Document zo5oJ8XMjBoqv1qrNqRy1Rxjm

Study Title Soil Adsorption/Desorption Study o f Potassium Perfluorooctanesulfonate (PFOS) Data Requirem ent Based on OECD 106 A u th o r M ark E. Ellefson Study Initiation Date October 17,2000 Study Completion Date Date o f Signing Performing Laboratory 3M Environmental Laboratory Building 2-3E-09,935 Bush Avenue S t Paul, MN 55106 Project Identification 3M Laboratory Report No: E00-1311 Amended Final Report Total Num ber o fPages 703 This page has been reserved for specific country requirements. 3M Environmental Laboratory Page 2 of 703 GLP Compliance Statement Study Title: Soil Adsorption/Desorption Study o f Potassium Perfluorooctanesulfonate (PFOS) Study Identification N um ber EOO-1311 This study was conducted in compliance with Toxic Substances Control A ct (TSCA) Good Laboratory Practice (GLP) Standards with the exceptions listed below: Exceptions to GLP compliance: 40 CFR 972.130(e): T hereis not an electronic audit trail o f corrections. Th authenticated hardcopy printouts are considered the original raw data. William K. Reagen, Testing Facility Management Date 3M Environmental Laboratory Page 3 of 703 Quality Assurance Statement Study Title: Soil Adsorption/Desorption o f Potassium Perfluorooctanesulfonate (PFOS) Study Identification N um ber E00-1311 This study was audited by the 3M Environmental Laboratory Quality Assurance Unit (QAU), as indicated in the following table. The findings were reported to the study director and laboratory m anagem ent. Inspection Dates 9/19/00 11/07/00 4/18/01 5/11/01 5/14/01 5/17/01 5/22/01 5/25/01 Phase Protocol In-phase Data (Tier I) Data (Tier H&HQ Data (Tier H&III) Data (Tier H&m) Data (Tier n& m ) Final Report D ate Reported to Management Study Director 9/20/00 9/20/00 11/07/00 11/07/00 4/18/01 4/18/01 5/11/01 5/11/01 5/14/01 5/14/01 5/17/01 5/17/01 5/22/01 5/22/01 5/25/01 5/25/01 QAU Representative Date 3M Environmental Laboratory Page 4 of 703 Table of Contents GLP Compliance Statement..................................................................................................................3 Quality Assurance Statem ent............................................................................................................... 4 List o f Tables......................................................................................................................................... 6 Study Personnel and C ontributors....................................................................................................... 6 Location, o f A rchives..............................................................................................................................7 Summary................................................................................................................................................ 7 In tro d u ctio n ........................................................................................................................................... 8 Purpose.............................................................................................................................................. 8 M aterials and M ethods......................................................................................................................... 10 Chemical Characterization........................................................................................ ...........................10 Method Summaries.............................................................................................................................11 Specimen Collection and Analysis................................ ....................................................................... 14 Results and Discussion..........................................................................................................................16 Data Quality Objectives......................................................................................................................16 Statistical Methods and Calculations................................................................................................... 16 Data Summary and Discussion............................................................................................................. 17 References..............................................................................................................................................23 S ig n a tu re s.............................................................................................................................................. 2 4 Appendix A: Study Protocol E00-1311- ..............................................................................................25 Appendix B: Analytical M ethods........................................................................................................ 51 ETS-8-159 "Preparation of Soil Samples for Preliminary (Tier I) Sorption Studies for Fluorochemicals as die Test Substance"........................................................... ..............................................................51 ETS-8-160 "Preparation of Soil Samples for Screening (Tier II) and Advanced (Tier III) Sorption Studies for Fluorochemicals as the Test Substance" ..............................................................................74 OECD 106 "Adsorption--Desorption Using a Batch Equilibrium Method"......................................... 