6.4 02:10 5.4 5.2 5.9 6.3 02:20 5.3 5.1 5.8 6.2 02:30 5.2 5.0 5.8 6.1 02AO 5.1 4.9 5.7 6.0 02:50 5.0 4.8 5.6 6.0 03:00 5.0 4.7 5.5 5.9 03:10 4.9 4.6 5.4 5.8 03:20 4.8 4.5 5.3 5.7 03:30 4.7 4.4 5.2 5.7 03:40 4.6 4.3 5.1 5.6 03:50 4.5 4.2 5.1 5.5 04:00 4.4 4.1 5.0 5.4 04:10 4.3 4.0 4.9 5.3 04:20 4.2 3.9 4.8 5.3 04.30 4.1 3.8 4.7 5.2 04.40 4.0 3.7 4.6 5.1 04.50 3.9 3.6 4.5 5.1 05:00 3.8 3.5 4.4 5.0 05:10 3.8 3.4 4.3 4.9 05:20 3.6 3.3 4.3 4.8 05:30 3.6 3.2 4.2 4.7 05:40 3.5 3.1 4.1 4.7 05:50 3.4 3.0 4.0 4.6 06:00 3.3 2.9 3.9 4.5 06:10 3.2 2.8 3.9 4.4 06:20 3.2 2.7 3.7 4.3 06:30 3.1 2.6 3.6 4.3 06-40 3.0 2.5 3.5 4.2 06:50 2.9 2.4 3.5 4.1 07:00 2.8 2.3 3.4 4.0 07:10 2.8 2.2 3.3 3.9 07:20 2.7 2.1 3.2 3.9 07:30 2.6 2.0 3.1 3.9 07:40 2.5 1.9 3.0 3.7 07:50 2.4 1.8 2.9 3.6 08.00 2.3 1.7 2.8 3.5 08:10 2.2 1.6 2.7 3.5 08:20 2.1 1.5 2.6 3.4 08:30 2.0 1A 2.5 3.3 08:40 1.9 1.3 2.4 3.2 08:50 1.9 1.2 2.3 3.2 09:00 1.9 1.1 2.2 3.1 09:10 1.7 1.0 2.2 3.0 09:20 1.6 0.9 2.1 3.0 09:30 1.5 - 2.0 2.9 09:40 1.4 - 1.9 2.8 09:50 1.3 - 1.8 2.7 10:00 1.2 - 1.7 2.6 Bold numbers indicatdeissolveodxygen concentrationusedtocalculatreespiratiroantes. PFOS 905 mg a.i./L 7.3 6.9 6.8 6.7 6.6 6.5 6.5 6.4 6.3 6.3 6.2 6.1 6.0 6.0 5.9 5.9 5.8 5.7 5.7 5.6 5.5 5.5 5.4 5.3 5.2 5.2 5.1 5.0 5.0 4.9 4.8 4.8 4.7 4.6 4.6 4.5 4.4 4.4 4.3 4.2 4.1 4.1 4.0 3.9 3.9 3.8 3.7 3.7 3.6 3.5 3.5 3.4 3.3 3.2 3.2 3.1 3.0 3.0 2.9 2.8 Control2 7.9 7.4 7.1 7.0 6.9 6.7 6.6 6.5 6.4 6.3 6.1 6.1 6.0 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.6 2.5 2.4 23 2..2 2.1 2.0 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.0 0.9 - AMENDED WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 -31APPENDIX R GraphicalPresentationof Percenthimbitionand PerfluorooetanSeulfonicAcid, PotassiumSalt(PFOS) Concentration WILDLIFE INTERNATIONAL LTD. -32APPE14DIX H PROJECTNO.: 454E-101 Percent Inhibition versus PFOS Concentration (mg/L) 40 - c 26 .C -S 20 ed r % lnhibition@ 10 5 0 1 10 100 PFOSConcentra(tmigo&n.IJL) -----1000 Figur1e.PerceInnthibitvieornsuPserfluorooSeutlafnoenAiccidP,otassiSuaml(tPFOS)Concentration ANENDED WILDLIFE INTERNATIONAL LTD. -33APPENDIX III Protocol,Amendment and Deviation PROJFCTNO.: 454E-101 WILDLIFE INTERNATIONAL LTD. -34APPENDIX III PROJECTNO.: 454E-101 PROTOCOL PFOS: AN ACITVATED SLUDGF, RESPIFTATIONR4MMON TEST Or@@ forE=mm CwperrtimandDaydopmeat OECD Oddelint209 and CAMCH OfFAUWM Cm=nW= Dkedive 67/54&qMC Am=V.GWdefimCli 3M 14b PequestNo.U2723 WILDLIFE Subwkodto 3MC=porem EnybommaWLabombuy P.O.Box 33331 St PauLMmocoft 55133 INTERNATIONAL SSN CAmomm Drin Entm Mayland21601 (410g)n46M LTD. Dm=bcr 1.1998 PROTOCOL NO.: 454/12019&/ASRrr/SUB454 3M LAB RBQLIEST NO. U2723 WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 WILDLIFF- INTERNATIONAL LTD. -35APPENDIX Ul -2- PFOS: AN ACTTVATED SLUDGE, RESPIRATION DIMMON TEST SPONS SPONSOR'S RRMESENTAMM TP-qT[NGFArTI-TTY gilinyntgp=opT.ATTORATORYMANA 3MCapxatim Envhamnead Labmv=y P.O.Box 33331 St Pxd,bfimwsota55133 h(L Suan A.Bewh VrddM bAcMadand lAd. 9599C4muom Drive EMm Maybod21601 Ed Sdnefcr Hmry 0. MnxW. PhD. MMW ofAqubc Twadou & Non-TargePtlm3ts FOR LABORATORY USE OM@Y ProposedDates: 12./17/ft StodDoW. i45qr-- ProjeaNo.: Tamhmfml StodyRoooL Vo...37 TCACM*Mhufmr IS.10,10I,MPSMImwq umw &_@ iqiikr 1 Ted Substmm M.: 1 PROTOCOT- APMVAL ST= DMEMR f 9 li IXI=-AMANAGMAM r DAIS DATE S9r:!S:OSWMSORRE-PSRLESREENTATIVE PROTOCOLNO.: 454/12019VASRrr/SUB454 C-21-7 DATE' 3M IAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 WILDLIFE INTE:RNA-NONAL LTD. -36APPENDIX IE -3- INTRODUMION The puqmc ofdo testisto provi&a =ccning methodtoWeatifynfttmm thatmay adyc@ affedmobir,==bmt bubx= plantasndtoindi suitablneon-WuUory tesstubstance comentifim foruseinbbdogradabuitoyo. OBJFJCTTW@ Ilm objectivoefthesh* willbetoasscmdw of d3a testsubstancoen activatesdludp bym=uing themphifim tab-A-n ECSO wilble c"ucd ifpossible, kL DFMGN Mm testwM contaian contrd,refuume,anducaunat group.Ilm controglroupisusedto ddenninediebadwound rcspirw= riftofOw zhwp andvM notbe avosw to&c testsubdaum The rcfercm groupwillbe dosedwith3 . a kwwn bd&itorof resphudona,t cmccubafim of3,15,and50mg/L The testobstmm willbetesteadt1.3.10,30,100,300a,nd 1000ml#L MATV,RTAT.lqAND MRTHODS Testmodw& m basedan dkepwoodm= spedw indw OECD GUWJ= forTestmgof CheniiWo Mc&od 209 (1)and Councilofdo Eampon CommoWdw GWdelintC.11.Acdvdod Sbdm Rapkgim bhlwm Tat(2@ h&mntiman6cdwndmizationaftest, 'ornfmwwmkst mm isnphw byGood