Document dn94B0xpjXVXoDZz7qEqG3zpe

A t 2 2 b - O '/ SOIL ADSORPTION - REVISED TEST SUBSTANCE_______________________________ _____________ Id e n tity : Perfluorooctanesulfonate; may also be referred to as PFOS or FC -95. (1Octanesulfonic acid, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-, potassium salt, CAS # 2795-39-3) Rem arks: The test substance is a white powder. Sample was re-crystalized from a production lot of FC-95. Purity determined to be 97.9% by LC/MS, 1H-HMR, 19F-NM R and elemental analyses techniques. METHOD_______________________________ '_________________ M ethod: Based on OECD 106 GLP (Y/N ): Yes Y ear com pleted: 2001. Amended report issued 2002 S tatistical m ethods: Statistical analysis and plotting o f the data was done according to OECD Method 106 using Microsoft Excel. Tem perature: Room Tem perature (19-30C ) Stock and tes t solution preparation: The test concentrations and conditions were determined in a Preliminary experiment. For the definitive experiment, test solutions were made by diluting a stock solution of un-radiolabeled Perfluorooctanesulfonate to a final test substance concentration of approximately 0 .5 mg/L in aqueous 0.01 M CaCI2. Soil C haracteristics: Soil Class C la y C lay Loam Source Lot Number Physical D e s c rip tio n % Organic Carbon % Sand % S ilt % C lay CEC (m eq/100g) Kittson County, MN 00-2407 1.00 mm airdried, 0-6" deep Grand Forks County, ND 00-2405 1.00 mm airdried, 0-6" deep 2.6% 2.6% 16% 21% 22% 46% 62% 33% 54.5 2 4 .7 pH in 0.01 M C a C I2 72 6.0 1Value is for pH in water not pH in 0.1 M CaCI2 Sandy Loam R iv e r Sedim ent Grand Forks County, ND Grand Forks County, ND 99-2564 00-2406 1.00 mm air- 1.00 mm air- dried, 0-6" deep dried, 0-6" deep 2.8% 13% 58% 39% 22% 42% 20% 19% 23.3 17.5 7 .8 1 7.7 Dom estic S lu d g e NIST, from Denver, CO POTW 2781 200 mesh, oven-dried, sterilized Not analyzed Not analyzed Not analyzed Not analyzed Not analyzed Not analyzed mi m.29 m9: ro cr> CONTAIN NO GBI 000255 T est C onditions: Adsorption Kinetics: Replicate study samples containing the soils (or sediments or sludges) were equilibrated by shaking for at least 12 hours at room temperature with 0.01 M CaCI2. Study samples were dosed with the test substance at approximately 0.5 mg/L and placed on an orbital shaker. Replicate sets o f these study samples were removed at designated time points throughout a 48 hour time period. Study samples were then prepared and analyzed for the target analyte. The adsorption kinetics were determined using this data. The last set o f study samples (48 hour) were saved and used for the desorption kinetics portion o f the method. Desorption Kinetics (One concentration): After the adsorption kinetics experiment, the 48 hour study samples w ere centrifuged and the aqueous phase removed. The volume o f solution removed was replaced by an equal volume of 0.01 M CaCI2 without test substance. The new mixture was agitated until the desorption equilibrium was reached. During a 48-hour period, at defined time intervals, small aliquots of the aqueous phase were removed and analyzed for the target analyte. The desorption kinetics were determined using this data. RESULTS Soil Type Clay Clay Loam Sandy Loam River Sediment Domestic Sludge Adsorption Kinetics of PFO S, 1:5 SoikSolution Ratio, 48 Hour Tim e Point_______ Average Distribution coefficient; K& L/Kg Percentage of Organic Carbon in Soil Average Organic Carbon normalized Adsorption Coefficient, K , L/Kg 18.3 26 704 9.72 26 374 35.3 28 1260 7.42 1.3 571 <0.120 Not available Not calculable The data indicate that adsorption occurred within the first few hours of exposure and the test substance concentration did not vary significantly after 16 hours. Apparent Desorption Kinetics of PFOS, 1:5 SoikSolution Ratio, 48 hour Tim e Point Soil Type Desorption Coefficient, IQa L/Kg Clay 47.1 Clay Loam 15.8 SandyLoam 34.9 River Sediment 10.0 Domestic Sludge <237 000256 The river sediment displayed the most desorption at 39% after 48 hours. The sludge samples did not desorb a detectable amount of test substance. Desorption that did occur was accomplished rather quickly; after the 8 hour time point the test substance concentration did not vary significantly. Adsorption Isot herm s Soil type Log KadV 1), L/Kg Regression constant, 1/n Regression Constant, n Clay 1.40 25.1 0.884 1.13 Clay Loam 1.15 14.0 0.841 1.19 Sandy Loam 1.45 2 8 .2 0.829 