89 ETS-8-155 "Analysis of Potassium Perfluorooctanesulfonate or Other Fluorochemicals in Waste Stream of Water Extracts Using HPLC-Electrospray/Mass Spectrometry" ........................................................133 ETS-8-110 "Analysis ofPotassium Periluorooctanesulfonate or Other Fluorochemicals in Water Extracts Using HPLC-Electrospray/Mass Spectrometry/Mass Spectrometry"........................................ 142 Appendix C: Sample Preparation Sheets............................................................................................. 151 Appendix D: Individual Sample Data...................................................................................................191 Appendix E: Quality Control Sample D ata...........................................................................................237 Appendix F: Notes to File and Deviation form s................................................................................. 274 Appendix G: Chromatograms................................................................................................................302 Appendix H: Raw Data Sum m aries...................................................................................................... 483 Appendix L Traceability Information.................................................................................................... 594 3M Environmental Laboratory Page 5 of 703 List of Tables Table 1. Summary Table o f PFOS Adsorb/Desorb Tier I Studies........................................................7 Table 2. Summary Table o f PFOS Adsorb/Desorb Tier II Studies......................................................8 Table 3. Summary Table o f PFOS Adsorb/Desorb Tier HI Studies.....................................................8 Table 4. Characterization o f the Test Substance, Test System, and Analytical Reference S u b sta n c e s......................................................... 10 Table 5. Test System Distribution for Study LRN-E00-1311 ............................................................. 13 Table 6. Sample Collection and Preparation for Study LRN-E00-1311 ............................................ 14 Table 7. Suitable Analytical M ethod Determ ination...,.........................................................................17 Table 8. Suitable Test Vessel D eterm ination........................................................................................ 17 Table 9. Equilibrium Time for Adsorption o f PFOS.............................................................................18 Table 10: Suitable Desorb Solvent, M ethanol.............................................................................. 19 Table 11. Stability o f PFOS during die Study Period.......................................................................... 20 Table 12. Adsorption Kinetics o f PFOS, 1:5 Soil:Solution Ratio, 48 hour Time Point....................20 Table 13. Desorption Kinetics o f PFOS, 1:5 Soil:Solution Ratio, 48 hour Time Point................... 21 Table 14. Adsorption Isotherms..............................................................................................................22 Table 15. Desorption Isotherm s..............................................................................................................23 Study Personnel and Contributors Study D irector Marie E. Ellcfson 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Sponsor W illiam K. Reagan, Laboratory M anager 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 3M Environm ental Laboratory and Professional Services Contributing Personnel Cindy M . C arlson (Pace Analytical Services, Inc., 1700 Elm S t, Minneapolis, MN 55144) Linda A. Goodspeed (Braun Intertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 55439) Kristin L. Terrell (Braun Intertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 55439) M ark L. Anderson (Braun Intertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 55439) 3M Environmental Laboratory Page 6 of 703 Location of Archives All original raw data and the report have been archived at the 3M Environmental Laboratory. The test m aterials and analytical reference standard reserve samples, as well as the samples pertaining to the analytical phase o f this study are archived at the 3M Environmental Laboratory. Reserve samples, digital copies o f original data and all original paper data w ill be retained in the archives o f 3M Environmental Laboratory for a period o f at least 10 years following the effective date o f die applicable final test rule. - Summary A preliminary, screening, and advanced study o f the soil adsorption/desorption o f Potassium Perfluorooctanesulfonate was performed to better understand partitioning under a variety o f environmental conditions. Specifically, three types o f soil, one sediment, and one sludge were tested. Analyses were conducted as described by 3M Environmental Laboratory Analytical Methods ETS-8-159 "Preparation o f Soil Samples for Preliminary (Tier I) Sorption Studies for Fluorochemicals as the Test Substance" and ETS-8-160 "Preparation o f Soil Samples for Screening (Tier II) 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 M ethod". Results