Labmemy PnAdw Sund" (Gin 40CFR Part160.13.Mo Spmw israqmsfflfot pmvidiag Yrddl&hd=afiooallAd.vu vaificdiodniadiew substancheu beendmscftizedacoorft toM2sprkrtouinginthatcsILU ausdodformIDENTIPICANON OFT= SUBSTANCK BY SPONSOR (Appeaft11)istobeusedtopvA& hdmadm noomm for02 compham If wfficabmofW Ud Wxbm &u=Wiudm n notWwAded toWildlifbewnabwd Lt&, itwillbenotedindw compeam stament ofdw finamlpmt PP.OTOCOLNO.: 454112019VASRrr/SUB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 WILDUFE INTERNATIONAL LTD. -37APPENDIX IR -4- Tbcspan= isrespowibkforallkdamndm rtwadtothetmtsubstancaendagrm tosoovt anyu=md tean6stam an&orteasubstanocoedam= tmming atdc cadoftk su*. lqtocSkobgionEMpsafgm A stocksohdicaoftheteasubstancweillbe prqmod ata nombw conomtradwof1000mg acdw& inbighquftwau (eg.Nmapam). Inadditioaudocksohdimof3,5-dichiolophweinloll prwarodby dissohin5g00mg in10mL ofIN NSOH anddm,4ihWo to30mL withhishquality waw. VAME suuin&enoughIN H2SO4(appro3imd*8 mL) willbe addedtomuk thepomtof b*iatfo*itafim Thtwhdim of3A4WA=Pbxkol d=wM be&hftdtoIL withhigh"ft yaw. Testrywwtitiarmw"Appw= catrolrcfwmee,md teabnottest willbeknbaud at20* 2*C andaaawd for3 ho= ata raWsufraciatto solidisnnspmskxl The willbepmparedand aerded m SM mL &stm Erkmqw flasiamnddm ummftw:dbfta300mL BW=icd OMM Dmand (BOD) bottlteodo condod&nohed oxysm (DO)maLimanctL AdWdoddodpfiomdiaPi Baywodmdff TodmcutPha wM bound ago bocdm forthetuL Tk ps BayFmliy.cody wams fim prod=bm* damutic , , The sWp wM beWavedufmga 2 mm mm anddmu odW fw qpomu* 30 mimam MO I ' ' *oso" sofwtilbleI * IandotoW==MW sorlC&M mw*Wm ofdwseW dWp wilbleddmniw&Baseadndoresodkoomomtmdow(dwdWp wiblel aftxftdto4OODmWL(:LIO%)byddutwidohmmkipdwato Ndit dWp cannotbeusedondw dayofcoucadworifdwam batchisroqwmdtobemcd on mbsecod dqs omdmm Em dqsl So mL ofqn&Wc wwav (Appeaft10wilble addedto eschlitwofacaydoddWpatdacodofa&woddogdiWT.&dWpwMbca&lftdovcmigbtat2O * 2*C. Bd= we, dw pH andtotanlupmdod solidcsoncenuatiomfgo acdvdadski* willbe d*mgmd nA ifnemmy, aozftdtopH 6.0-8.0anda solidasmombidw of4000mgll(& 10%). PROTOCOLNO.: 45MI2019VASP.IT/StJB454 3M LAB REQUM NO. tl2723 WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 -38- APPENDIX III WILDUFF- INTERNA-NONAL LTD. -5- Procodm Test wM beprepa-cdat15 -i- kftvab statingwithdc fim contml The cot&ol wM contai9n.6mL ofryndwdc sewage,120 mL ofhmdwn and cam& munkipal watertobringthe totdvobm up to300 mL Ma mbdm willbe prmvtly sarded ata ratesnfficip-ttokeepthesolids insimmim SW=qumt appmptide vokmic ofw * 1 willcontain9.6mL ofqndwdc wwam or I-r, stocks"on nd cxm& 120 mL offimcub- ft municipalwatertobdn do toW vokme up to300 mL Fmally,a scowd coftd wM be pmparcd. Allmbamm wM be aauw fardm= bourl Emmwe Aubmis Afbcrftwhours ofumbak the ofdiefirsvtmd willbe umsferred tDa BOD botdo md ffircesphifimratcvm be measured overa periodof apto 10-i-stes. DL%sdvadarygcnrcadings willbe recordedevay 10 scowd for10-i- oruntildieDO dmps below 1.0mrl, wbich am c@ fi@ Ile resphibm rateinrawqucnt vesselwsM be ddawhked inan idea" umma at15 hdcrah sodut thecoated6= of*a testsubstmw withdw activateWdWV isdm houm A resphifimratewm be calcwdod foreachtca mbmzt end i itmLg O)LAww. Ilm rft wM be eakdated uft DO vahm bdwom qvrwdmatdy 6.5ng ())L and 25 mg OX or over a 10 mwft podad ifdo DO does not rewh qvroxbod* 2.5 ng C))L llwp=mtMMmforcKhtmtsdwimanamuWmwEbe e*mdm and pioftdagm= owcwtmm m logpaper. cdoolmdusmSdoMowmg Percent Inhibition = 1 2R. x 100 Rci + RC2 PROTOCOL NO.: 454/120199/ASRIT&IJB454 3M LAB RBQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-loi WILDUFE INTERNATIONAL L-rD. -39APPENDIX III -6- Vlh= P, P,q PC, - oxygm convmpdm mto ata givenconomdradon of thetestsubsm= oxygm coanm4)dm rate,C4atml I oxygm conumq)tim rateC,ontrol2 An W.50 valuewM bedaiv4 ifposnble,basedon ft percentioh@ibimv=us testnbsta= emommm Cmfida= hmsts(95Y*f)i)dro =0 willbe d*=wd umg amdad AdubW procc&m (3). ilc testiscwddmvd validonlyifdc Mowing atmu am met thetwo controlnopkadw raw am wdwn 15% ofeachodw; &c EM (3hom) of3,,-@@ isindkeamqpw rop of5 to30 mg/L RRMRM TO IFtlMtAMATNvn P@e=& tobe--6mh-A wM iociu&butnotBmW W@ do MowinX I A eM ofdkes4ped pmtoool 2. idadficstionand dwsaninfim ofdietog substmm asprovidedby Sponsor. 3. Ted inwadw md tmmkofim ddm 4. Eqaimc"bffidionsndkm*mfmdatcL 5. stocksoba= cowwwdm cdcwzdm and solutiopnWmdiaL 6. Acdvdod *adp a- rPod pmftdment dewe 7. Ted t=v p 1, nd dm*ioil a. Pcferme abstmm - li 9 AR dosdned oxygm mmsmmatl 10. Tcoqxzv&m raW pp@ 1-4 dwing testperiod. ll. IabaMm curveand umthod forcalculatioonf BCSO. 12. IfcolaildodBCSO md 95% confidmw limits. 