1.21 River Sedhnerrt 0.939 8 .7 0 0.989 1.01 Domestic Sludge 2.53 338 1.26 0.795 (1) Freundlich adsorption coefficient. The units forth e isotherm assum e that the term n=1. More accurately, the units are (yg1`1,n(L)'!,"Kg`1) Desorption Isotherm s Soil Type Log K*F L/Kg Regression C onstant 1/n Regression Constant, n Clay 2.02 105 0.860 1.16 Clay Loam 1.78 60.2 0.954 1.05 Sandy Loam 1.97 94.0 0 .9 8 5 1.02 River Sediment 1.65 4 4 .6 1.02 0.981 Domestic Sludge 3 .5 0 3130 0.977 1.02 (2) (1) Freundlich desorption coefficient. . The units for the isotherm assum e that the term n=1. More accurately, the units are (pg1'1/n(L)1JhKg`1) Freundlich adsorption isotherms relate the amount of 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 of magnitude is slightly non-linear. CONCLUSIONS Perfluorooctanesulfonate (PFO S) appeared to adsorb to all of the soil/sediment/sludge matrices tested. In either case, adsorption or desorption, an equilibrium is achieved in less than 24 hours, with substantial adsorption (>50% ) occurring in some of the time 0 samples after approximately 1-minute of contact. Subm itter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 000257 DATA QUALITY R eliability: Klimisch ranking 1. REFERENCES 3M Technical Report "Soil Adsorption/Desorption Study of Potassium Perfluorooctanesulfonate (PFO S)". Mark E. Ellefson, Project Number E00-1311, Final Report Completion Date June 4, 2001. Amended Report Completion Date May 2 4 ,2 0 0 2 . OTHER Last Changed: June 12, 2002 000258 Study Title Soil Adsorption/Desorption Study of Potassium Perfluorooctanesulfonate (PFOS) Data Requirement Based on OECD 106 A u th o r Mark 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 Number o fPages 703 000259 This page has been reserved for specific country requirements. 3M Environmental Laboratory 0 t 2 6 0 Page 2 of 703 GLP Compliance Statement Study Title: Soil Adsorption/Desorption Study o f Potassium Perfluorooctanesulfonate (PFOS) Study Identification Number: E00-1311 This study was conducted in compliance with Toxic Substances Control Act (TSCA) Good Laboratory Practice (GLP) Standards with the exceptions listed below: Exceptions to GLP compliance: 40 CFR 972.130(e): There is 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 000261. Page 3 of 703 Quality Assurance Statement Study Title: Soil Adsorption/Desorption o f Potassium Perfluorooctanesulfonate (PFOS) Study Identification Number: EOO-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 die study director and laboratory management. 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 (Tiern&IH) Data (Tier Il&m) Data (Tier n& m ) Data (Tier n&III) Final Report Date 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 000262 Table o f Contents GLP Compliance Statement..............................................................................................................3 Quality Assurance Statement.................................................. ....................... ................................. 4 List o f Tables.....................................................................................................................................6 Study Personnel and Contributors................................................. ...................................................6 Location, o f Archives........................................................................................................................ 7 Summary........................................................................................................................................... 7 Introduction....................................................................................................................................... 8 Purpose.....................................................................................,..................................................... 8 Materials and Methods................... ..................................................................................................10 Chemical Characterization........................................... ............................ .......................................10 Method Summaries......................................................................................................................... 