o f the study are presented in the following tables: Table 1. Sum m ary Table of PFOS Adsorb/Desorb H e r I Studies Question Is the analytical method appropriatefadequalc for the study? What is the best test vessel to use? What is the equilibrium rime and amount adsorbed at equilibrium ? What is a suitable desorption solvent? What is the optimal soilsolution ratio? Conclusion The methods ETS-8-159 and ETS-8-160 provide sufficient recovery o f the test substance. Polypropylene tubes w ill be used throughout this study. The 1:5 soilrsofcirion ratio shows a >50% adsorption for both so ils tested. The equilibrium time is 48 hours. Methanol is a suitable desorption solvent The optimal soihsolution ration is 1:5 Is the test substance sufficiently stable during die study period? The test substance is stable during the course o f the study. 3M Environmental Laboratory Page 7 of 703 Table 2. Summary Table o f PFOS Adsorb/Desorb Tier H Studies .Soil I s pc \s er.m c Distnhmii'ti t n.lliiicMt. K... 1. I.u IVrcciti.1 of ( ) r;iniV ( ,u lull in Soil. CUy (ST-1) Clay Loam (ST-Z) Sandy Loam (ST-3) River Sediment (ST-Sed) Domestic Sludge (ST-SIg) T*-- r 18.3 9.72 35.3 7.42 <120 2.6 2.6 2.8 U NA As 1 i; s<,l Out. \ nii C Mil;< )n Niikm si i/ i I) ADMIKri ION C<11 11 l( l i s i , Is,,,. 1. k<J 704 374 1260 571 NA Table 3. Summary Table of PFOS Adsorb/Desorb Tier in Studies Soil Tspc D o irp lio n Coefficient. K,,,,. L ki! Sandy Loam Clay Loam Clay River Sediment Domestic Sludge 34.9 15.8 47.1 10.0 <237 28.2 14.0 25.1 8.70 338 94.0 60.2 105 4 4 .6 3130 Note: The units for the isotherms assume that the term n = l. More accurately, the units are (pgM'* (I.)1'" kg'1) Introduction P o t a s s iu m P e r f l u o r o o c t a n e s u l f o n a t e (PFOS) CAS N um ber 2795-39-3 Chemical Formula: CjF^SCbK M olecular W eight: 538.22 g/mol Purpose Adsorption/desorption studies are useful for generating essential information on the m obility o f chemicals and their distribution in the soil, water, and air compartments o f our biosphere. They can be used in the prediction or estimation o f the availability o f a chemical for degradation, transformation and uptake by organisms; soil leaching profile; volatility from soil; and run-off from land surfaces into natural waters. Adsorption data can also be used for comparative and modeling purposes. 3M Environmental Laboratory Page 8 of 703 The distribution o f a chemical between soil and aqueous phases is a complex process depending on a number o f different factors: the chemical nature o f the substance, the characteristics o f the soil, and climatic factors such as rainfall, temperature, sunlight and wind. Thus, the numerous phenomena and mechanisms involved in the process o f adsorption o f a chemical by soil cannot be completely defined by a simplified laboratory model such as the present guideline. However, even if this attempt cannot address all o f the environmental possibilities, it provides valuable information on the environmental relevance o f the adsorption o f a chemical.1 OECD guideline 106 is aimed at estimating the adsorption/desorption behavior o f a substance on soils. The goal is to obtain a sorption value that can be used to predict partitioning under a variety o f environmental conditions. Therefore, equilibrium adsorption coefficients for a chemical onto various soils are determined as a function o f soil characteristics. D ifferent soil types must be used in order to emulate the interactions o f a given substance with naturally occurring soils. The soil param eters that are believed most important for adsorption are pH, organic carbon content, clay content, and soil texture. The procedures outlined in the guideline are designed to evaluate the adsorption o f a chemical on different soil types that have a varying range o f pH, organic carbon content, and soil texture. The guideline is comprised o f three tiers: 1.1 Tier I: The Prelim inary Study 1.1.1 The prelim inary study is designed to determine: a) a suitable analytical method b) the adsorption o f the test substance onto the surfaces o f the test vessels c) the equilibration time for adsorption and the amount o f test substance adsorbed at equilibrium d) a suitable desorption solvent e) tiie soil:aqueous solution ratio f) the stability o f the test substance during the study period 1.1.2 The preparatory methodology for Tier I is described in the 3M Environmental Laboratory M ethod ETS-8-159: Preparation o f Soil Samples for Preliminary (Tier I) Sorption Studies for Fluorochemicals as the Test Substance (based on OECD Guideline 106). 1.2 Tier II: Screening Study: 1.2.1 The screening study is designed to study the adsorption o f 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) determination o f distribution coefficients Kj and K. 1.2.2 The preparatory methodology for Tier II is described in the 3M Environmental Laboratory M ethod ETS-8-160: Preparation o f Soil Samples for Screening (Tier II) and Advanced (Tier HI) Sorption Studies for Fluorochemicals as the Test Substance (based on OECD Guideline 106). 