13. A oW ofditfinarleporl PILOTOCOLNO.: 454/12019VASPJT/SUB454 3M LAB PJBQUW NO. U2723 WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 WILDLIFE INTERNANONAL -40APPENDIX III LTD. -7- FTNAL REPORT A findrepcxtofdwremb ofditsb*vm be p-ep-P byVddffchdanadoagIjdrwmport isto kdude, but isnotlidtadto,diefodowing when applicable: 1. Nux ad addnm officirtpyufa@ ft d*. 2. Dam an which the studyva WWxbod and compktcd. 3. A sutmm ofcompliam signedby do StudyDk=w addresdagany =options to Good LabmVAry PracticeStmdatds. 4. Objo*mwdpmoc&mddodindnqVwvodpwk=kWdo& anycb-osintbcod&d PMU=L S. kkaffeafm anddwa=uzbm ofgn testsdrm= asprovidodbySpoom mobid;n an= CASmmbcr,patmtacftm=dodierdwadmsbco6tfpo"dedbydeSpwm 6. A dcsm*ion ofdc 6 wd= andc" pafamaed m diedatl 7. A desodptim afthe mcdxds usedand mfa=m toany xtod-d awthod emplqa 2. A dweripfimofthetea qswx 9. A &=Wm of dc pvaadm of dw ka wbWov4 dieusdog omowuWj*sL I - - - tiona.ndthe&rafm ofdo tcsl die route of 10. A desuiptimof allchemstmm dut may of affimwdft qualitoyriawpty ofdo ddL 11. Tw no= of&t study &cow. *a nmw of odff sdowsm or pmftdonok and &a nmm of alluwvismy-pasound, kvohed indiestudy. 12. Mcipod ad ddod 1epmrtoof each of ft bdhidual odathu or otherpmfi=iwais bmahed iadostody.EqVHcdd& 13. 7be knofim where do raw daft and &W upod am tobe d=W 14. A dd=md pqwod by do Qwft Anwaam U* Esdog&o ddm dut &c 9* b4*Wm and auditswm made anddo data of oW 6--fin mn reportetdodo SWO Duraw and 15. Ut isnoccomyto mdm cmncdons or toa findrepmt da ithasbeen such dmgm wM bomabinge famatmammkaftisswdbygo StudyDkeam. MwmmdmW wM dmiy kkntifydo partof dw findrepordtw isbeingammdod andto rasm aniandinatad willbe dped by dw StudyDkeew. ft *c PP,OTOCOL NO.: 454/12019&/ASRrr/SUB454 3M LAB PJBQUEST NO. U2723 WILDLIFE INTERNATIC)NAL LTD. WILDLIFE INTF-RNATlOt4AL LTD. -41APPENDIX Ul PROJECTNO.: 454E-101 CHMGINGOFPROTOCOT, Plm=dd=gmtotheprokwlwfflbcimthtf(xmofwd= dgwdbydicsb* DiectorandtheSpm&s Rqrmmtadm A w!U be cmddered aspad oftheprotowland wM besuadzdtothefindpmwoot Any adierdmgm wfllbe indw formofwrittedncvwm dgued by theStudyDucew andfilewdkh Ow raw daL AU changestodw pmtood wM be haeatod inthe finarleparl roonlAIROItALTORYPRACTICILq Thissb* wfflbecondi=W i2wwahm wi& Good Labmatotyhid= SftwludsforEPA (40CFR Pfft16D)O,BM PzmcipleosfGood lab@ Prwbm (OCDEIGD (92)32.Mmkomat Mmopuph No 45),andiqm MAFF (59N&Sav6 NoerAum No.3850,Apmhwd hoductl= Bwm). Ewh studycm&xftd byWM& bkmadmd IAL isroutim*=mined by dieWddffc kw=bong lAcLQudq Aummm Umt forcomphw= withGood LabmUmy Pracboe4SWWad OpustingPmwdmm andtheW=fiod FaWcoL A damucat ofcm*hm= withGood Ubmdmy Pngd=vMbel rl-p4for&Rpm*= afto studycoa(ixfbtydYrddi& hacmatmd U& Rawdeft foroRwodcpakrmd atvrdd& ktcmdimd Ui imdacopyoftheftd =portwM befiW by prcjft number inadih= locateodn *c VrddffohumafionalLt& siV,oratanshumativekmfm tobe specifieidndw findreparl PROTOCOL NO.: 454/12019&tASRIT/SUB4.54 3M LAB REQUES-T NO. U2723 WILDLIFE INTERNATIONAL LTD. WILOUFF- INTERNA-NONAL LrD. -42APPENDIX IH -9- RIRFV,RV,NC.TS PROJECTNO.: 454E-101 I OrganisatfiornEconomiCcooperatiaonndDevelopmmt1.989.ActftteSdludge RespiradIonnhibitTiaotn.OECD OWdeUm209. 2 CouncHaftbeEmWmCommunitieL Dkoctivv67/54&WC An=V. OukWineC.11, AethwedSludgePespirado&nkbidon Test. 3 Stephan,CJL 1977.*McdmxlfsorCalodatinagn 100,' AquaticTo;awkV andh=ard Evahmdm. AmaicanSocietfyorTestiqmgd MatcrWL PubficadmNumberSTP 634,pp 6594. PROTOCOL NO.: 454/12019$/ASRIT/SUB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 -43WILDLIFE INTF-RNA-NONAL LrD. APPENDIX III . -10- iDe,rrmcAnoN oFiET'sMTANcE By SPONSOR To beCompkftd by Sponsor L Tea Substm= IdadW (nam tobeusedinthereport):EffflugED2ctaw,-mfonAiccidLPofjL%+mSnalt SampleCodeorBatchNumber Tot7l7 Pwity(V.Acdwbpdcnt@ 999'/- ExpkatimDdo- 7008 IL TestSubstmm Chmictuization H.ayethekmk.n&Y,. uriyland Om Ltm ge EOM = VARr&rs prior Yes- No -X- 13L TestSubst@ Stmp Cwftw Pica= Wicift6e tooommmiedmp cmditkmatVrddHfbat=ationdlAd. ,AmbienrtoornICMPCM=Iona condw= 'mptf=:,",ItmhwC&tg=? Odierpafimasttabiuklfyo@ Yes No IV. Tmicitybfmmadm Mamm9ioL RiLLtD50 -21LMgikL-Mom MM ML Aquatic: brvatcbnfTtow* 0301IC50) Dvbwn 7"99A*77 mvfl. FahTwi&Y (LC50) Fainbawftm*-11ingil D=bWm imsm !ioMI& Emdmd Mim= 39mgfl Odwr Twmdy bf=om (mdabog 6-4- ofdwmc md mbdwmc kai@ PROTOCOL NO.: 