Document 3J88ZY2ozbY9nO5oGnr8rGNp3

Study Title Soil Adsorption/Desorption Study of Potassium Perfluorooctanesulfonate (PFOS) Data Requirement Based on OECD 106 Author MarkE. Ellefsoft Study Initiation Date October 17, 2000 Study Completion Date Date of Signing Performing Laboratory 3M EnvironmentalLaboratory Building2-3E-09, 935 Bush Avenue St. Paul, MN 55106 Project Identification 3M LaboratoryReport No: E00-1311 Amended Final Report Total Number of Pages 703 This page has been reserved for specific country requirements. 3M EnvironmentalLaboratory Page2 of703 GLP Compliance Statement ; StudyTitle: SoilAdsorption/DesorpSttiuodnyofPotassiuPmcrfluorooctanesulfonate t (PFOS) Study Identification Number:. E00-1311 This study was conducted in compliance with Toxic Substances Control Act (TSCA) Good LaboratoryPractice (GLP) Standardswith the exceptions listed below: Exceptions to GLP compliance: * 40 CFR 972.130(e): There'is not an electronic audittrail of corrections. The authenticatheadrdcoppyrintouatrseconsideretdheoriginraalwdata. _k E. E_lefson, Study Dir-_ctor _ - William K. Reagen, Testing Facility Management D_te " Date 3.MEnvlronmenfalLaboratory Page 3 of 703 Quality Assurance Statement ,t: StudyTitle: Soil Adsorption/Desorption of Potassium Perfluorooctanesulfonate (PFOS) Study Identification Number:. E00-1311 This study was audited by the 3M Environmental LaboratoryQuality Assurance Unit (QAU), as indicated in the following table. The findings were reportedto the study director andlaboratory management. Inspection Dates 9119/00 11/07/00 4/I8/01 5/I1/01 5/14/01 5/17/01 5/22/01 5/25/01 ,, H Phase Protocol In-phase Data(TieDr Data(TieIrI&IID Data('I'Ui&_IrIl) i Data(TkaII&IID Data(TieIrf&HI) Final Report Date Reported to Management StudyDirector 9/20100 9/20/00 11/07/00 11/07/00 4/1g/01 4/18/01 5/I1/01 5/11/01 5/14/01 5/14/01 5/17101 5117/01 5/22_/01 5/22/01 5/25101 5/25/0 1 QA U R epreesr_ative Date 3M Envi:onmentalLaborato_' Page 4 of 703 Table of Contents GLP Compliance Statement .................................................................................................. 3 Quality Assurance Statement ................................................................................................ 4 List of Tables ...................................................................................................................... 6 Study Personnel and Contributors ......................................................................................... 6 Location, of Archives ........................................................................................................... 7 .........i.........................................................................................7........................ Introduction ........................................................................................................................ 8 Materials and Methods ......................................................................................................... 10 _cal Characterization................................................................................................................ 10 Method Suranmries.......................................................................................................................... 11 Specimen Collection andAnalysis................................ ..................................................................... 14 Results and Discussion ......................................................................................................... 16 ' Data Quality Objectives ................................................................................................................... 16 Sta_tical Methods and Calculations ................................................................................................. 16 Data Sunmm_ and Discussion ......................................................................................................... 17 Refereaees .......................................................................................................................... 23 Si_a_re, s .......................................................................................................................... 24 Appendix A: Study Protocol E00-131 I-. ................................................................................ 25 Appendix B: Analytical Methods .......................................................................................... 51 ETS-8-159 "Preparationof Soil Samples for Preliminary (Tier I) SorptionStudies for Fluorochemicals as the Test Substance". ..................................................................................................................... 51 ETS-8-160 "Preparationof Soil Samples for Screening (Tier H) and Advanced (Tier HI) Sorption Studies for Fluorochemicals as the Test Substance"............................................................................ 74 OECD 106 "Adsorption- Desorption Using a Batch Equih'brinmMethod". ........................................ 