1.3 T ie rlll: Adsorption Isotherms and Desorption Kinctics/Desorption Isotherms 1.3.1 The advanced study is designed to: a) determine the Freundlich adsorption isotherms that, in turn, determine the 1 According to OECD Guideline 106 3M Environmental Laboratory Page 9 of 703 influence o f concentration on the extent o f adsorption onto the soils, sediment and sludge. b) study desorption by means o f determining desorption kinetics/Freundlich desorption isotherms 1J<2 The preparatory methodology for Tier E l is described in the 3M Environmental Laboratory M ethod ETS-8-160: Preparation o f Soil Samples for Screening (Tier E) and Advanced (Tier QI) Sorption Studies for Fluorochemicals as the Test Substance (based on OECD Guideline 106). Materials and Methods Chemical Characterization Table 4. Characterization o f the Test Substance, Test System, and Analytical Reference Substances Test Substance Source Expiration Date Storage Conditions TCR Identification Number Physical Description Purity PFOS 3MSpecialtyChemicals, Bldg. 2361B-10 8/31/2001 Frozen TCR-00017-046 White Powder 97.9% THPFOS SynQuestLabs none Frozen TCR-00017-047 WhitePowder TBD S o lM -n t P F O S S o lu b ility ASTM Type I Water Natural Seawater (C o rre c te d fo r P u rity ) 6 8 0 u g /m L * 1 2 .7 u g /m L * * Aqueous Solotioa o f35% Sodium Chloride 2 0 .2 u g /m L * * B -O danoi 5 6 .0 u g / m L * * * As reported by 3M EnvironmentalLaboratory Report UEOO-I716 Phase: Solubility o fPFOS in Water, ** Phase: Solubility o f PFOS in Natural Seawater and an Aqueous Solution a f3.5% Sodium Chloride, and *** Phase: Solubility o fPFOS in n-Octanol. All solubility determinationsofPFOS TCR-00017-046were conducted a t22-25 C. For PFOS stability information refer to 3M Environmental Laboratory report W -l 878 (PFOS hydrolysis study). 3M Environmental Laboratory Page 10 of 703 Soil Type Source Expiration Date Storage Conditions Chemical Lot Number Physical Description % Organic Caibon % Sand %sat %Clay Clay Agvise 1231/2015 Room Temperature 00-2407 Dried and sieved 26% 16% 22% 62% Barnes Loam Agvise 12/31/2015 Room Temperature 00-2404 Dried and sieved 4.9% 39% 50% 11% Clay Loam Sandy Loam River Sediment Agvise Agvise Agvise 12/31/2015 8/1/2015 12/31/2015 Room Room Temperature . Temperature Room Temperature 00-2405 99-2564 00-2046 Dried and sieved Driedand sieved Dried and sieved 26% 28% 13% 21% 58% 46% 22% 33% 20% 39% 42% 19% Domestic Sludge NIST 1031/2005 Room Temperature 2781 Dried and sieved N/A N/A N/A ' N/A Method Summaries ETS-8-159 "Preparation o f Soil Samples for Preliminary (Tier 1) Sorption Studies for Fluorochemicals as the Test Substance" Suitable Analytical Method: A soil o f high adsorbability (high organic caibon and clay content) is agitated with an appropriate volume o f 0.01 M CaCl2 solution at a 1:5 (w:v) ratio for a minimum o f 4 hours. The mixture is centrifuged and the aqueous phase filtered, if necessary. This "matrix solution" is then prepared by adding lOOuL o f 500mg/L PFOS in a 10ml volumetric flask to reach a nominal concentration within the concentration range that is likely to occur during die test. This "study sample" is then analyzed using HPLC/MS. After the study sample has been analyzed, a determination is made as to whether HPLC/MS is a suitable analytical method for the test substance. Suitable (M inimally Adsorbing) Container Up to five containers comprising a variety o f m aterials are exposed to a 0.01 M CaCl2 aqueous solution dosed with the test substance at a concentration o f 0. lOmg/L and l.Omg/L for a minimum o f 24 hours. The resulting solution is analyzed for the test substance using HPLC/MS. In addition, an extraction o f the container walls is made with methanol. This extract is analyzed as well. Any container that adsorbs less than 10% o f the test substance onto its walls is considered suitable for use as a study container. Alternatively, the container demonstrating the least amount o f test substance absorption is chosen from those tested. Selection of Optimal Soil: Aqueous Solution Ratio, Determination of Equilibration Tim e, and Stability o f the Test Substance Under the Conditions o f the Study The optimal soil: aqueous ratio is determined by using two types of soils and three soil: solution ratios. An aqueous solution in contact with the soil is spiked with 125uL o f 3M Environmental Laboratory Page 11 of 703 500mg/L PFOS to a concentration of 5.0rag/L. Sufficient tubes are prepared such that tubes can be removed at intervals (spanning 0 to 48 hr) and the aqueous portion analyzed. Equilibrium is determined by plotting the adsorption o f the test substance over time. The optimal soil: solution ratio is determined by comparing o f die amount o f adsorption o f die test substance at equilibrium for the various soil: solution ratio study samples. Acceptable values are soil: solution ratios that give a depletion o f the test chemical greater than 20% and preferably greater than 50% at equilibrium. Stability is determined by a mass balance determination following a methanol extraction o f the soil. The mass balance determination is conducted on the one soil:solution ratio per soil that gives a depletion o f the test chemical above 20% and preferably above 50% at equilibrium . Suitable 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 jig, 7.5 pg). The test substance was then extracted from the study samples three times with methanol. The combined methanol extracts are then prepared for analysis by HPLC/MS. hi all cases, adequate quality assurance samples were prepared and analyzed. The equilibration steps were performed at 19 to 30 degrees C. ETS-8-160 "Preparation o f SoO Samples for Screening (Tier II) and Advanced (Tier H i) Sorption Studies for Fluorochemicals as the Test Substance" Tier II: Adsorption Kinetics (One concentration): Appropriate soils and/or sediments and/or sludges were selected for the study. Replicate study samples containing the soils (or sediments or sludges) are equilibrated by shaking for at least 12 hours at room temperature with 0.01 M CaCl2. Study samples are dosed with the test substance at approximately 0.5 mg/L and placed on an orbital shaker. Replicate sets o f these study samples are removed at designated time points throughout a 48 hour time period. Study samples are then prepared and analyzed for the target analyte. The adsorption kinetics are determined using this data. The last set o f study samples (48 hour) are saved and used for the desorption kinetics portion o f the method. Tier HI: Desorption Kinetics (One concentration): After the adsorption kinetics experiment, the 48 hour study samples are centrifuged and the aqueous phase removed. The volume o f solution removed is replaced by an equal volume o f 0.01 M CaCl2without test substance. The new mixture is agitated until the desorption equilibrium is reached. During a 48 hour period, at defined time intervals, small aliquots o f the aqueous phase are removed and analyzed for the target analyte. The experiment then continues with the original mixture. The desorption kinetics are determined using this data. Tier ID: Adsorption Isotherms (Five concentrations): Five test substance concentrations are used, covering two orders o f magnitude. Study samples containing soil (or sediments or sludges) in contact with 0.01 M CaCl2 are equilibrated for a minimum of 12 hours. After equilibration, the study samples are dosed with test substance. The samples are then gently agitated until adsorption equilibrium is reached. Sample sets are removed from the orbital shaker at designated time intervals. The study samples are then prepared and analyzed for the target analyte. The adsorption 3M Environmental Laboratory Page 12 of 703 isotherms are calculated using this data. The study samples from the last time interval are saved for the desorption isotherm study. T ier H I: D esorption Isotherm s: The study samples from the adsorption isotherm study are used for the desorption isolherm study. These samples are centrifuged and die aqueous layer removed. An equal volume of fresh 0.01 M CaCl2solution 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 prepared and analyzed for the target analyte. (These study samples are saved and used to determine mass balance.) The desorption isotherms are determined using this data. T ier H I: M ass Balance: The study samples from the desorption isotherm study are used for the mass balance study. The study samples are centrifuged and the aqueous layer removed. Three portions o f methanol are added to the study samples. W ith each addition o f methanol, the study samples are agitated, centrifuged, and the methanol removed and placed in a second container. These subsequent (methanol) study samples are then prepared and analyzed for the target analyte. Mass balance is determined using this data. hi all cases, adequate quality control samples are prepared and analyzed. Additionally, the equilibration steps were carried out at between 19 and 30 degrees C. T ables. Test System Distribution for Study LRN-E00-1311 Population T ie rI"Suitable Analytical Method" Test Substance Solutions Control Blanks Tier I "Suitable Desorption Solvent" i Tier I "Suitable (M inim ally Adsorbing) Container" Tier I "Selection of Optimal Soil: Solution Ratios" Test Substance Solutions Control Blanks Test Substance S o lu tio n s Control Blanks Test Substance Solutions Control Blanks Tier II "Adsotption Kinetics" Test Substance Solutions Control Blanks Tier m "Desorption Kinetics" Test Substance Solutions Control Blanks Totiil Selected for LRN-EOO-Ul 1 45 45 i 15 15 18 + 6M atrix Spikes 9 + 3 matrix spikes 18 + 6 Matrix Spikes 9 + 3 matrix spikes 60+ 16Matrix Spikes 30 + 8 matrix spikes 60+ 16 Matrix Spikes 29 + 8 matrix spikes 171+57 Matrix Spikes 171 + 57 Matrix Spikes 63+21 matrix spikes 144+48 Matrix Spikes 63 + 21 matrix spikes 139 + 48 Matrix Spikes 36+ 12 matrix spikes 36 + 12 matrix spikes 126 + 42 Matrix Spikes 115 + 42 Matrix Spikes 126 + 42 Matrix Spikes 126 + 42 Matrix Spikes 3M Environmental Laboratory Page 13 of 703 Tier HI "Adsorption Isotherms" Tier in "Desorption Isotherms" Tier HI "Mass Balance" Test Substance Solutions Control Blanks Test Substance Solutions Control Blanks Test Substance Solutions Control Blanks 180 + 60 Matrix Spikes 36 + 12 matrix spikes 90 + 30 Matrix Spikes 18+ 6 matrix spikes 90 + 30 Matrix Spikes 18+ 6 matrix spikes 180 + 60 Matrix Spikes 36 + 12 matrix spikes 89 + 30 Matrix Spikes 18 + 6 matrix spikes 89 + 30 Matrix Spikes 18 + 6 matrix spikes Specimen Collection and Analysis During the course o f the study, aliquots o f the test systems were collected at predetermined tim e intervals. Some sample aliquots were diluted with methanol. The following table describes the sampling regim en information: Table 6. Sample Collection and Preparation for Study LRN-E00-1311 Step Tier I "Suitable Analytical Work" Tier I "Suitable Container" Tier I "Suitable Desorption Solvent' Procedure Each ofthe three soils, the