Document mpa99Jog6MKBOv5Vm4abrk77Z

20) OECD 106-OPPTS 835.1220, Adsorption / Desorption, 023-048 21) OPPTS 835.1110, Activated sludge sorption isotherm (incorporated with OECD 106) FINAL REPORT STUDY TITLE DEC 0 9 2003 ADSOFPl?IOh AND DESORPTION STUDY TO DETERMINE THE A v A 9 B I L I T Y AND DISTRIBUTIONOF PERFLUOROBUTANESULFONICACID INSOIL DATA REQUIREMENTS OECD Guideline for Testing of Chemicals, 106 STUDY DIRECTOR Kevin Lloyd STUDY COMPLETED ON March 8,2001 TESTING LABORATORY Centre Analytical Laboratories, Inc. (Centre) 3048 Research Drive State College, PA 16801 Phone (814) 231-8032 STUDY SPONSOR 3M Environmental Technology and Safety Services (3METSS) Building 2 - 3 5 0 9 PO Box 33331 St. Paul, MN 55133-3331 Phone: (651) 778-5631 STUDY IDENTIFICATION NUMBER Centre Study Number 023-048 Total pages 74 DEC 0 9 2S003 ~ ~ ~ T \ Z E D Centre Study No. 023-048 GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT Centre Study Number 023-048, entitled "Adsorption and Desorption Study to Determine the Mobility and Distribution of Perfluorobutanesulfonic Acid in Soil" conducted for 3M Environmental Laboratory, was performed in compliance with US EPA Good Laboratory Practice Standards (40 CFR Part 160) and the OECD Principles of Good Laboratory Practice (Monograph No. 45) by Centre Analytical Laboratories, Inc. with the following exceptions: 1. The test substance lacked full characterization per EPA 160.105 and OECD 1.1.2.p. 2. Test substance storage between receipt and login was not documented (EPA 160.107, OECD 6.1) 3. Occasionally data were not recorded promptly at the time of observation (EPA 160.130, OECD 8.3.3). 4. Computerized systems were not fully validated (OECD 1.2.2.9. 5. Computerized data lack a full audit trail (OECD 8.3.5). Kevin Lloyd Date Study Director Centre Analytical Laboratories, Inc. 3048 Research Drive State College, PA 16801 Phone (814) 231-8032 SponYor Kepresentative - 3M Environmental Technology and Safety Services (3h4ETSS) Centre Analytical Laboratories, Inc. Page 2 of 74 Centre Study No.023-048 QUALTITY ASSURANCE STATEMENT Centre Study Number 023-048 entitled "Adsorption and Desorption Study to Determine the Mobility and Distribution of Perfluorobutanesulfonic Acid in Soil" was reviewed by Centre Analyt~calLaboratories' Quality Assurance Unit, All reviewed phases were reviewed for conduct according to Centre Analytical Laboratories' Standard Operating Procedures, the Study Protocol, and all applicable Good Laboratory Practice Standards. All findings were reported to the Study Director and to management. - Phase 1. Protocol Review 2. In-Phase Audit 3. Raw Data Review Draft Report Review 4. Final Report Review Date Inspected 12/14/00 12/27/00 1/22-25/01 U28/01 Date Reported to Study Director and Centre Management 12/19/00,1U20/00 1/11/01, 1/12/01 3/8/01,3/2/01 3/8/0 1 Date Reported to Sponsor Management 12/21/00 2/9/01 3/8/01 3/8/01 u-1 J+-Jp---- Naomi Lovallo Senior Quality Assurance Auditor 3 f f hI Date Centre Analytical Laboratories, Inc. Page 3 of 74 Centre Study No. 023-048 CERTIFICATION OF AUTHENTICITY This report, for Centre Study Sumber 023-048, is a true and complete representation of the raw data for the study. Submitted by: - Centre Analytical Laboratories, Inc. 3048 Research Drive State College, PA 16801 Author, Centre: Willia-m Spare, T-echnical Lead QAU Study Director, Centre: -, i,hia 7- Kevin Lloyd - ~- Date Study Director Centre Analyticd Laboratories, Inc. Centre Analytical Laboratories, Inc. Facility Management: - / I Richard A . w i n i , Ph.D. President - Centre Analytical Laboratories, Inc. - 8 - m -0 I Date Centre Analytical Laboratories, Inc. Page 4 of 74 . ITIZED DEC 09 2003 Centre Study No.023-048 STUDY IDENTIFICATION ADSORPTION AND DESORPTION STUDY TO DETER- THE MOBILITY AND DISTRIBUTION OF PERFLUOROBUTANESULFONICACID IN SOIL - TYPE OF STUDY: adsorption/desorption TEST SYSTEM: Domestic sludge (NIST #2781), river sediment, soils TEST SUBSTANCE: PFBS CENTRE STUDY NUMBER: 023-048 STUDY PROTOCOL NUMBER: OOP-023-048 SPONSOR STUDY MONITOR: 3M Environrnentai Technology and Safety Services STUDY DIRECTOR: Kevin Lloyd Centre Analytical Laboratories, Inc. Phone: (814) 23 1-8032 TESTING FACILITIES: Centre Ana1ytical Laboratories, Inc. (Centre) 3048 Research Drive State College, PA 16801 Phone: 814-231-8032 STUDY TIMETABLE: Study Initiation Date: Experimental Start Date: Experimental Termination Date: October 23, 2000 December 11,2000 January 9,2001 Centre Analytical Laboratories, Inc. Page 5 of 74 Centre Study No. 023-048 STUDY PERSONNEL The Study Director for this project was Kevin Lloyd at Centre Analytical Laboratories, Inc. The following personnel from Centre Analytical Laboratories, Inc., were associated with various phases of the study: Name William Spare Brent McCracken Matthew S. Yasovsky Rick Keller John Flaherty - Title Technical Lead QAU Scientist Technician Sample Custodian Operations Manager Centre Analytical Laboratories, Lnc. Page 6 of 74 . Centre Study No 023-048 TABLE OF CONTENTS Title Page ................................................................................................................. 1 Good Laboratory Practice Compliance Statement .................................................. 2 Quality Assurance Statement................................................................................... 