89 ETS-8-155 =Analysis of Potassium Perfluorooctanesulfonateor OtherFluorochcmicals in Waste Stream of Water ExtractsUsing HPI.,C-Eleclrospray/MassSpectrometry". ...................................................... "!33 ETS-g-u0 "Analysis of PotassiumPerflttorooctancsulfonateor OtherFluorochemicals in Water ExtractsUsing HPLC-Electrospray/MassSpectroraetty/lVlassSpec_metry". ....................................... 142 Appendix C: Sample Preparation Sheets ................................................................................ 151 Appendix D: Individual Sample Data ................................................................................................ 191 Appendix E: Quality Control Sample Data ............................................................................. 237 Appendix F: Notes to File and Deviation forms ...................................................................... 274 Appendix G: Chromatograms ............................................................................................... 302 Appendix H: Raw Data Summaries ....................................................................................... 483 Appendix I: Traceability Information ..................................................................................... 594 3M Environmental Laboratory Page 5 of 703 List of Tables Table 1. SummaryTable ofPFOS Adsorb/DesorbTier I Studies..................................................... 7 Table 2. Summary Table ofPFOS Adsorb/Desorb Tier II Studies ................................................... 8 Table 3. SummaryTable ofPFOS Adsorb/DesorbTier IHStudies .................................................. 8 Table 4. Characterizationof the Test Substance, Test System, and Analytical Reference Substances ....................................................... .................................................................. 10 Table 5. Test System Distn'oution for StudyLRN-E00-1311 .......................................................... 13 Table 6. Sample Collection andPreparationfor Study LRN-E00-1311 .......................................... 14 Table 7. Suitable Analytical Method Determination......................................................................... 17 Table 8. Suitable Test Vessel Detcrmination.................................................................................... 17 Table 9. Equilibrium Time for Adsorption of PFOS......................................................................... 18 Table 10: Suitable Desorb Solvent, Methanol.................................................................................. 19 Table 11. Stability of PFOS during the Study Period....................................................................... 20 Table I2. Adsorption Kinetics of PFOS, 1:5 Soil:Solution Ratio, 48 hourTime Point.................... 20 Table 13. Desorption Kinetics of PFOS, 1:5 Soft:Solution Ratio, 48 hour Time Point.................... 21 Table 14. Adsorption Isotherms......................................................................................................... 22 Table 15. Desorption Isotherms......................................................................................................... 23 Study Personnel and Contributors Study Director Mark E. Ellfson 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Sponsor William K. Reagan, Laboratory 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Manager 3M Environmental Laboratory and Prefessional Services Contributing Personnel Cindy M. Carlson (PaceAnalyticalServices,Inc., 1700ElmSt., MinneapolisM, N 55144) Linda A. Goedspeed (BraunIntertecCorporation6,875WashingtonAve. South,Minneapolis,MN 55439) Kristin L. Terrell (BraunIntertecCorporation6, 875WashingtonAve. South,MinneapolisM, N 55439) Mark L. Anderson (BraunIntertecCorporation6,875WashingtonAve. South,MinneapolisM, N 55439) 3M EnvironmentalLaboratory Page 6 of 703 Location of Archives All original raw data and thereporthave been archivedat the 3M EnvironmentalLaboratory. Thetesmtaterialasndanalyticraelferencsetandarrdeservseamplesa,swellasthesamples pertainitnogtheanalyticpahlaseofthistudyarcarchiveadtthe3M EnvironmentLaalboratory. Reservesamplesd,igitcaolpieosforigindaaltaandalloriginpaalperdatawillberetaineidnthe archiveosf3M EnvironmentLaalboratorfyoraperioodfatleasIt0yearsfollowintgheeffective date of the applicable final test rule. Summary A preliminary, screening, and advancedstudy of the soil adsorptiorddesorptionof Potassium Perfluorooctanesulfonatc was performedto better understandpartitioningunder a variety of environmental conditions. Specifically, threetypes of soil, one sediment, and one sludge were tested. Analyses were conducted as describedby 3M EnvironmentalLaboratory Analytical Methods ETS-8-159 "Preparationof Soil Samples for Preliminary(Tier I) Sorption Studies for Fluorochemicals as the Test Substance" and ETS-8-160 "Preparationof Soil Samples for Screening (Tier ID and Advanced (Tier HI) Sorption Studies for Fluorochemicals as the Test Substance" (Appendix A), according to OECD Guideline 106 "Adsorption- Desorption Using a Batch Equilibrium Method". Resultosfthestudyarepresenteidnthefollowintgables: Table 1. Summary Table of PFOS Adsorb/Desorb Tier I Studies Question Is the analytical me_od appmpfiate/adequnte forthestudy? What is the best test vessel m use7 What is the equilibrium time and amount adsorbed at equih'b_um? What is a suitable desorption ro,lvenO What is the optimal soft:solution ratio7 Conclusion The methods ETS-8-159 and ETS-8-160 provide suffu:ient reeovay of the mt substance. Pol3,_cOyJene _bea will be used throughout this study. The 1:5mil:mlufion ratio shows a >50_ __Jy__r_pfion for both _oils test_. The equili_um thne is 48 hours. Methanol is a suitable desmption solvenL The optimal soil:solution ration is 1:5 Is the test substance sufficiently stable during the study pcfiod? The test subst_cc is stablc during thc course of the study. 