sediment, and the sludge are equilibrated with 0.01M CaCh in triplicate. This "matrix solution" is then removed and dosedwiththe testsubstance, and the resulting solution analyzed. Four types oftest vessels, each ofa different material, are exposedto the test substance for 24 hours. The resulting solutionis analyzed for the test substanceto measure anyloss to the container. The test vessel is then extracted to measure anytest substance thatmayhave adsorbed onto the sides ifthe container. Two types ofsoil arc dosed withthe test substance, and the soil is extractedwith methanol three tunes. The extracts are combined andanalyzed to measure the suitability ofthe solvent R e p lic a te s Each "matrix solution" is dosed intriplicate, and one control sample is prepared. D a te(s) P e rfo rm e d Samples aliquotted 11/02/00 Each type ofcontainer is Aqueous samples dosed at two concentrations, aliquotted 11/14/00 and a setofcontrols is also Methanolextractions prepared. Every vessel is aliquotted 11/15/00 extractedwith methanol after 1 the test substancehasbeen removed. Each type ofsoilis dosed at Methanol extractions two concentrations, and a set aliquotted 1/22/01 ofcontrols is also prepared. TierI ! Two types ofsoil are prepared in three "Selection of soilrsolutian ratios to determine the optimal Optimal Soil: ratio to use in theremainder ofthe study. Solution Samples are prepared atseveral timepoints to Ratios and determine Aretime required for the solutionto Mass Balance" reach equilibrium, and a mass balance calculation is performed. Eachsoil/ratic/time combination is prepared in triplicate, one matrix spike is performed, and one control is prepared. Aqueous samples aliquotted 11/29/00- 12/4/00 Methanol extractions aliquotted 12/7/00 3M Environmental Laboratory Page 14 of 703 Tierfi "Adsorption Kinetics" Tier in "Desorption Kinetics" Tierm "Adsorption Isotherms" Tierm "Desorption Isotherms" Tierm "Mass Balance Determination tl Three soils, one sediment, and one sludge are prepared in die soil:solution ratio indicated in the Tier I study. The samples are dosed with die test substance andplaced on a shaker, samples are then pulled at several time points. The aqueous layer is removed fromdie 48 hour samples from the above step. Fresh CaCb is added to the test vessel and the vessel is placed on a shaker. Small samples are taken at several time points, and additional aqueous solution is added to replace die sample taken. Three soils, one sediment, and one shidge are prepared in the soil-solutionratio indicated in dieTier I study. The samples are dosed with the test substance (at one of 5 concentrations) and equilibrated for either 0 or 48 hours. The aqueous layeris removed fromthe 48 hoursamples from the above step. Fresh aqueous CaQ2solutionis addedto die test vessel and die vessel is placed on a shaker for 48 hours. The aqueous solution is removed fromdie 48 hoursamples in the above step. The remaining soil is then extracted withthree portions ofmethanol, each time the solution is decanted into die same vessel. Eachsoil/time combination is prepared in triplicate, one matrix spike is performed, and a set ofcontrols is prepared. Each48 hour sample vessel from die above step produces 9 samples overthe course ofthe desorption (seven timepoints and two matrix spikes). Each soil/concentratkm/time point combination is preparedin triplicate, one matrixspike is performed. Aqueous samples aliquotted 2/1/01- 2/7/01 Aqueous samples aliquotted 2/13/01- 2/15/01 Aqueous samples aliquotted 2/14/01- 2/15/01 Each 48 hourvessel produces one sample, and every thirdsample is also prepared as a matrix spike. Aqueous samples aliquotted 2/21/01 Each48 hourvessel produces one sample, and every third sample is also prepared as a matrix spike. Methanol extractions aliquotted 2/22/01- 2/26/01 Diluted samples (i.e. sample extracts) containing 250 ng/mL THPFOS as internal standard were analyzed using high-performance liquid chromatography/mass spectrometry (HPLC/MS) in die negative ion mode. PFOS levels were evaluated versus standard curves ranging in concentration from 2.5-1000 ng/mL PFOS and 250 ng/mL THPFOS. Internal Standard quantification was used to best fit and report the data. Target ions were deprotonated PFOS (m/z = 499), and deprotonated THPFOS (m/z = 427). Analytical details arc included in the file for this study that is maintained by the 3M Environmental Laboratory; the study folder is located in the 3M archives. A ll study samples . were generated and analyzed at flic 3M Environmental Laboratory. No chain o f custody forms were generated or required. Reserve samples o f reference m aterials from the 3M Environmental Laboratory will be stored at the 3M Environmental Laboratoiy for a period not less than 10 years following the effective date o f the final test rule, or until the quality o f the preparation no longer affords evaluation. Reserve samples o f the reference m aterials 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 D ata Q uality Objectives The following data quality objectives are from the methods used in the present study. The data quality objectives were met, except as documented in raw data. Coefficient of Determination (r1). The coefficients o f determination (r2) for the calibration curves were 0.985 or greater. The curves were examined closely for accuracy o f quantitation at the