11 Specimen Collection andAnalysis............... ......................................................... ...........................14 Results and Discussion........................................................................................... .......................... 16 Data Quality Objectives.................................................................................................................. 16 Statistical Methods and Calculations..................................... ...........................................................16 Data Summaryand Discussion............ .............................................................................................17 References.............................................................................................................. .......................... 23 Signatures..........................................................................................................................................24 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 Flnorocbemicals as Ae Test Substance"......................................................................................................................51 ETS-8-160 "Preparation ofSoil Samples for Screening (Tier II) and Advanced (Tier HI) Sorption Studies for Fluorochemicals as the Test Substance" ........................................................................... 74 OECD 106 "Adsorption-Desorption Using a Batch Equilibrium Method" ........................................89 ETS-8-155 "Analysis ofPotassiumPerfluorooctanesulfonate or Other Fluorochemicals in Waste Stream ofWater Extracts Using HPLC-Electrospray/Mass Spectrometry" ...................................................... 133 ETS-8-110 "Analysis ofPotassiumPerfluorooctanesulfonate 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 Summaries.................................................................................................. 483 Appendix I: Traceability Information...................... ......................................................................... 594 3M Environmental Laboratory Page 5 of 703 000263 L ist o f 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 Substances..................................................... 10 Table 5. Test System Distribution for Study LRN-E00-1311 ............. 13 Table 6. Sample Collection and Preparation for Study LRN-EOO-1311..........................................14 Table 7. Suitable Analytical Method Determination.................. ...17 Table 8. Suitable Test Vessel Determination..................................................................................... 17 Table 9. Equilibrium Time for Adsorption of PFOS.......................................................................... 18 Table 10: Suitable Desorb Solvent, Methanol........................................................................... ....... 19 Table 11. Stability o f PFOS during the Study Period....................................................................... 20 Table 12. Adsorption Kinetics of 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 Isotherms......................................................................................................... 23 Study Personnel and Contributors 3M Environmental Laboratory and Professional Services Contributing Personnel Cindy M . Carlson (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) Mark L. Anderson (Braun Intertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 55439) 000264 Location o f Archives All original raw data and the report have been archived at the 3M Environmental Laboratory. The test materials and analytical reference standard reserve samples, as well as the samples pertaining to the analytical phase of this study are archived at the 3M Environmental Laboratory. Reserve samples, digital copies o f original data and all original paper data will be retained in the archives of 3M Environmental Laboratory for a period o f at least 10 years following the effective date o f the applicable final test rule. Sum m ary A preliminary, screening, and advanced study o f the soil adsorption/desorption o fPotassium Perfluorooctanesulfonate was performed to better understand partitioning under a variety o f environmental conditions. Specifically, three types of soil, one sediment, and one sludge were tested. Analyses were conducted as described by 3M Environmental Laboratory Analytical Methods ETS-8-159 "Preparation of 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 