3M EnvironmentalLaboratory Page 7 of 703 I I IIIIII r_ Table 2. Summary Table ofPFOS Adsorb/Desorb Tier II Studies (Jay f_T-l) Clay Loam (ST-2) Sa,,dy i, mm (ST-3) II I River Sediment (ST-See') l}mnesdcSludge (ST-SII0 18.3 9.72 35.3 7.42 < 120 7.6 7O4 2.6 374 7.8 1260 mll 1.3 571 NA NA Table 3. Summary Table of PFOS Adsorb/Desorb Tier HI Studies Sandy Loam 34.9 28.2 94.0 F Clay Loam Clay Ri_rSedlmmt Dome_ic Sludge 15.8 .... 47.1 lOgO < 237 14.0 25. l 8.70 338 60.2 105 ' 44.6 3 _30 Note: The units for the isotherms assume that the term r_l. Morn accurately, the units am (pgt.V= (L)t:a kg-i) Introduction FF F-,,,_Fr/ _r,/ F F F FF FF F: :d 7d c ,<o _r,/ _r,/ fF F F /?o _e+ _"K+ O POTASSIUM PERFLUOROOCTANESULFONATE CAS Number. 2795-39-3 Chemical Formula: CsFITSO_K Molecular 0PFOS) Weight: 538.22 g/tool Purpose Adsorption/desorption studieasreusefulfor generating essential information on the mobility of chemicals and their distribution in the soil, water, and air compartments of our biosphere, They can be used in the prediction or estimation of the availability of a chemical for degradation, transformation and uptake by organisms; soil leaching profile; volatility from soil; and rtm-off fromland surfacesintonatural waters. Adsorptiondata can also beused for comparativeand modeling purposes. 3M Environmental Laboratory Page 8 of 703 The distribution of a chemical between soil and aqueous phases is a complex process depending on a numberof different factors: the chemical natureof the substance, the characteristics of the soil, and climatic factors such as rainfall, temperature,sunlight andwind. Thus, the numerous phenomena and mechanisms involved in the process of adsorption of a chemical by soil cannot be completely def'medby a simplified laboratorymodel such as the present guideline. However, even if this attemptcannot address all of the environmentalpossibilities, it provides valuable informationon the environmentalrclevance of the adsorptionof a chemical, t OECD guideline 106 is aimed at estimating the adsorption/desorption behavior of a substance on soils. The goal is to obtain a sorption value that can be used to predict partitioning under a variety of environmental conditions. Therefore, equilibrium adsorption coefficients for a chemical onto various soils are _ed as a function of soft characteristics. Different soil types must be used in order to emulate the interactions of a given substance with naturally occurring soils. The soil parameters thatare believed most importantfor adsorptionare pH, organic carboncontent, clay content, and soil texture. The procedures outlined in the guideline are designed to evaluate the adsorption of a chemical on different soil types thathave a varying range ofpH, organic carbon content, andsoil texture. The guideline is comprised of three tiers: 1.1 Tier I: The Preliminary Study 1.1.1 The preliminarystudy is designed to determine: a) a suitable analytical method b) the adsorption of the test substance onto the surfaces of the test vessels c) thc equilibrationtime for adsorption and the amount of test substance adsorbed at equilibrium d) a suitable desorption solvent e) the soil:aqueous solution ratio f) the stability of the test substance during the study period 1.1,2 The preparatorymethodology for Tier I is descn_oedin the 3M Environmental Laboratory Method ETS-8-! 59: Preparationof Soil Samples for Preliminary (Tier I) Sorption Studies for Fluorochemicals as the Test Substance (based on OECD Guideline 106). 1.2 Tier H: Scr_ning Study: 1.2.1 The screening study is designed to study the adsorption of the test substance in three different soil systems, one sediment, and one dried sludge by means of: a) adsorption kinetics at a single concentration b) de_-mination ofdis_lmtion coefficients I_ and K_ 1.2.2 The prepsratory methodology for Tier H is described in the 3M Environmental Laboratory Method ETS-8-160: Preparation of Soil Samples for Screening (Tier H) and Advanced (Tier HI) Sorption Studies for Fluorochemicals as the Test Substance (based on OECD Guideline 106). 