454/12019&/ASRfT/SUB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. WILDLIFE INTERNA-noNAL LTD. -44APPENDIX III PROJECTNO.: 454E-101 APPEt4DIX IL SYNTHMC SEWAGF- The syndictiscewageprovw= do necessarnyab=ft req=ed forbactmd m&Abohm dasolvmgtheMawmg uwuats of substanceisnI fiteorfnnmicipdwater. Itispreparebdy 16.0g poptone 11.0g nwa extmct 3.0g uma 0.7g Naa 0.4g CaCI22H20 02 g MGSO,,7E60 2.8g KIM4 Rce gra&ch=icalarbettcrwmbousodvibmavaillaubcka,nsdftaftofdw ryndodeseww= not bwvn tocontamanycontm- dw am remocablecgccwd tobe prcsmtand am knovvntobe apkle of btafirinwgi& &c study. PROTOCOL NO.: 454/120199/ASRrr/SUB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. WILDLIF*E INTERNATIC)NAL LrD. -45APPENDIX M PROJECTNO.: 454E-101 PROJKTNO.: 454F,101 Pap Iof2 AMENDMENT TO STUDY PROTOCOL STUDY TNILE: PPOS:AN ACTWATM SLUDGF, PMP]3tATION DMMMON TEST PROTOCOL NO.: 454/12019$/ASRrr/SUB454 AMIENDUMM NO.: 1 SPONSOR. 3M Capamtim PROJECR NO.: 454B-101 3M LAB REQUEST NO.- Lr2723 AMZMN3=: Add- Pop 3;Ted Substem The testobdam vM be a&mstcmd by dued wcqft adddm Duod we& addidw isdc mostwrwrige,, ofadmhdst=m oftestabstoom did m reladvelhylsolublienwew. REASON: Route of admumstsum was dmgcd fimm volumetnead(ribmofan aqumn stock solutiotno daid vu& addtm beemm of dielow wam solubft of thetest substm=. EFFECRIVE DATE: 21 December 1999 AbMWbMNT: Dolds- Pop 4;StockSobtionPrepwtion A stockwW= of&c ta nbstmm wdl be pqmod ata mm indcoo=mdm of 1000mg acdvdlimbigbqmd* vidm(e,&Nmopure). REASON: Pm* of admwisbatiowna ch-ead fiamvobmwft addkionof an squwa stock solubm to dhft wcqft adddm bwmm of do low "am sob*ft of dw test xubdance. EFFECTIVEDATE: 21 Doo=bcr 1998 WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 -46- WILDUFE INTERNA-NONAL LTD. APPENDIX III PROJECT NO.: 454E-101 Page 2 of2 AMENDMENT: Change: To: Page5;Proood= Testmmtww willbepreparedat15mmuto intervaslMsrUngwiththefirsotmtrol ne controlwillcontain9.6 mL of s3mthedcsewage,120 mL ofkoculon and enough municipalwatertobringdw totalvolumeup to300 mL. Tlw mixtt=willbepromptly aamw ata raw suffmicttokwp thesolidisnsuspensionS.ubscqmmtmbmnis will contain9.6mL ofsyndode sewage,120 mL ofbmdura, theappropriatveolumeof teaorrd=we substancdeock sdutioc@andcam& municipawlta tobringthetotal volumeup to300mL Fmaffy,a secondcontrowlillbeprqpami Allmum= win be a=Ued fi)dram bo=. Testmbdtm willbeprepareadt15-im in@ stwtinvgft thefirsctontmllU conud wfflconui,9.6mL of qmdodo wwam 120 mL of bmW= andenough mu*ipd watertobringdo totdvolumeup to300mT- Themb=c va bepromptly amued ata mtooffmiattobxp Ow solidisnaspmoial Subwqtxmtmbdim will ewtain 9.6mL ofsyndzdr.wwar, 120 mL -ofhmuhim, theappropriaatmeountof testvavmw orvolumeofreferencseubstancsetocksolutiona,ndenough=-icipal watertobringthetotalvolume up to300 mL PhuMy, a secondcontrolwillbe prepuc& AR mbdmts willbeaamw ford= hm=. REMON: R@ of administratiwoans changedfi-omvolumctdcadditimofan aqumm stock solutio-ntoduca weigh additiobnw4tuw of the low waa solub&tyof the t= stibstano-- EFFECTIVE DATE: 21 December 1999 ,A DUMMIC DATE A-To4R WL,KNAGEMENT 9POWSOIVSREPRESENTATRVE DAT]R cl DAlt WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 WILDUFE -47INTERNA'NONAL LTD. APPENDIX III DEVIATION TO STUDY PROTOCOL PROJECTNO.: 454E-tOl Page IofI STUDY TITLE: PFOS: AN ACTIVATED SLUDGE, RESPIRATION DUUBMON TEST PROTOCOL NO.: 454/12019&/ASRrr/SUB454 DEVIATION NO.: I SPONSOR. 3M Cmpmldm PROJECRNO.: 454E-101 DATE OF DEFACRO DEVUTION- D=mber 12,1999 DEVIATION: Prooedum Page-5-: lU 3 mg/L 3,5-Echlorc)ph=ml-dtnwasaciledforttauhoursad onemmute. REASON: luadvatmtam by sWy p=onnel- IWACR: Mu &-vmaondidna =paa dc mtegq of*c stvay. STUDYDMECTOIL LABdLU@OkY MMAGEMENT DAlt WILDLIFE INTERNATIONAL LTD. -48APPENDIX IV Report Amendment PROJECTNO.: 454E-101 I . OriginalReport: Pages 1-5 and 7 Amendment: The pageswere changed toincludetheamaided reportdate,revisedpage numbers, and new sigaaftm and datesdue totheadditionof the reportamendment as Appendix IV. Reason: To reflectheissuingof an amended report. 2. OriginalReport: Page 2 Amendment: Compliance statementwas revised. Reason: To clarifhyow thetestsubstancewas characterized. 3. OriginalReport -- Amendment: Page 10 Informationprovidedby the Sponsor reflectintghe reanalysisof testsubstance, includingthe reanalysisdateand the puri@,was added to the Test Substancesection. Reason: To reflecthe currenttestsubstanceinformationprovidedby theSponsor. 