III) Sorption Studies for Fluorochemicals as the Test Substance" (Appendix A), according to OECD Guideline 106 "Adsorption - Desorption Using a Batch Equilibrium Method". Results of the study are presented in the following tables: Table 1. Summary Table of PFOS Adsorb/Desorb Tier I Studies Question Is the analytical method appropriate/adequate for the study? What is the best test vessel to use? What is die equilibrium time and amount adsorbed at equilibrium? What is a suitable desoiption solvent? What is tin optimal soilrsolution ratio? Conclusion The methods ETS-8-159 and ETS-8-160 provide sufficient recovery o f the test substance. Polypropylene tubes will be used throughout this study. The 1:5 saihsohition ratio shows a >50% adsorption for both soils 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 000265 Table 2. Summary Table o f PFOS Adsorb/Desorb Tier n Studies Soil I'p c \ \ DiMf btKfi n ( n:lik'k'iif. h ,., I. U*j f \ r t ciliari.- of Or'iMmV ( ,il {.x;n if) ''Ml!. "JK' Clay (ST-1) G ay Loam (ST-2) Sandy Loam (ST-3) River Sediment (ST-Scd) Domestic Sludge (ST-Slg) 183 9.72 353 7 . <120 2.6 2.6 28 13 NA A' I K u,l ()U(, W K (' N i i m u i/ i i ) A l l 'l 'KT 1ION t i l l l i l ( I I M , |V j , . i, K " 704 374 1260 571 NA Table 3. Summary Table o f PFOS Adsorb/Desorb Tier m Studies Soil TA p|Kc' Dim .i iiion ('efficient. K ....L.hij Iv Sandy Loam Clay Loam Clay River Sediment DomesticSludge 34.9 15.8 47.1 10.0 <237 28.2 14.0 25.1 8.70 338 94.0 603 105 44.6 3130 Nate: The units fix-the isotherms assume that the farm n = l. Mote accurately, the units are (jig " "(L)'" kg'*) Introduction Ff "^C / Ff POTASSIUM PERFLUOROOCTANESULFONATE (P F O S ) CAS Number 2795-39-3 Chemical Formula: C8F17SO3K Molecular Weight: 538.22 g/mol Purpose Adsorption/desorption studies are useful for generating essential information on the mobility 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 000266 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 of the substance, the characteristics of 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 of 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. Different soil types must be used in order to emulate the interactions o f a given substance with naturally occurring soils. The soil parameters 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 of a chemical on different soil types that have a varying range of pH, organic carbon content, and soil texture. The guideline is comprised o f three tiers: 1.1 Tier I: The Preliminary Study 1.1.1 The preliminary study is designed to determine: a) a suitable analytical method b) the adsorption of the test substance onto the surfaces o f the test vessels c) die equilibration time for adsorption and the amount o f test substance adsorbed at equilibrium d) a suitable desorption solvent e) the 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 Method 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 K* and K*. 1.2.2 The preparatory methodology for Tier II is described in the 3M Environmental Laboratory Method ETS-8-160: Preparation o f Soil Samples for Screening CTier II) and Advanced (Tier ID) Sorption Studies for Fluorochemicals as the Test Substance (based on OECD Guideline 106). 1.3 Tier HI: 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 1 According to OECD Guideline 106 3M Environmental Laboratory Page 9 of 703 000267 influence of 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 1.3.2 The preparatory methodology for Tier III is described in the 3M Environmental Laboratory Method ETS-8-160: Preparation o f Soil Samples for Screening (Tier D) and Advanced (Tier HI) Sorption Studies for Fluorochenricals as the Test Substance (based on OECD Guideline 106). M aterials and M ethods Chemical Characterization Table 4. Characterization of the Test Substance, Test System, and Analytical Reference Substances T est S ubstance S o u rc e E xpiration D ate Storage C onditions T C R Identification N um ber Physical D escription P urity PFO S 3M Specialty Chemicals, B ldg 236tB -10 m m ooi Frozen TCR-00017-046 White Powder 97.9% THPFOS SynQuest Labs none Frozen TCR-00017-047 White Powder TBD Solvent P F O S Solubility ASTM Type I Water Natural Seawater AqueousSolution o f35% Sodium Chloride (C orrected for Purity) 680 ug/m L * 12.7 ug/m L ** 20.2 ug/m L ** n-Octanol 56.0 ug/m L *** * As reported by 3MEnvironmental Laboratory Report KEOO-1716 Phase: Solubility o fPFOS in Water, ** Phase: Solubility o f PFOS in NaturalSeawater and an Aqueous Solution o f3.5% Sodium Chloride, and *** Phase: Solubility o fPFOS in n-OctanoL AHsolubility detaminationsofPFOSTCR-00017-046were conducted at22-25C. For PFOS stability information refer to 3M Environmental Laboratory report W -l 878 (PFOS hydrolysis study). 