1.3 Tier IlI: Adsorption Isotherms and Desorption Kinetics/Desorption Isotherms 1.3.1 The advanced study is designed to: a) determine the Freundlich adsorption isotherms that, in turn,determine the 1Accordingto OECD Guideline106 3M EnvironmentalLaboratory Page 9 of 703 I I III influence of concentration on the extent of adsorption onto the soils, sediment and sludge. b) study desorption by means of determining desorption ldnetics/Fretmdlioh desorption isothen_ 1.3.2 The preparatory methodology for Tier 11Iis described in the 3M Environmental Laboratory Method ETS=8-160: Preparation of Soil Samples for Screening (Tier Io and Advanced (Tier HI) Sorption Studies for Fluorochemicals as the Test Substance (based on OECD Guideline 106). Materials and Methods ChemiC.Characterizaeon Table 4. Characterization of the Test Snbstance, Test System,and Analy_cal Reference Substances T. Substance Sota'ce F_zrmti_otne StorageConditions TCR Identification Nu_r Plrysicai Description Purity J PFOS 3IME_ISOpecialty Chemical, s/3V2001 Frozen TCR-000 !7-046 Bid& 236- White Pow_ 97.9./, I ,T.'PHI_S S3_)ta:st La_ _o_ Frozen TCR-00017-047 White Powder TBD FM)c_ma * AJ reported by 3M En_iromnemal Laboratory Report #E00-1716 P_" Solubii#y of PFOS in Water. ** Pbase...,_lubili 0, of PFOS in Namral Seawater and aa Aqueo.. Solulion of 3.5_ Y_tdium Cldorid_ and Phase: Solubility af PFOS in n-Octar_l. All solubilitydL_rninaticvsofPFOSTCR-00017-046were_ at22-25_. For PFOS stability informationrefer to 3M EnvironmentalLaboratoryreportW-1878 (PFOS hydrolysis study). 3M EnvironmentalLaboratory Page 10of 703 sea Type "source DExaptieration Stmage Cnndiliom _cal LotNxm/_ Ph3mical ,Dmai_on %CaOrrbpohinc % Sand % Silt % Clay Clay _e 12/31/2015 Room Tempemtu_ 00-2407 Driedand sieved 2.6% 16% 22% ,, 62% ii BLaoranmes _ 12/31/2015 Room Tempetattae 00-2404 Driedand sieved 4.9% 39% 50% I I% ClayImam ^_se 12/31/2015 SandyLoam Ague 8/1/2015 SeRdiivmerent A_ 12/31/2015 DSolmudegsteic _ 10/'31/2005 Room Tenaperalx_ 00-2405 Driedand sieved 2.6% 21% 46% 33% Room Tempeamae 99-2564 D_aland deved 2.8% 580,6 22% 20% Room Terrcemttae 00-2046 Driedand sieved !.3% 39% 42% ,,,, 19% Room Ternpemtt_ 2781 Driedand sieved N/A N/A N/A N/A Method Summaries ETS-8-1S9 "Preparation of Soil Samples for Prellm/nary (Tier 1) Sorptlon Studies for Fluoroehemicats as the Test Substance" Suitable Analytical Method: A soil of high adsorbability(high organic carbonand clay content) is agitated with an appropriatevolume of 0.01 M C.aC12solution ata 1:5 (w:v) ratio for a minimum of 4 hours. The mixture is centrifuged and the aqueous phase filtered, if necessary. This "matrix solution" is then preparedby adding 100uL of 500mg/L PFOS in a 10ml volumetric flask to reach a nominal conce_atrationwith/n the concentrationrange that is likely to occur during the test. This "study sample" is then analyzed using HPLC/MS. After the study sample has been analyzed, a determinationis made as to whether HPLC/MS.is a suitable analytical method for the test substance. Suitable (M!n!mally Adsorbing) Container Up to five containers comprising a variety of materials are exposed to a 0.01 M CaCI2 aqueous solution dosed with the test substance at a conoentration of 0.10mg/L and 1.0mg/L for a minimum of 24 hours. The resulting solution is analyzed for the test substance using HPLC/MS. In addition, an extraction of the container walls is made with methanol. This extract is analyzed as well. Any container that adsorbs less than 10%of the test substance onto its walls is considered suitable for use as a study container. Alternatively, the container demonstrating the least amount of test substance absorption is chosen from those tested. Selection of Optimal Soil: Aqueous Solution Ratio, Determination of EqulUbratlon Time, and Stability of the Test Substance Under the Conditions of the Study The optimal soil: aqueous ratio is det__-,inedby using two types of soils and three soil: solution ratios. An aqueous solution in contact with the soil is spiked with 125uL of 3M EnvironmentalLaboratory Page 11 of 703 500mg/L PFO$ to a concentration of 5.0mg/L. Sufficient tubes are preparedsuch that tubes canbe removed at intervals (spanning 0 to 48 hr) and the aqueous portion analyzed. Equilibriumis determinedby plotting the adsorptionof the test substance over time. The optimal soil: solution ratio is determined by comparing of the amount of adsorptionof the test substance at equilibriumfor the various soil: solution ratio study samples. Acceptable values are soil: solution ratios thatgive a depletion of the test chemical greaterthan 20% and preferablygreater than 50% at cquilibtium. Stability is determinedby a mass balance determinationfollowing a methanol extraction of the soil. The mass balance determination is conducted on the one soil:solution ratio per soil that gives a depletion of the test chemical above 20%and preferably above 50%at equilibrium. 