low and high ends o f the curve. Quadratic curve fit was applied to calibration standards and sample data to improve quantitation over the concentration range appropriate to file data. Method Blanks. M ethod blanks (applicable sample matrix taken through the entire sample preparation, dilution, and analysis process) provided a measure o f laboratory contamination. Acceptable values for the blanks were less than 50% o f the lim it o f quantitation (LOQ), defined herein as the concentration o f the lowest standard. M atrix Spike Recoveries. A post-preparatory m atrix spike sample for each o f the sample groups used in the study was prepared by adding aliquots o f test-analyte solution according to 3M M ethod ETS-8-159 and 160. The spike recoveries for >80% o f the samples w ere. acceptable (100 30%). Instances where spike recoveries outside o f file control range were observed are indicated in Appendix E. Sample Triplicates. The Relative Standard Deviations o f triplicate samples were acceptable when at least 80% o f them were less than or equal to 30%. Q-tests were used to exclude outliers in data sets. Continuing Calibration Verification. If the percent difference for the amount o f quantified analyte was greater than 30% from the true value relative to the initial standard curve, only those samples analyzed before the last acceptable calibration check standard were used. The remaining samples were analyzed with a new curve. Lim it of Quantitation (LOQ). The LOQ was equal to file lowest acceptable standard in the calibration curve. Calibration Standards. Eleven standards ranging in concentration from approximately 2.5 to 1000 ng PFOS/mL methanol were used for the calibration curves. Calibration curves were run before and after every analytical sequence. Solvent Blanks. Solvent (M ethanol) blanks provide a measure o f instrumental contamination. Acceptable values for the blanks were less than 50% o f the lim it o f quantitation, defined herein as the lowest calibration standard. System Suitability. W ithout performing a method validation, system suitability was demonstrated by acceptable instrumental checks (e.g. abbreviated m/z check-tune, or full auto-tune routines). Statistical Methods and Calculations M eans and standard deviations were calculated using functions provided in Microsoft Excel software. Calculations with the raw data were made using the equations described in the OECD M ethod 106 (see Appendix B). 3M Environmental Laboratory Page 16 of 703 Data Summary and Discussion Appendices D and E summarize individual sample data. Representative chromatograms are presented in Appendix G. All concentrations and calculations can be found in the data tables, along with the log plots used to determine the isotherm values. These data are used in all subsequent tables and figures in this report Results o f the Tier I study are presented in table 7 through 11: Table 7. Suitable Analytical Method Determination . S o il T > p e Barnes Loam (ST-1) Clay Loam (ST-2) C h y (ST-3) River Sediment (ST-Scd) Domrstie Sludge (ST-SJg) S u it i).0 I M C \C i.: S o lu tio n I I) E00-13U -0001,-0002,-0003 EOO-1311-0004, -0005, -0006 E00-I311-0007, -0008, -0009 EOO-1311-0010, -0011,-0012 EOO-1311-0013, -0014, -0015 \v iT .r jc R e co * cl \ u f I'FO.s fn > n i i T i i i i m M lfu tlO ll, % 115% 115% 99.8% 116% 883% % RSL) 731 4.92 21.8 8.88 16.0 Table 8. Suitable Test Vessel Determination C e n trifu g e T u tte T \ pe P o ly p ro p y len e P o ly sty r n e G lass T eflo p . e r a " 0 R ce o re ry i f l.llimy L P I O S A f t e r A lleni i) S te p . % 9 6 .2 % 943% 9 6 .7 % S 9 J% \\craiic C ullLClUl ittioli o f I ' H J S F. > t r a e t e t i b ru m Tesi Vt-sscN D urili" D esorb Step. 1TH 244ppb 172ppb 398ppb 9 4 .4 p p b a a h u .i M u u i \ Spiri. R k o \ i:KV u r n a d ' o k b A M ) Lit - o t t i i S i i 116% 203% 206% 176% It was determined that the polypropylene centrifuge tubes were suitable for this study. These tubes had the least amount o f extractable PFOS, and were the only tubes with acceptable matrix spike recoveries. 3M Environmental Laboratory Page 17 of 703 Table 9. Equilibrium Time for Adsorption of PFOS Soil T \p e SuiJ.Soluiimi R;itw Time Pemt. Iluur.s C lay Sedim ent 1:1 1:5 1:25 1:1 1J 125 24 36 48 24 36 48 24 36 48 24 36 48 24 36 48 24 36 48 \ \ ne\CK R d i U H i t oiPFO S (in s o u n o \ ) ", i 17.6% 21.0% 12.7% 21.6% 215% 19.7% 57.4% 602% 66.8% 11.0% 143% 10.6% 45.9% 45.0% 422% 653% 673% 68.0% Adsorption Equilibrium Plot 20 40 E quilibrium T im e, hours *1:1 Ratio (d ay) -1:5 Ratio (day) 1:25 Ratio (day) 3M Environmental Laboratory Page 18 of 703 Adsorption Equilibrium Plot Sc S 2 60.0 co HQ. , o2 ow 40.0 0 . T<3 20.0_ -1:1 Ratio (Sedim ent) -1 :5 Ratio (sedim ent) 1:25 Ratio (sedim ent) 0 20 40 60 Equilibrium Time, hours The test substance appeared to reach equilibrium after 24 hours in all o f the soiltsolution ratios. The clay appeared to take more tim e to reach equilibrium, therefore the 48 hour time point was used as the equilibrium time for the remainder o f the study. This ensured that all five o f the soils were given ample tim e to equilibrate. Table 10: Suitable Desorb Solvent, Methanol Sdii T>I!t` Tlieoreticol Test Sulist.ince Coiaeiitnilidii In Ewir.U. Hit L 0 .0 C lay Sedim ent 100 1000 on 100 1000 Uern2e Recover). it;:'!. " A \ FUACF. R l ( O V h lU O t n os\, < 25.0 - 71.2 591 -1 <250 96.0 601 N/A 71.2% 59.1% N/A 96.0% 60.1% Despite using methanol, an excellent solvent for PFOS, the average percent recovery o f PFOS ranged from zero to 96%. It is unlikely that a different solvent would yield better recovery. Previous results in this study have indicated that the test substance is readily and rapidly adsorbed on the soil, and is not likely to be completely extracted from it. The optimal soil:solution ratio was determined to be 1:5 (refer to Table 9 for applicable data). This ratio demonstrated average adsorption percentages o f PFOS ranging from approximately 75% in clay to 55% in sediment. 