3M Environmental Laboratory Page 10 of 703 000268 S oil T ype C lay S o u rc e E x p iratio n D ate S to ra g e C onditions C hem ical L otNum ber P h y sic a l D esorption % O rganic C arb o n % Sand % S ilt % C lay Agvise 12/31/2013 Room Temperature 00-2407 Dried and sieved 2.6% 16% 22% 62% B arnes L oam Agvise 12/31/2015 Room T em perature 00-2404 Dried and sieved 4.9% 39% 50% 11% C lay L oam Agvise Sandy Loam Agvise R iver S edim ent 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 Dried and sieved Dried and sieved 2.6% Z8% 1.3% 21% 58% 46% 22% 33% 20% 39% 42% 19% D om estic S ludge N IS T 10/31/2005 Room Temperature 2781 Dried and sieved N/A N /A N/A ' N/A M ethod Summaries ETS-8-159 "Preparation o f Soil Samples for Preliminary (Tier I) Sorption Studies for Fiuorochemicals as the Test Substance" Suitable Analytical Method: A soil o f high adsorbability (high organic carbon and clay contort) is agitated with an appropriate volume of 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 1OOuL of 500mg/L PFOS in a 10ml volumetric flask to reach a nominal concentration within the concentration range 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 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 materials are exposed to a 0.01 M CaCl2 aqueous solution dosed with the test substance at a concentration o f O.lOmg/L and l.Omg/L for a minimum of 24 hours. The resulting solution is analyzed for the test substance using HPLC/MS. hi 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% of the test substance onto its walls is considered suitable for use as a study container. Alternatively, die container demonstrating the least amount of test substance absorption is chosen from those tested. Selection o f Optimal Soil: Aqueous Solution Ratio, Determination o f 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 000269 5Q0mg/L PFOS to a concentration of 5.0mg/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 die test substance over time. The optimal soil: solution ratio is determined by comparing of the amount of adsorption o f the test substance at equilibrium for the various soil: solution ratio study samples. Acceptable values are soil: solution ratios that give a depletion of 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 of the soil. The mass balance determination is conducted on the one soilsolution ratio per soil that gives a depletion o fdie 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 pg, 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 IIPLC/MS. In 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 Soil Samples for Screening (Tier II) and Advanced (Tier III) Sorption Studies for Fluorochemicals as the Test Substance" T ie r ll: 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 flie test substance at approximately 0.5 rng/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 of the method. Tier IH: 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 of 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 of 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. T ierm : 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 CaCl2are 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 000270 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: Desorption Isotherm s: 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 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. H ie study samples are centrifuged and the aqueous layer removed. Three portions o f methanol are added to the study samples. With each addition o fmethanol, 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. In all cases, adequate quality control samples are prepared and analyzed. Additionally, the equilibration steps were carried out at between 19 and 30 degrees C. Table 5. Test System Distribution for Study LRN-EO0-1311 Population T ierI"Suitable Test Substance Analytical Method" j Solutions 1i Control Blanks Tier I "Suitable Test Substance Desorption Solvent" Solutions Control Blanks T ierI"Suitable (Minimally Adsorbing) Contain" Test Substance Solutions Control