8uitable Desorption Solvent: Methanol was investigated as the suitable desorption solvent for the test substance. A high clay content soil was dosed with the test substance at two levels (0.75 Izg,7.5 gg). The test substance was then extractedfi'om the study samples three times with methanol. The combined methanol extracts are then preparedfor analysis by HPLC/MS. In all cases, adequate quality assurance samples were prepared and analyzed. The equilibration steps were performed at 19 to 30 degrees C. ETS-g.160 "Preparation of Soil Samples for Screening (Tier IO and Advanced Crier HI) Sorptioa Studies for FInoroehemicals as the Test Substance" Tier H: Adsorption Kinetics (One concentration): Appropriatesoils and/or sediments and/or sludges were selected for the study. Replicate study samples containingthe soils (or sediments or sludges) are equil_rated by shaking for at least 12 hours at room temperaturewith 0.01 M CaClz. Study samples are dosed with the test substanceat approximately0.5 mg/L and placed on an orbital shaker. Replicate sets of these study samples are removed at designated time points throughouta 48 hour lime period. Studysamples are then prepared and analyzed for the target analyte. The adsorption kinetics are determined using this data. The last set of study samples (48 hour) arc saved and used for the dcsorptionkinetics portion of the method. Tier HI: Desorption Kinetics (One concentration): After the adsorption kinetics experiment, the 48 hour study samples are centrifugedand the aqueous phase removed. The volume ofsohtion removed is replacedby an equal volume of 0.01 M CaCI2without test substance. The new mixture is agitated until the desorption equilibriumis reached. During a 48 hourperiod, at defined time intervals, small aliquots of the aqueous phase are removed and analyzed for the targetanalyte. The experiment then continues with the original mixture. The desorption kinetics are deteiiained using this data. Tier m: Adsorption Isotherms 0ive concentrations): Five test substance concentrationsare used, coveting two orders of magnitude. Study samples containing soil (or sediments or sludges) in contact with 0.01 M CaC12are equil_rated for a minimum of 12 hours. After equilibration, the studysamples are dosed with test substance. The samples are then gently agitated until adsorptionequilibriumis reached. Sample sets are removed from the orb/tal shaker at designated time intervals. The study samples are then preparedand analyzed for the target analyte. The adsorption 3M EnvironmentalLat_omtory Page 12of 703 isotherms are calculated using this data. The study samples fi,om the last time interval are saved for the desorption isotherm study. Tier HI: Desorption Isotherms: The study samples from the adsorption isotherm study are used for the desorption isotherm study. These samples are centrifuged and the aqueous layer removed. An equal volume of fresh 0.01 M CaCI=solution containing no test substance is added to each sample. The samples are placed in the orbital shaker and equilibrated for 48 hours. The samples are then pr_ared and analyzed for the target analyte. (These study samples are saved and used to determine mass balance.) The desorption isotherms are detea-t_inedusing this data. Tier m: Mass Balance: The study _unplcs fromthc dcsorption isotherm study arc used for the mass balance study. The study samples are centrifuged and the aqueous layer removed. Three portions of methanol are addedto the study samples. With each additionof methanol, the study samples arc agitated, centrifuged, and the methanol removed and placed in a second container. These subsequent (methanol) study samples arc then preparedand analyzed for the targetanalytc. Mass balance is determined using this data. In all cases, adequatequality control samples arc prepared and analyzed. Additionally, the equilibration steps wcrc carriedout at between 19 and 30 degrees C Table 5. Test System Distribution for Study LRN-E00-1311 Tier I "Suitable Analytical Method" Tier r'Suitable DcsorptionSolvent" TierI"Suitablc (Minimally Adsorbing)Container" TierI "Selection of Optimal Soil: Solution Ratios" Tier H "/_dsorption Kinetics" Tier IR "[ksorption Kinetics" Test Substance Solutions ConU'olBlanks Test Sobstance Solutions ControlBlanks Test Substance Solulioo_s ConlrolBlanks Test Substance Solutions Conlml Blankq TestSubstance Solutions Control Blanks Test Substance Solutions ControlBlanks 45 45 15 15 18 + 6Matrix Spik_ lg + 6Matrix Spikes 9 + 3 matrixspikes 60+ 16 Matrix Spik_ 30 + 8 matrixspikes 171+ 57 Matrix Spik_ 63 + 21 matrix spikes 9 + 3 matrixspikes 60+ 16Matrix Spikes 29 + 8matrixspikes 171 + 57 MatrixSpikes 63 + 21 rm_ix spikes 144+ 48 Malrix Slffl0_ 36 + 12raah'ix spikes 139 + 48'MatrixSpikes ' 36 + 12matrixspikes 126 + 42 Matrix Spilms 115+ 42 MatrixSpikes 126 + 42 Matrix Sp/l_s 126+ 42 MatrixSpikes ,,,=, ,,, ,,, 3M EnvironmentalLaboratory Page 13 of 703 TierIH"Adsorption TestSubstance 180+ 60Matrix Isothem_" Solutions Spikes Tier Isotherms" ControlBlanks Test Solutions 36 + 12matrix spikes +30 Spikes TierHI_Mass Balance" Conlrol Blaal_ Test Substance Solutions lfl'+ 6 malrix spil_ 90 + 30 Malrix Siz_es IS0+ 60MauixSpikes 36 + 12 matrix spikes 89+30 Spik 18+ 6rnatfsipxikes 89+ 30 MatrixSpik_ Specimen Collection and Analysis During the course of the study, a|iquots of the test systems were collected at predcterm/ned time intervals. Some sample aliquots were diluted with methanol. The following table describes the sampling regimen information: Table 6. Sample Coileetlen and Preparation for Stady LRN-E00-1311 Step Procedure Re _licates Date(s_ Performed TierI "Suitable Work" Eachofthtel_emeilst,hesedime_andthe shuigaerecquih'brwaitteh0d.01M_ in uipr_-__:_."nmrixsolutiiosnt"hen removedanddosedwilhthetestsubmnce, andthe solutioanmly=d. Each"matrixsolntiiosn" Sampleasliquotted doseidnt_plicatnedo,ne 