4. OriginalReport: Entirereport Amendment: All testsubstanceconcentrationwsere changed to reflecthe purityof the test substanceas determinedby the Sponsor in a reanalysiosf the testsubstance(FC-95, Lot 217). Test concentrationosriginauywere reportedinmg/L. The certificaotfe analysisDated March 9, 2000 indicateda purityof 90.49%. Therefore,alltest substance concentrationwsere recalculateadnd reportedas mg a.i./Lbased on the 90.490/opurity. Reason: To reportthermft ofthetestbased on thesubstancepurityof 90.49% attherequest of theSponsor. AMENDED WILDLIFE INTERNATIONAL LrD. -49APPENDIXIV - Continued Report Amendment PROJECTNO.: 454E-101 AMENDMENT SIGNATURES: ((,)/,, i o .4,1 @L Edward C. Schaefer Manager, Biodegradation @/.@ DATE Henry Kr6gd, Ph.D. DirectorA,quaticToxicologyand Non-TargetPlants REVIEWED BY: Marsho T.Hy@s Quali@ AssuranceonProgramSu(e/rvi'sor DATT DATE AMENDED WILDLIFE INTERNATIONAL lm LTD. AMENDMENT TO STUDY PROTOCOL PROJECTNO.: 454E-101 Page I of2 STUDY TITLE: PFOS: AN ACTIVATED SLUDGE, RESPIRATION INHD3ITION TEST PROTOCOL NO.: 454/120198/ASRIT/SUB454 AMENDMENT NO.: I SPONSOR: 3M Corporation PROJECR NO.: 454E-101 3M LAB REQUEST NO.: U2723 El AMENDMENT: Add: REASON: Page 3;Test Substance The testsubstancewiR be atitninistebryeddirectweight addition.Directweight additionis themost appropriatreouteof administratioonf testsubstancesthatare relativeilnysolublienwater. Route of atimintiafionwas changed from volumetricadditionof an aqueousstock solutionto directweightadditionbecauseof the low water solubiliotfy the test substance. Ed FFECRIVE DATE: 21 December 1998 AMENDMENT: Delete: Page 4; StockSolutionPrepartion A stocksolutionof thetestsubstancewiU be preparedat a nommal concentrationf 1000 mg active/iLnhighqual4 water(e.gN.anopure). REASON:' Route of administratiwoans changed from volumetricadditionof an aqueousstock solutionto directweightadditionbecauseof the low water solubiliotfy the test substance. EFFECRIVE DATE: 21 December 1998 o,.-PA 17-71 WILDLIFE INTERNATIONAL LTD. PROJECTNO.: 454E-101 Page 2 of2 AMENDMENT: Change: To: Page 5;Procedure Testmixtureswillbe preparedat15 minuteintervalsstartinwgiththefirsctontrol.The controlwillcontain9.6 mL of synthetiscewage, 120 mL of inoculumand enough municipalwatertobringthetotavlolume up to300 mL. The mixturewillbe promptly aeratedata ratesufficienttokeep the solidsinsuspension.Subsequentmixtureswill contain9.6mL of synthetiscewage,120 mL of inoculum,theappropriatveolume of testorreferencseubstancestocksolutiona,nd enough municipalwatertobringthetotal volume up to300 mL. Finallya,secondcontrolwillbe prepared.Allmixtureswin be aeratedforffim hours. Testmixtureswillbe preparedat 15 minuteintervalsstartinwgiththefirsctontrol.The controlwillcontain9.6 mL of synthetiscewage,120 mL of inoculmnand enough municipalwatertobringthetotalvolume up to 300 mL. The mixturewin be promptly aeratedata ratesufficientto keep thesolidsin suspension-Subsequentmixtureswill contain9.6inL of synthetiscewage,120 mL of inoculunit,heappropriataemount of testsubstanceor volume of referencesubstancestocksolutiona,nd enough municipal waterto bringthetotalvolume up to 300 mL. Finallya, secondcontrowlillbe prepared.Allmixtureswillbe aeratedforthreehours. REASON: Route of administratiownas changed from volumetiicadditionof an aqueous stock solutionto directweight additionbecauseof the low watersolubilitoyf the test substance. EFFECRIVE DATE: 21 Decmnber 1998 STUDY DIRECTOR DATE LABOlkATOR YMANAGEMENT L SPONSOR'S REPRESENTATRVE DAlt WILDLIFE INTsc-'R-NATIONAL.,-TD. DEVIATION TO STUDY PROTOCOL PROJECTNO.: 454E-101 Page I of I STUDY TITLE: PFOS: AN ACTIVATED SLUDGE, RESPIRATION INHIBITION TEST PROTOCOL NO.: 454/120198/ASRIT/SUB454 DEVIATION NO.: I SPONSOR: 3M Corporation PROJECTNO.: 454E-101 DATE OF DEFACTO DEVIATION: December 12,1998 DEVIATION: Procedure,Page -5-: The 3 mg/L 3,5-dichlorophenmoilxturewas aeratedforthreehoursand one minute. REASON: Inadvertenetrrorby studypersomel. IMPACT: This deviatiodnidnotimpacttheintegritoyfthestudy. STUDY DIRECTOK LA.B-O'R'ZOPY MANAGEMENT DATE DATT PROTOCOL PFOS: AN ACTIVATED SLUDGE, RESPIRATION RQBMITION TEST OrganisatiofnorEconomic Cooperationand Development OECD Guideline209 and CouncilofEuropean Communities Directiv6e7/548/EEC Annex V, GuidelineC.11 3M Lab RequestNo. U2723 Submiffedto 3M Corporation EnvironnumtalLaboratory P.O.Box 33331 St.Paul,Minnesota 55133 WILDLIFE INTERNATIONAL LTD. 8598 