Blanks Tier I "Selection of Optimal Soil: Solution Ratios" Test Substance Solutions Control Blanks Tier II "Adsorption Kinetics" Test Substance Solutions Control Blanks Tier in "Desorption Kinetics" Test Substance Solutions Control Blanks Tota! 45 Selected for L R N -E O O -lJli 45 15 18 + 6Matrix Spikes 9 + 3 matrix spikes 60+ 16 Matrix Spikes 30 + 8 matrix spikes 171+ 57 Matrix Spikes 63 + 21 matrix spikes 144+48 Matrix Spikes 36+ 12 matrix spikes 126+42 Matrix Spikes 126+ 42 Matrix Spikes 15 18 + 6 Matrix Spikes 9 + 3 matrix spikes 60 + 16 Matrix Spikes 29 + 8 matrix spikes 171 + 57 Matrix Spikes 63+21 matrix spikes 139+48 Matrix Spikes 36 + 12 matrix spikes 115+42 Matrix Spikes 126 + 42 Matrix Spikes 3M Environmental Laboratory Page 13 of 703 0002*71 Tier HI "Adsorption Isotherms" Tier IE "Desorption Isotherms" Tier E "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 + 6matrix spikes Specimen Collection and Analysis During the course o f the study, aliquots o f the test systems were collected at predetermined time intervals. Some sample aliquots were diluted with methanol. The following table describes the sampling regimen information: Table 6. Sample Collection and Preparation for Study LRN-EOO-1311 Step Tier I "Suitable Analytical Work" Tierl "Suitable Container" Tierl "Suitable Desorption Solvent" Procedure Each o ffee three soils, the sediment, andthe sludge are equilibratedwith 0.01M CaCl2in triplicate. This``matrix solution" is then removed anddosed with the testsubstance, and die resulting solution analyzed. Fourtypes oftest vessels, each ofa different material, are exposed to die test substance for 24 hours. The resulting solution is analyzed forthe testsubstance tomeasure anyloss to die container. The testvessel is then extracted to measure anytest substance thatmayhave adsorbed onto the sides ifthe container. Two types ofsoil are dosed withthe test substance, andthe soil is extractedwith methanolthreetimes. The extracts are combined andanalyzed to measure the suitability o fdie solvent Replicates Each"matrixsolution" is dosed intriplicate, and (me control sample is prepared. Each type ofcontainer is dosed at two concentrations, and a set o fcontrols is also prepared. Everyvessel is extractedwithmethanol after tile test substancehasbeen removed. Each type ofsoil is dosed at two concentrations, and a set ofcontrols is also prepared. Date(s) Perform ed Samples aliquotted 11/02/00 Aqueous samples aliquotted 11/14/00 Methanol extractions aliquotted 11/15/00 Methanol extractions aliquotted 1/22/01 Tierl Two types ofsoil areprepared in three Each soil/ratio/time Aqueous samples "Selection of soihsolution ratios to determine die optimal combinationis preparedin aliquotted 11/29/00- Optimal Soil: 1 ratio to use in theremainder ofthe study. triplicate, one matrixspike is 12/4/00 Solution Samples arcprepared atseveraltimepoints to performed, andone control Methanol extractions Ratios and determine die time requiredfordie solutionto is prepared. aliquotted 12/7/00 Mass Balance" reachequilibrium, anda mass balance calculation is performed. i i 3M Environmental Laboratory Page 14 of 703 000272 Tierll "Adsorption Kinetics" Tier IH "Desorption Kinetics" Tierin "Adsorption Isotherms" TierM "Desorption Isotherms" TierHI "Mass Balance Determination Threesoils, one sediment, andone sludgeare preparedin die soiksohition ratio indicated in theTier I study. The samples aredosed with the test substance andplaced on a shaker, samples arethenpulled atseveral time points. The aqueous layer is removed fromthe 48 hour samples fromthe above step. Fresh CaCl2is added to the testvessel andthe vessel is placed on a shaker. Small samples are taken at several time points, and additional aqueous solution is added to replace the sample taken. Three soils, one sediment, andone sludge are preparedinthe soiksohitionratio indicatedin theTier I study. The samples are dosed with the test substance (atore o f 5 concentrations) and equilibrated foreither 0 or 48 hours. The aqueous layeris removed fromthe 48 hoursamples from die above step. Fresh aqueous CaCl2solution is addedto die test vessel and the vessel is placed on a shakerfor 48 hours. The aqueous solution is removed fromthe 48 hoursamples in the abovestep. The remaining soil is thenextractedwith three portions ofmethanol, each time file solution is decanted intodie samevessel. Eachsoil/time combination is preparedin triplicate, one matrix spike is performed, and a set o fcontrols is prepared Each48 hoursamplevessel fromdie above step produces 9 samples overdie course ofdie desorption (seven timepoints and two matrix spikes). Bach soiFrereentration/tirne point combination is preparedin triplicate, ore matrixspike is performed. Each 48 hourvessel produces one sample, and every thirdsample is also preparedas a matrixpike. Each 48 hourvessel produces one sample, and every thirdsample is also preparedas a matrixpike. 