11102/00 conuoslampleis prepared. Tierl '_'uitable Conlainm_ Fourtypesoftc_vtesselse,schofa different Each typeofconlaincirs materiala,re_ tothetrotmbslaxw.feor dosedattwoconcen_tk)m, 24hours.Theresultingsolutionis mmly-z_ andasetof controlsis also Aqueoussan_es aliquotted11/14/00 M_qlmnoelxtr_tions forthetesstubstantcomeeasuraenylostso prepareEdv.eryvesselis aliquotItIeId15/00 theconmin_,l"hetestvesselis thenextmcted extractedwithmedmmlafler tomt:mm-acnytestsubstancethatmayhave adsorbedontothesidesif thecontainer, thetestsuteutm_hasbeen removed. T'w.I_ "Suitable - Demrption Solvenf' Twotypesofsoilaredosedwiththete_t " Eacht3_ ofsoilis dosedat Methanoelxtractions substancea,ndthesoilis extractedwith twoconcenwatioma,ndaset aliquattedi/22/01 mee_taolthreetimes.The _ are ofcontroilsaslso prepared. combinedandamlyzedtomeasurethe suitabiolftihteysolvent. "_electionof OptimaSl oi_ Solution Ratioasnd MassBalance" soft:solutiornatiosto determinteheoptimal meom use intheremain_ ofthe stndy, Sampleasrepreparaetdsevertailmepointso &t_u_e thetimerequiredfogthemlufionto reachequih])tiuma,nda massbalance , , _tion is performed. combinatioins preparedin triplica_o, nema_ixspikeis performeadn,donecontrol is prepared, ., aliquotted11/2910012/4/00 Methanoexltractions aliquot1t2c/d7/00 3M EnvironmentalLaboratory Page 14 of 703 Tie_H "Adsorption Kinetics" Three soils, one sediment,andone sludge'are preparedill the soi]:soh_on ra_o/n_Jc?t__Iin the Tier I study. The samples are dosed with the test substameandpi_d on a shaker, samples are then Ixdledat _'veraltime points, Tier IU "Desorpfion Kinet/c" The aqueouslayeris _removedfromthe 48 hoursamples from the abovestep. Fzesh CaCIzis added tothe test vessel andthe vemel is placed on a slmk_. Small san_les am taken at severalt_e points, and_,t_ional aqueous solmion is added to replm:ethe rumple _ Tier HI Three soils, one sediment,and one sludgeare "Adsorplion prepareidnthesol,solutriaotniiondicatiend Isolhenm" the TiexI study. The samples aredined with the testmbstance(at one of 5 confemmfions) andequih'Ixa_ for eiflaet0 ot 48 houra. Tier rll "Desorplion Iso_zmz_" The aqueouslayeris removedfromthe 48 hotwsamplesfrom the eJmvestep. Fresh aqueous CaCI2solution is addedto_e test vessol andthe vessel is placed on a shakerfor 48 l_ers. Tier IU "Mass Balance Detemfinafion " The aqueoussol'don is removed firm the 48 lxmr_ar._lesind_e aboves_-p. The xen_i-2 soil is li_enexwactedwith tlaee portions of mzG_-_ol,inch time the solutionis decantedinto the same vessel. Eachsoil/t/mecomb/nation is preparedin Ir/p___, one malrixspike is performed, anda set of controlsi_ pt_ered. Each48 lmtwm_le vessel firm the aixrvestep pcoduces9 samples over the cotz_ offl3e desorptic_ (seven time pointsandtwo rmtrix s_). Each aoil/cowamtmfion/lime poinctombinatiiosn _ in trip_w_mone malfix _T,e is perfimmd. Each48 hour_vex_.l producesone _ and everythirdsample is also preparedas a matrixspike. E_ 48 hourvessel producesone s_,./e, and evewlhirsdmnpleisalso ptepaxedas a malxixspi_. Aqueoussamples aliquotted2/I/01- 2/7/01 Aqueoussamp!_ aliquotted Z/13/01- 2/15/01 Aqueoussamples aliquott2e/d14/01- 2/15/01 Aqueous samples aliquotted2/21/01 Methanol_ atiquott2e/d2_DI- 2/26/01 Diluted samples (i.e. sample exlracts) c,on_dning 250 ng/mL THPFOS as internal standard were analyzed using high-performance liquid chromatography/mass sp_hometry (HPLC/MS) in the negative ion mode. PFOS levels were evaluated versus standard curves ranging in concentration from 2.5-I 000 ng/mL PFOS and 250 ng/mL THPFOS. Internal Standard quantifi_tion was used to best fit and report the data. Target ions were deprotonated PFOS (m/z ffi499), and depmtonatedTHPFOS (m/z= 427). Analytical details are included in the file for this study that is maintained by the 3M EnvironmentalLaboratoryt;h,estudyfolderis located in the3M archives. All study samples were generated and analyzed at the 3M Environmental Laboratory. No chain of custody forms were generated or required. Reserve samples of reference materials from the 3M Environmental Laboratory will be stored at the 3M Environmental Laboratorfyor a periodnot less than 10 years following the effective date of the f'mal test rule, or until the quality of the preparation no longer affords evaluation, Reserve samples of the reference materials from the contract laboratory will be returned to the 3M Environmental Laboratory for retention and archiving. 