Commerce Drive Easton,Maryland 21601 (410)822-8600 4@, st I . December 1,1998 PROTOCOL NO.: 454/120198/ASRIT/SUB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. -2- PFOS: AN ACTIVATED SLUDGE, RESPIRATION D4MBITION TEST SPONSO SPONSOR!S REPRESENTATIVE: TESTING FACILIT STUDY DIRECTO LABORATORY MANAGEMENT: 3M Corporation EnvironmentalLaboratory P.O. Box 33331 St.Paul,Minnesota 55133 Ms. Susan A. Beach WildlifeInternationaLltcL 8598 Cormneme Drive Easton,Maryland 21601 Ed Schaefer Henry 0. Krueger,Ph.D. Manager of AquaticToxicology& Non-Target Plants FOR LABORATORY USE ONLY Proposed Dates: Experunental StartDate: ProjectNo.: ie- TestConcentrations: @@P0,10,100,500)lw Test Substance No.: Experimental TerminationDate- 14 f7 /ft Study Room: vo.-.* 3-1 int/Date: ReceiptDate: PROTOCOL APPROVAL STUDY DIRECTOR DATE LAB(YRAT014Y MANAGEMENT 157ATE SPBWSOR!S RFPRESEgfATIVE PROTOCOL NO.: 454/120198/ASRIT/SUB454 DATE 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LrD. -3- INTRODUCTION The purpose of thistestisto providea screeningmethod to identifsyubstancesthatmay advms* affectaerobicmicrobialtmlunentPlantsand to indicatesuitablenon-inhibitortyestsubstance concentrationsforuse inbiodegradabilittyests. OBJECRIVE The Objectiveof thestudywillbe to assessthe effectsof thetestsubstanceon activatedsludge microorganisms by measuring therespiratiornate.An EC50 willbe calculatedi,fpossible. EXPERU*IENTAL DESIGN The testwillcontaina controlr,eferencea,nd treatmentgtoup. The controlgroup isused to determinethebackground respiratiornateof the sludge and willnot be exposed tothetestsubstance. The referencegroup willbe dosed with 3,5-dichlorophenoaL known mlubitorof respirationa,t concentrationosf 3, 15,and 50 mg/L. The testsubstancewillbe testedat 1,3, 10,30, 100, 300, and 1000 mg/L. MATERIALS AND METHODS Test methods are based on the proceduresspecifiedin the OECD Guidelinefor Testingof Chemicals, Method 209 (1)and Councilof the European Communities, GuidelineC.11,Activated Sludge,RespiratioInnhibitioTnea (2). Test Substance Informationon thecharactmizationof test,controlor referencesubstancesisrequiredby Good LaboratoryPracticeStandards(GLP), 40 CFR Part 160.31. The Sponsor isresponsibleforproviding VtrlldliIfnetemationaLltd.writtenverificatiotnhatthe testsubstancehas been charactmizedaccording toGLPS Priortousmg.m thetest.The attachedform IDENTIFICATION OF TEST SUBSTANCE BY SPONSOR (Appendix ]I)isto be used to provideinformationnecessaryforGLP compliance. If writtenverificatioofnGLP testsubstancecharacterizatiiosnnot providedto WildlifeInternationaLltd., itwillbe notedin thecompliancestatementof thefinalreport. PROTOCOL NO.: 454/120198/ASRIT/SUB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. -4- The Sponsorisresponsibleforallinformationrelatedto thetestsubstanceand agreesto accept any unused testsubstanceand/ortestsubstancecontainersremaining atthe end of thestudy. Stock SolutionP=aration A stocksolutionofthetestsubstancewillbe preparedata nominal concentratioonf looo mg activ/eL inhighqualitwyater(e.gN.anopure). In additiona,stocksolutionof 3,5-dichlorophenowlill prepared by dissolving500 mg in 10 mL of IN NAOH and thendilutingto3Q mL withhigh quality water. V&Ue sfininge,nough IN HS04 (approximately8 ML) willbe added toreachthepointof incipienptrecipitatioTrhle solutionof3,5-dichlorophenotlhenwillbe dilutedto I L withhigh quality water. Test Conditionsand &12aratas Control,referencea,nd treatmenttestmixtureswillbe incubatedat20 20C and aeratedfor3 hours at a ratesufficienttomaintainsolidsin suspension.The mixtureswillbe preparedand aerated in 500 mL plastiEcrlemneyerflasksand thentransferreidntoa 300 mL BiochemicalOxygen Demand (BOD) bottletotheconductdissolvedoxygen (DO) measurements. Test Ino ActivaWd sludgefrom theProspectBay WasWwater TreaftnenPtlantwillbe used as the inocwum for thetest The ProspectBay Facilitryeceiveswastes from predominantlydomesticsources.The sludge willbe sievedusing a 2 nun screenand then settledfor approximately30 minutes. The supernatantabove thesettledsolidswillbe drainedand thetotalsuspended solids(TSS) concentration of the settlesdludgewillbe detmmhw& Based on theresultt,heconcentratioonfthesludgewillbe adjustedto 4000 mg/L (:h10-/,b)y dilutinwgithmunicipalwater. Btat, - Ifthesludgecannotbe used on theday of collecfioonrifthesame batchisrequiredto be used on subsequentdays(maximum fourdays),50 mL ofsyntheticsewage (Appendix