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 Aqueous sanples aliquotted 2/21/01 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 the 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. All study samples were generated and analyzed at the 3M Environmental Laboratory. No chain o f custody forms were generated or required. Reserve samples o f reference materials from the 3M Environmental Laboratory will be stored at the 3M Environmental Laboratory for a period not less than 10 years following the effective date o f the final test rule, or until the quality of the preparation no longer affords evaluation. Reserve samples o f 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 000273 R esults and D iscussion Data Quality 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 D eterm ination (r2). 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 of the curve. Quadratic curve fit was applied to calibration standards and sample data to improve quantitation over the concentration range appropriate to the data. M ethod Blanks. Method 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 limit o f quantitation (LOQ), defined herein as the concentration of the lowest standard. M atrix Spike Recoveries. A post-preparatory matrix spike sample for each o f the sample groups used in the study was prepared by adding aliquots of test-analyte solution according to 3M Method ETS-8-159 and 160. The spike recoveries for >80% o f the samples were, acceptable (100 30%). Instances where spike recoveries outside o f the control range were observed are indicated in Appendix E. Sample Triplicates. The Relative Standard Deviations of 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 V erification. 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 Q uantitation (LOQ). The LOQ was equal to the 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 (Methanol) blanks provide a measure o f instrumental contamination. Acceptable values for the blanks were less than 50% o f the limit of quantitation, defined herein as the lowest calibration standard. System Suitability. Without performing a method validation, system suitability was demonstrated by acceptable instrumental checks (e.g. abbreviated talz check-tune, or full auto-tune routines). Statistical Methods and Calculations Means 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 Method 106 (see Appendix B). 3M Environmental Laboratory Page 16 of 703 000274 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 . Soil T ype Barnes Loam (ST-1) Clay Loam (ST-2) Clay (ST-3) RiverSediment (ST-Sed) Domestic Sludge (ST-Slg) S o il 0.0 l.M C a C l , S olution ID EOO-1311-0001,-0002,-0003 00-1311-0004, -0005, -0006 00-1311-0007,-0008,-0009 E00-1311-0010,-0011,-0012 EOO-1311-0013, -0014, -0015 A verage Recovery of I'FOi) from matrix, solution, % 115% 115% 99.8% 116% 88.3% ToRSD 7.51 4.92 21.8 8.88 16.0 Table 8. Suitable Test Vessel Determination C entrifuge T u b e Tv pe Polypropylene Polystyrene Glass T eflon A verage Recovery of l.Umg/L PF O S A fter A dsorb Step, % 96.2% 945% 96.7% 89-5% A verage Concentration of P f O S fcAtructed F r o m f e s t V essel.1 D uring D esorb Step, mi 244ppb m ppb 398ppb 94.4ppb Avtai.vca: M vrm \ Spike RtCOVKIiV POR Al)iORl! A M ) DlAORU Srtl'S , % 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 000275 Table 9. Equilibrium Time for Adsorption of PFOS Soil T y p e Soil:So!uSiim Ratio Tim e Point, H ours Clay Sediment 1:1 15 125 1:1 15 125 24 36 48 24 36 48 24 36 48 24 36 48 24 36 48 24 36 48 A \ ERAtiE R t:ro\ t Kt o f P F O S SOLITION)0/ 17.6% 21.0% 12.7% 21.6% 235% 19.7% 57.4% 602% 66.8% 11.0% 145% 10.6% 45.9% 45.0% 422% 655% 675% 68.0% 3M Environmental Laboratory Page 18 of 703 000276 Adsorption Equilibrium Plot -1:1 Ratio (Sediment) -1 :5 Ratio (sediment) -1:25 Ratio (sediment) The test substance appeared to reach equilibrium after 24 hours in all o f the soil:solution ratios. The