3M Environmental Laboratory Page 15 of 703 Results and Discussion DataQualityObjectives The following data qualityobjectives are from the methods used in the present study. The data quality objectives were met, except as documented in raw data. Coefficient of Determination (r_). The coefficients of determination(r2) for the calibration curves were 0.985 or greater. The curves were examined closely for accuracy of quantitation at the low and high ends of the curve. Quadratic curve fit was applied to calibration standardsand sample data to improve quantitation over the concentration range appropriate to the data. Method Blanks. Method blanks (applicable sample matrix taken throughthe entire sample preparation,dilution, and analysis process) provided a measure of laboratorycon_-nination. Acceptable values for the blanks were less than 50% of the limit of quantitation (LOQ), defined herein as the concentration of the lowest standard. Matrix Spike Recoveries. A post-preparatory ma_ix spike sample for each of the sample groups used in the study was preparedby adding aliquots of test-analyte solution according to 3M Method ETS-8-159 and 160. The spike recoveries for >80% of the samples were acceptable (100 30%). Instances where spike recoveries outside of the control range were observed are indicated in Appendix E. Sample Triplicates. The Relative StandardDeviations of triplicate samples were acceptable when at least 80% of them were less than or equal to 30%. Q-tests were used to exclude outliers in data sets. Continulag Calibration Verification. If the percent difference for the amount of quantified analyte was greater than 30% from the true value relative to the initial standardcurve, only those samples analyzed before the last acceptable calibration check standardwere used. The remaining samples were analyzed with a new curve. Limit of Qaantitatioa (LOQ). The LOQ was equal to the lowest acveptable standardin the cal_ration curve. Calibration Standards. Eleven standardsranging in concentration from approxin_tely 2.5 to 1000 ng PFOS/mL methanol were used for the calibration curves. Calibration curves were runbefore and after every analytioal sequence. Solvent Blanks. Solvent (Methanol) blanks provide a measureof instrumental contamination. Acceptable values for the blanks were less than 50% of the limit of quantitation, defined hereinas the lowest calibration standard. System Suitability. Without performing a method validation, system suitability was demonstratedby acceptable instrumentalchecks (e.g. abbreviatedm/z check-trine,or furl auto-tune routines). StatisticalMethods and Calculations Means and standard deviations were calculated using functions provided in MicrosoftExcel_ software. Calculations with the raw data were made using the equations described in the OECD Method 106 (see Appendix B). 3M EnvironmentalLaboratory Page 16 of 703 Data S_annary and Discussion Appendices D and E summa_e individual sample data. R_resentativc ohromato_'ams presented in Appendix G. All concentrations and calculations can bc found in the data tables, along with the log plots used to determine the isotherm values. These data arc used in all subsequent tables and figures in this rClmrt. Results of the Tier I study arc presented in tabl7 through 11: Table 7. Suitable Analytical Method Determination Bin-ramLearn (b"r-I) E00-1311-0001, -0002, .0(}03 11.5% 7.51 Clay Imm _'!'-2) E00-1311-0004, -0005, -0006 115% 4.92 Clay (ST-3) E00-1311-0007, -0008, -0009 99.80/, 21.8 River Selat_ (ST-Sod) E00-1311-0010, 4]011, 4}012 116% 8.88 Domestic Sludge (ST-Slg) E00-I 3114)013, 4)014, 4)015 883% 16.0 Table 8. Suitable Test Vessel Determination "Fef6on 9_% 94._ 9_ 89..5% 244ppb 172_ 398ppb 94.4ppb 176% It was determined thatthe polypropylene centrifuge tubes were suitable for this study. These tubes had the least amount of extractablePFOS, and were the only tubes with acceptable matrix spike recoveries. 3M EnvironmentalLaboratory Page 17of 703 Table 9. Equii_brhnn Time for Adserption of PFOS J Elay i Se_mem 1:1 1".5 1".25 . l:I 1"5 ! '25 24 3468 24 36 48 24 36 48 ill 24 36 48 24 36 48 24 36 48 17.6% 21]2..07_'/, 21.6% 23.5% 19.7% 57.4% 60_ 6_t 11.0% I43% 10.6% 45.9% 45.O% 42.2% 65.3% 673% 68.0% AdsorpUon Equilibrium Plot 100.0 80.0 o=" 60.0 _-_..._ ,,,_,,..._ ..'" "._.._........_..,._- [,-_-_-_.___=.,_ _._ _' ":':'_'- - L.] "" '" _ : _'_-...,_-. "_. ._,_ _._.t:=_ '_-,_;P_"; ;_"._'i_,',_."=:;"_: ---e-- 1:1 Ratio (day) --ll--l:SRaUo(day) _4.0.0:20.0 _ 0 _-___:;__ _:_ _('$d_a_y=_)_:_,-_.._._____ -_ 20 40 80 IEqullibrlumTime, houm --1:25 Ratio 3M Environmental Laboratory Page 18 of 703 Adsorption Equilibrium Plot I 100.0 ; =.. _ ..... : :..:, _80.0 ...... " ": "....... _'"" l'-a-- 1:5Ratio(sediment) g.u_o.,4uu0u.0 " ."'.:... ." ..;: ...." ../:.'_.:._."..";:.::_.i_.;...I1--.-_-0-.-"1.1:2:15RRaatitoio(S(seeddimimeennt)tI) no _ 20.0 ".... "..-_ "--- - "-'.--;'-::__ ,._:.._:-._ 0.0 _::"!" 0 20 '"""""_ 40 60 Equilibdum Time, hours The test substance appear_ to reach equilibriumafter 24 hours in all of the soil:solution ratios. The clay appeared to take more time to reach equilibrium, therefore the 48 hour time point was used as the equilibrium time for the remainderof the study. This ensured thatall five of the soils wore given ample time to equilibrate. Table 10: SuitableDesorb Solvent, MethJmol Clay Sallmmt 0.0 1O0 I000 O.0 100 I000 <25.0 71.2 591 < 25L) 96.0 601 WA 71.2% 59.1% WA 96.0% 60.1% Despite using methanol, an excellent solvent for PFOS, the average percentrecovery of PFOS ranged from zero to 96%. It is unlikely that a different solvent would yield better recovery. Previous results in this study have indicated thatthe test substance is readily and rapidly adsorbed on the soft, andis not likely to bc completely extracted from it. The optimal soil:solution ratiowas determined to be 1:5 (refer to Table 9 for applicable data). This ratio demonstratedaverage adsorptionpercentages of PFOS ranging from approximately 75% in clay to 55% in sediment. 