U) willbe added to each liteorf activatesdludgeattheend of each working day. The sludgewillbe aeratedovernightat20 2*C. Before use,thePH and totalsuspended solidsconcentratioonf theactivatesdludgewillbe det=2ined md, ifnecessarya@djustetdo pH 6.0-8.0 and a solidsconcentratioonf4000 mg/L (@:10*/o). PROTOCOL NO.: 454/12019&/ASRIT/SU]3454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. -5- Pro Testmixtureswillbe preparedat 15 nunute intervalstartinwgth thefirstcontrol.The control willcontain9.6mL of syntheticsewage, 120 mL of inoculum and enough municipalwater to bringthe totalvolume up to300 mL. The mixtureWillbe promptly aeratedat a ratesufficientto keep thesolids inSuW=iOrL Subsequentmixtureswillcontain9.6 mL of syntheticsewage, 120 mL of inoculum,the appropriatveolume of testor referencesubstancestocksolutiara4nd enough municipalwater to bring thetotavlolume UP to300 mL. Finallya,secondcontrolwillbe prepared,An mixtlm willbe aerated forthreehours. Sa=le AnW3ig Afterdm hoursOf =ation, thecontentsofthefu'svtesselwillbe transferretdoa BOD bottle and therespirafimratewillbe measured over a periodof up to 10 minutes. Dissolvedoxygen readings willbe recordedevery 10 secondsfor 10 minutesor untiltheDo dropsbelow 1.0mg/L ,which ever cOnIm ftst The respiratiornatein subsequentvesselswillbe determinedin an identicamlanner at 15 minute intervalso thatthe contactume of thetestsubstancewith ft activatedsludgeisthreehours. Calculations A respiratiornatewin be calculatedforeach testmbdm and expressedinmg OAAour. The ratewillbe calculateudsingDo valuesbetween approximately6.5mg OA and 2.5mg 02/L,or over a 10 minute periodiftheDO doesnotreachapproximately2.5mg OA. The percentmhibibonforeachtestsubslmw cmcentratimwillbe calculateudsingthefollowing equationand Plottedagainstconcentratioonn log paper: Percent inhibition 2RS x 100 RC, + RC2 PROTOCOL NO.: 454/120198/ASRIT/SUB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. -6- where It. RC, = RC2 = oxygen consumption rateata given concentrauonof thetestsubstance oxygen consumption rate,Control I oxygen wmmption mte,Control2 An EC50 valuewillbe derivedi,fpossibleb,ased on thepercentinhibitiovnersustestsubstance concentration.Confidencelimits(950/of)orthe EC50 willbe determinedusing standardstatistical procedures(3). El C@aalityControl The testisconsideredvalidonlyifthefollowingcriteriaaremet: - thetwo controlrespiratiornatesare within15% of each other; - theEC50 (3hows) of3,5-&cblorophenoilsin the acceptedrangeof 5 to 30 mgAL. RECORDS TO BE MAM Records to be mmntamed vau mclude,but not limitedto,the fouowmg: I- A copy of thesignedprotocol. 2. Identificatioand charactmizatioonf thetestsubstanceas providedby Sponsor. 3. Test initiatioannd terminationdates. 4. Experimentalmitiatimand wrminatlondates. 5. Stock solutionconcentratiocnalculationasnd solutionpreparation. 6. Activatedsludgesourceand prebratmentdetails. 7. Test temperatureand durationS. Reference substanceresults. 9. AU dissolvedoxygen meww=mts. 10. Temperature rangerecordedduringtestperiod. 11. Inhibitioncurve and method forcalculatioonf EC50. 12. IfcalculatedE,C50 and 95% confidmce limits. 13. A copy of thefinalreporl PROTOCOL NO.: 454/120198/ASRIT/SLlB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. -7- El FINAL REPORT A finarleporotftheresulotftshesh* vaUbepreparbeydWildliIfneternatiLotnda.Tlhereport istoincludeb,ut isnotlimitedto,thefollowingwhen applicable: 1 - Name and addressof facilitpyerformingthe study. 2. Dates on which the studywas initiateadnd completed. 3. A statementof compliancesignedby the Study Directoraddressingany exceptionstoGood LaboratoryPracticeStandards. 4. Objectivesand Proceduresstatedin theapproved protocolincludingany changes in the original protocol. 5. Identificatainodn dmractmizationof thetestsubstanceasprovidedby Sponsor includingname, CAS number, percentactive,and othercharacteristicisf,providedby the Sponsor. 6. A descriptioonf thebmmformations and calculationpserformedon thedata. 7. A descriptioonf themethods used and referenceto any standardmethod employed. 8. A descriptioonf thetestsystem 9. A descriptioonfthepreparatioonf the*tesstolutionst,h,etestincgoncentration(st)h,erouteof administrationa,nd thedurationof thetest 10. A descriptioonfallcirm@ces thatmay of affectedthequalityorintegritoyfthedata. 11. The name ofthestudydirectort,henames of otherscientistosr professionalsa,nd thenames of allsupervisorypersonnel,involvedin thestudy. 