clay appeared to take more time to reach equilibrium, therefore the 48 hour time point was used as die equilibrium time for the remainder o f the study. This ensured that all five of the soils were given ample time to equilibrate. Table 10: Suitable Desorb Solvent, Methanol Soil T ype Clay Theoretical Test Substance C on cen tratio n In E xtract, ug/L 0.0 100 1000 Sediment 0.0 100 1000 Average Recovery, u g ' 1. <25.0 71.2 591 <25.0 96.0 601 Average R e c oyerx of FFOS% 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 soihsolution ratio was determined to be 1:5 (refer to Table 9 for applicable data). This ratio demonstrated average adsorption percentages of PFOS ranging from approximately 75% in clay to 55% in sediment. 3M Environmental Laboratory Page 19 of 703 000277 Table 11. Stability of PFOS during the Study Period Soil T ype Clay Sediment SoikSolution Ratio. l ime Point 1:1 1:5 105 1 1:1 15 135 l ime Point, hours 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 I'otal Recovery o r P F O S 0. > 46.2 53.2 71.3 i 34.3 i 35.6 Tube Broke 833 913 96.3 43.7 48.1 24.7 57.6 78.7 59.5 73.6 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 of die 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 of PFOS conducted at the 3M Environmental Laboratory have demonstrated test substance stability in aqueous matrices. The results o f the Tier II study are presented in Table 12: Table 12. Adsorption Kinetics o f PFOS, 1:5 SoiI:SoIution Ratio, 48 Hour Time Point Soil T ype C ity (ST-1) Clay Loam (ST-2) Saady Loam (ST-3) A verage Distribution C oefficient, K d. I ..'Kg 183 9.72 353 Percentage of O rganic Carbon in Soil, " h o c 2.6 2.6 2.8 A \ FRACK O liC A N K C VRHON Nt IHMVI l / l n Adsorimion C o e f f i c i e n t , K0O L / R g 704 374 1260 RiverSediment (ST-Sed) Domestic Sludge (ST-SIg) 7.42 <120 U 571 NA NA 3M Environmental Laboratory Page 20 of 703 000278 Adsorption Percentage as a Function of Time All o f the soil/sediment/sludge matrices adsorbed die test substance to varying degrees. The sludge samples, in the adsorption portion o f the kinetics study, demonstrated the most adsorption (>96%) and PFOS 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 16 hour time point. The results o f the Tier IH study are presented in Tables 13 through 15: Table 13. Desorption Kinetics o f PFOS, 1:5 SoJkSolution Ratio, 48 hour Time Point Soil T y p e Ctay (ST-1) Clay Loam (ST-2) Sandy Loam (ST-3) Desorption Coefficient. 47.1 15. 34.9 L /K g Biver Sediment (ST-Sed) Domestic Sludge (ST-Slg) 10.0 <237 3M Environmental Laboratory Page 21 o f 703 000279 D esorption Percentage as a Function o f Tim e The test substance was poorly desorbed from die soil/sediment/sludge matrices during the 48-hour study period. The river sediment displayed die most desorption at only 39% after 48 hours. The sludge samples did not desorb a detectable amount oftest substance. Desorption that did occur was accomplished rather quickly, after the 8 hour time point the test substance concentration did not vaiy significantly. Table 14. Adsorption Isotherms Soil T y p e L o g K :' Jsf K "lst , L / K g Regression Constant, l/n Regression Constant* h Gay 1.40 25.1 0.884 1.13 Clay Loam 1.15 14.0 0.841 1.19 Sandy Loom 1.4S 28.2 0.829 1.21 RiverSediment 0.939 8.70 0.989 1.01 Domestic Sludge 2-53 338 126 ! 0.795 Note: The units for the isotherm assume that the term n H . More accurately, the units are (|igw h (L)l/nKg'1) 3M Environmental Laboratory Page 22 of 703 000280 Table 15. Desorption Isotherms Soil T ype l . o K dcV K '" \; L ' K g Regression C onstant. In Regression Constant, n Clay Clay Loam Sandy Loam River Sediment Domestic Sludge Z02 1.78 1.97 1.65 3.50 105 602 94.0 44.6 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 = l. More accurately, the units are (L)" *Kg'1) Freundlich isotherms relate the 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. R eferen ces 1. Adsorption-Desorption Using a Batch Equilibrium Method (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 3,14 and 15 as well as raw spreadsheets on pages 205-233 were corrected follow ing 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 modified to indicate this report has been amended. The signature page was re-signed following the amendments. 3M Environmental Laboratory Page 23 of 703 0002SJ. 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 Date 3M Environmental Laboratory Page 24 of 703 0002S2