3M EnvironmentalLaboratory Page 19 of 703 Table 11. Stability of PFOS during the Study Period 48 J Clay ...... Selfimml 1:1 1:5 1".25 1:1 i ".5 1:25 48 71.3 48 34,3 48 35.6 48 Tube Broke 48 832. 48 912. 48 96.3 48 43._/ 48 48.1 48 24,7 48 57.6 48 78.7 48 59.5 48 73.6 48 87.4 48 83.1 According to OECD guideline 106, the mass balance calculation should show at least 90% recovery of the test substance for the test substance to be considered stable over the course of the study. The recovery of the test substance was lower than the OECD guideline, l_ely due to the incomplete desorption of the test substance from the soft. Hydrolysis studies of PFOS conducted at the 3M Environmental Laboratory have demonstrated test substance stability in aqueous matrices. The results of the Tier II study are presented in Table 12: Table 12. Adsorption Kinelics of ]PFOS, 1:5 Soil:Solulion Ratio, 48 Hour Time Point C_tST-I) Gay Loam (s'r-z) su_ tram IST-3) rover SeOhaem ts'r-Se_ I_ Sludp _'I'._IK) tX3 9.72 353 7.42 < 120 7-6 2.6 2.8 13 571 NA NA 3M Environmental Laboratory Page 20 of 703 AdsorptionPercentageas a Functionof'rime 1oo_"":'"....... ......_....._........:._.....!_.i..,._.. 80 " " - " " ':":" ' ' .......... i 7500 -}/I'f"/_/__:.__:,: ' " ""'"" ,:_i: --*x--Clrai_yerSmimen! ._."._'_',,',__' "i:... ' " ._'-_.."..".. "' :.".:""" .......,_. <......._ :, .._"'_," ,._ ,_ , t r,:. :,.. _'_=_" ,. "_'--,-.__ . . , ._. ._ , .'.'.;: --:'-. "_ " ..;--: i 0 10 :.,:" _ ,," ''" i .,,. .. j ._ ..... _- , , .,_ _ .. ,_ --',:.'-"-"._ _ ";..'r::_- _". ,:,.._--:._, "*. _ "'-; _"._,_-,.-* | 20 30 40 50 Time, hours All of the soil/sed]menVsludge matricesadsorbed the test substanceto varying degrees. The sludge samples, in the adsorption port/on of the kinetics study, demonstrated the most adsorption (>96%) andPFOS was not detected in the samples. The data indicates that adsorption occurred within the first few hours of exposure and the test substance concentration does not vary significantly after the 16hour t_ne point. The results of the Tier I]I study are presented in Tables 13 through 15: Table 13. Desorptlon Kinetics of PFOS, 1:5 Soil:Solution Ratio, 48 hour Time Point 3M EnvironmentalLaboratory Page 21 of703 Desorptlon Percentage as a Function of Time 1 80.00 I ....... ,. ....... , ..... ..... ........ .] 70.00 _,"".. _.,._._...'.:_:_"'.:'_:.. :...;.:.':..,:--_.-- ::_.:_" ,.'.:-_';h_ ._;" . _._.:.=_ " ." _..: ; : :..." _'.,.. . ,:, ,,.:. ,t: S "_':-"" .. ,',. ..,,,._.k?. 60.00 --B--Clay .".-._ r':" .,-.-.-._:.":" _..s;L=+.--'._.-'.;_,_,: ."..':..:.:,.=.mJ'%_ I-_.,".=_:_? 1!_:_..._.'.-.'!.-_"',;_-".";.-":-"_;,-__-,.?__-.'._;.._.'.._'.::__:,'=_-?_I?__'_'_-":;-"r_.:._.'_"='_.-I ...4p_y Loam ]/ _0 --'-- :._::_" _: - : -. :-.: .*_-b,.::_.:_:.:! :.;.-:.:.,,:. ._ ..- -_;'.-_._. :,...._-.-. t_-=___'-'_1 r_ ou.uu_,_:___1 I_:___' "_""'_-_,-,,,; _:i_ ,T-_- -_,,,_._,,_d_r;__'.ti :< RiverSedimentI L_-_ k:-' '_ ............. _ __,_:'._ _';._a:_---_..'-_:'.l o.oor.' 0 , ,,, .... , .... ..,..... 10 20 30 40 50 Time, hours The testsubstancewaspoorlydesorbedfromthesoiFsedimenffsludmgeatricesduringthe4g-hour studyperiod.Theriversedimmtdisplayedthemostdcsorptionat only39%after48 hours.The sludgesamplesdidnot dcsorbad_t_tablcamountof testsub_m_. Desorptionthatdidoccurwas accomplisherdatherquickly,afterthe8 hourtimepointthetestsubstanceconcentratiodnidnotvary significantly. Table 14.AdsorptionIsotherms Clay 1.40 25.1 0.884 Oty I,otm !.15 14.0 0.841 SandyLoam 1.45 28.2 0.829 Rive_Sedlmem 0.939 8.70 0.989 DmaestJSludge 2.53 338 1.26 Note:Theunitsfortheisotharn assumethatthe termn_l. Moreaccuratelyt,heunitsare(pgt-U.(L)U_if.g-t) 1.13 1.19 ! .2! 1.01 0.795 3MEnvironmentaLlaboratory Page22of703 Table 15. Desorption Isotherms Clay 2.02 105 0.860 ClayLoam 1.78 60.2 0.954 $am'yLeam 1.97 94.0 0.985 RiverSed_mt 1.65 44.6 1.02 Deme_ie Sludge 3.50 3130 0.977 Note:The unitsforthe isothermassumethatthetermnffil. Mote acctwatetyl,hv unitsare0_ "t_(1.)_ Kg"l) 1.16 1.05 1.02 0.98I ! .02 Freundlich isotherms relate the amount of test substance adsorbedon the soil to the amount present in the aqueous solution at cquih'brium.The values calculated for the regression constant indicate that the data obtained for thc test substance over two ordersof magnitude are slightly non-Sncar. References 1. Adsorption-Desorption Using a Batch Equilibrium Method (OECD 106), January 2000. Report Amendments The organic carbon normalized adsorptioncoefficient (Ke)values contained in tables 2 and 12, isotherm values contained in tables 3, 14 and 15 as well as raw spreadsheets on pages 205-233 were ton'coted following clarification of calculations described in OECD guideline 106. Table 13had 2 values switched and was corrected. The conclusion section was removed. The title page was modified to indicate this reporthas been amended. The signature page was re-signed following the amendments. 3M EnvironmentalLaboratory Page23 of 703 Ill I Signatures The amended final draft of this reportis a true representationof the data developed in this study. Ithas been issued by: William K. Reagan, Testing Facility Management Date 3M EnvironmentalLaboratory Page 24 of 703