12. The signedand datedreportsof each of theindividualscientistosr otherprofessionalisnvolved in thestudy,ifapplicable. 13. The locationwhere the raw dataand finalreportareto be stored. 14. A suten=t preparedby theQualityAssuranceUnit listintghedatesthatthesu* inspections and auditswere made and the datesof arryfindingswere reportedto the Study Directorand Management 15. Ifitisnecessarytomake correctionosr additionsto a finalreportafterithas been accepted,such changeswillbe made intheform of an amendment issuedby the StudyDirector.lie amendment willclearliydentifythepartof thefinalreportthatIsbeing amended and thereasonsforthe amendment, and willbe signedby the Study Director. PROTOCOL NO.: 454/120198/ASRIT/SUB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. -8- CHANGING OF PROTOCOL Plannecdhangestotheprotocowlillbe intheformofwritteanmendmentssignebdy theStudy Directorand theSPonsc)esRepresentative.Amendments willbe consideredas partof theprotocoland willbe attachedto thefinalPmtocoL Any otherchanges willbe inthe form of writtendeviationsigned by theStudy Directorand filedwiththeraw dat& Allchangestotheprotocolwillbe indicatedinthe finalreport. GOOD LABORATORY PRACRICES Tins studywillbe conductedinaccordancewithGood LaboratoryPracticeStandardsforEPA (40CFR Part160);OECD Principleosf Good LaboratoryPractice(sOCDETGD (92)32,Environment Monograph No. 45);and Japan MAFF (59 NohSan, NotificatioNno. 3850,AgriculturaPlroduction Bureau). Each studyconductedby WildlifeIntemafionaLltcLisroutinelmyamined by theWildlife InternationaLltcLQualityAssurance Unitforcompliancewith Good LaboratoryPracticesS,tandard OperatingProceduresand thespecifiepdrotocol.A statementofcompliancewith Good Laboratory Practicewsillbe preparedforallportionsofthestudyconductedby WildlifeInternationLatlcL Raw data forallwork performedatWildlifheftmtional Ltd.anda copy ofthefinalreportwillbe filedby project number in archiveslocatedon theWildlffeInternationaLltd.siteo,r atan alternativIemfion tobe specifieidnffief,mid =pod. PROTOCOL NO.: 454/120198/ASRIT/SUB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. -9- REFERENCES I Organisation for Economic Cooperation and Development. 1989. ActivatedSludge RespirationInhibitioTnest.OECD Guideline209. 2 Council of theEuropean Communities. Directiv6e7/548/EEC. Annex V. Guidelinec.ii, ActivatedSludge RespirationInhibitioTnest. 3 Stephan, C.E. 1977. "Methods forCalculatinagn LC50," AquaticToxicologyandhazard EvaluationsA.mericanSocietfyorTestingandMaterialsP.ublicatioNnumber STP 634,pp 6584. PROTOCOLNO.: 454/120198/ASRIT/SUB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL L-rD. -10- APPENDIX I IDENTIFICATION OF TEST SUBSTANCE BY SPONSOR To be Completed by Sponsor 1. Test SubstanceIdentity(name tobe used inthereport): @erfllja=tane SulfonicAcid-PotassiumSalt (Fkus) Sample Code orBatchNumber. Lot 217 Purity(% ActiveIngredient-)-:98.9% H. Test Substance Characterization ExpirationDate: 2008 Have theidentitys,trenlethg,metty and compositionorothercharacteristics which &Proyriatelyle e e testsubstancebeen determinedprior to the o thisitidyinaccordancevnthGLP Standards? Yes-No X III. Test Substance StorageConditions Pleaseindicatetherecommended storageconditionsatWildlifeInternationaLltd. Ambient room I=Mmt=- Has thestabilitoyf the testsubstanceunder thesestorageconditions been detenninic@idn accordance with GLP Standards? Other pertinentstabilitiynformation: Yes-No X IV. ToxicityInformation: Mammalian: Aquatic: Rat LD50 251 me/ke Mouse LD50 YZL InvertebratTeoxicity(EC/LC50) FishToxicity(LC50) Dndm@a maizna:27 mgl Rainb.owtrout:II mgl DapbWa mamia: 50 me/L Fathead minnow- 38 mpJL Other TO)acityInformation(mcluchngfindmgsofchromc and subcbrome tests): See MSDS- PROTOCOL NO.: 454/120198/ASRIT/SUB454 3M LAB REQUEST NO. U2723 WILDLIFE INTERNATIONAL LTD. kPPENDIX U. SYNTHETIC SEWAGE The syntheticsewage providesthenecessarynutrientrsequiredforbacteriamletabohsrm itispreparedby dissolvingthefollowingamounts of substancesin I liteorfmunicipalwater: 16.0 g peptone 11.0 g meat extract 3.0g urea 0.7g NaCl 0.4g CaCI2 2H20 0.2 g MgSO,4 7H20 2.8 g K2BPO4 Reagent graded=ncals or betterwillbe usedwhen available.The constituentosf the synthetiscewage arenot known to contain any contanunantsthatarereasonableexpectedto be presentand areknown tobe capableof interferinwgith the study. PROTOCOL NO.: 454/120198/ASRIT/SUB454 3M LAB REQUEST NO. U2723