3M Environmental Laboratory Page 19 of 703 Table 11. Stability ofPFOS during the Study Period Soil Type Q ty Sedim ent SoihSolotion Ratio, lim e Point 1:1 15 135 1:1 15 135 Time Point, hours 48 48 48 . 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 Uv.'M. Rl.L'>v"; y or p[ OS o 46.2 53.2 71.3 34.3 35.6 Tube Broke 83.2 91.2 96.3 43.7 48.1 2 4 .7 57.6 7 8 .7 59.5 7 3 .6 87.4 83.1 According to OECD guideline 106, the mass balance calculation should show at least 90% recovery o f the test substance for the test substance to be considered stable over the course o f the study. The recovery o f the test substance was lower than the OECD guideline, likely due to the incomplete desorption o f the test substance from the soil. Hydrolysis studies o f PFOS conducted at the 3M Environmental Laboratory have demonstrated test substance stability in aqueous m atrices. The results o f the Tier II study are presented in Table 12: Table 12. Adsorption Kinetics of PFOS, 1:5 Soli:Solution Ratio, 48 Hour Time Point Soil l}p e a * y (ST-1) d a y Loam (ST-2) Seed y Loam (ST-3) \\<.jriiL*e Distribution Coelllcicnt, k , f. I 183 9.72 353 PtrciMUam* ot U r e m ie ( ;irlmn in Soil. " 2.6 2.6 2.8 V\ i It S(.I OUl.AMt ( r u m s Ni u m M 1/1 1) An'-uiii'l ion C o t m t I K M . K lk, L;Ksj 704 374 1260 River Sediment (ST-Sed) Domestie Sludge (ST-SIg) 7.42 <120 13 571 NA NA 3M Environmental Laboratory Page 20 of 703 All o f the soil/sediment/sludge m atrices adsorbed the test substance to varying degrees. The sludge samples, in die adsorption portion o f the kinetics study, demonstrated die m ost adsorption (>96%) and PFOS was not detected in the samples. The data indicates that adsorption occurred within die first few hours o f exposure and the test substance concentration does not vary significantly after die 16 hour time point. The results o f the Tier III study are presented in Tables 13 through 15: Table 13. Desorption Kinetics o f PFOS, 1:5 Soil:Solution Ration 48 hour lim e Point Soil 1'vpc CUy (ST-1) Clay L oan (ST-2) Sandy Loam (ST-3) River Sediment (ST-Sed) Dom estic Stodge (ST-Slg) Desorption Coeificient. K^.., L-Kfi 47.1 15.8 34.9 10.0 <237 3M Environmental Laboratory Page 21 of 703 Desorption Percentage as a Function of Time Ii --C lay Clay Loam A Sandy Loam X--River Sediment I The test substance was poorly desorbed from die soil/sedhnent/sludge matrices during die 48-hour study period. The river sediment displayed the most desorption at only 39% after 48 hours. The sludge samples did not desorb a detectable amount o f test substance. Desorption that did occur was accomplished rather quickly, after die 8 hour time point the test substance concentration did not vary significantly. Table 14. Adsorption Isotherms Soil T \ pe Log K ,JV k " \ , L k i! RL^rc^sion Coustnnr. In R c^rt^ion Const.ini, ii C lay 1.40 25.1 0.884 1.13 Clay Loam 1.15 14.0 0.841 1 .1 9 Sandy Loam 1.45 28.2 0.829 1.21 River Sediment 0 .9 3 9 8.70 0.989 1.01 Domestic Stodge 2.53 338 1.26 0.795 Note: The units for the isotherm assume that the term n=-l. More accurately, the units are (Mg1'1'* (L)1'* Kg'1) 3M Environmental Laboratory Pago 22 of 703 Table 15. Desorption Isotherms Siiil T y p e lu g fv'% K ' ' , . L fv'g Regress m Constant. In Regression Constim i, n C lay Clay Loam Sandy Loam River Sediment Domestic Sludge 2 .0 2 1.78 1.97 1.65 3 .5 0 105 60.2 9 4 .0 4 4 .6 3130 0.860 0.954 0.985 1.02 0.977 1.16 1.05 1.02 0.981 1.02 Note: The units for the isotherm assume that the term n=J. More accurately, the units are (L)1*1K g 1) Freundlich isotherms relate die amount o f test substance adsorbed on the soil to the amount present in the aqueous solution at equilibrium. The values calculated for the regression constant indicate that the data obtained for the test substance over two orders o f magnitude are slightly non-linear. References 1. Adsorption-Desorption Using a Batch Equilibrium M ethod (OECD 106), January 2000. Report Amendments The organic carbon normalized adsorption coefficient (K*.) values contained in tables 2 and 12, isotherm values contained in tables 3 ,1 4 and 15 as well as raw spreadsheets on pages 205-233 were corrected following clarification o f calculations described in OECD guideline 106. Table 13 had 2 values switched and was corrected. The conclusion section was removed. The title page was m odified to indicate this report has been amended. The signature page was re-signed following the amendments. 3 M Environmental Laboratory Page 23 of 703 Signatures The amended final draft of this report is a true representation o f the data developed in this study. It has been issued by: William K. Reagan, Testing Facility Management Date 3M Environmental Laboratory Page 24 of 703