3 Certification of Authenticity.................................................................................... 4 Study Identification ................................................................................................. 5 Study Personnel ....................................................................................................... 6 Table of Contents..................................................................................................... 7 1.0 Summary...................................................................................................... 9 2.0 Introduction.................................................................................................. 9 3.0 Test System................................................................................................ 10 4.0 Test Soils. Sediment and Sludge ............................................................... 10 5.0 Test Substance........................................................................................... 11 6.0 Analytical Method ...................................................................................... 11 7.0 Experimental Conditions ........................................................................... 12 Tier 1 -- Preliminary Study........................................................................ 12 Tier 2 -- Sorption Kinetics ......................................................................... 13 Tier 3.......................................................................................................... 13 8.0 Calculations............................................................................................... 14 9.0 Results and Discussion .............................................................................. 15 10.0 Circumstances That May Have Affected the Data .................................... 16 11.0 Retention of Data and Samples.................................................................. 17 12.0 References.................................................................................................. 17 LIST OF TABLES Table 1: Soil. Sediment. and Sludge Characterization .......................................... 18 Table 2: Solution Values from Tier 1Testing ....................................................... 19 Table 3: Soil Values from Tier 1 Testing .............................................................. 20 Table 4: Mass Balance from Tier 1 Testing .......................................................... 21 Table 5: Solution Values from Tier 2 Testing ....................................................... 22 Table 6: Soil and Sludge Values from Tier 2 Testing ........................................... 23 Table 7: Tier 2 Mass Balance ................................................................................ 24 Table 8: Adsorption Solution Values (C, ) from Tier 3 Testing ............................ 25 Table 9: Desorption Solution Values (C,) from Tier 3 Testing............................. 26 Table 10: Soil and Sludge Values (x/m) from Tier 3 Testing ............................... 27 Table 11: Mass Balance for Don Uglem Loam -- Tier 3 Testing.......................... 28 Table 12: Mass Balance for Kittson Clay -- Tier 3 Testing .................................. 29 Table 13: Mass Balance for Broeren Clay Loam -- Tier 3 Testing....................... 30 Table 14: Mass Balance for River Sediment-- Tier 3 Testing............................... 31 Table 15: Mass Balance for NIST Sludge -- Tier 3 Testing.................................. 32 Table 16: Freundlich Adsorption Isotherm............................................................ 33 Table 17: Freundlich Desorption Isotherm ............................................................ 34 Table 18: pH Readings During Tier 1 and 2 Testing............................................. 35 Table 19: pH Readings During Tier 3 Testing ...................................................... 36 Centre Analytical Laboratories. Inc. Page 7 of 74 . Centre Study No 023-048 LIST OF FIGURES Figure 1:Representative Standard of PFBS at 500ppb ............................................ 37 Figure 2:Kittson Clay 48 Hour CaC12 Solution ..1/1 Ratio Tier 1 ......................... 38 Figure 3:Don Uglem Loam 48 Hour Soil Extract ..111 Ratio Tier 1.....................39 Figure 4:Kittson Clay Blank Solution at 24 Hours 1/1 Ratio Tier 1 ....................... 40 Figure 5 : Fortified Control From Tier 2 Testing Nominal lOOOppb ........................ 41 Figure 6:Broeren Clay Loam 24 Hour CaC12 Solution -- 1/1 Ratio Tier 2..............42 Figure 7: Goose River Sediment 24 Hour CaC12 Solution -.1/1 Ratio Tier 2.........43 Figure 8: NIST Sludge 24 Hour CaC12 Solution ..1/5 Ratio Tier 2 ........................ 44 Figure 9:NIST Sludge 24 Hour Solids Extract ..1/5 Ratio Tier 2.......................... 45 Figure 10: Tier 3 Kittson Clay Adsorption Solution Nominal lOOOppb .................4.6 Figure 11:Tier 3 Broeren Clay Loam Adsorption Solution Nominal 500ppb.........47 Figure 12: Tier 3 Don Uglem Loam Adsorption Solution Nominal 250ppb ...........48 Figure 13: Tier 3 Goose River Sediment Adsorption Solution Nominal lOOppb ....49 Figure 14:Tier 3'Broeren Clay Loam Desorption Solution Nominal 50ppb...........50 Figure 15: Tier 3 Goose River Sediment Desorption Solution Nominal 1000ppb...51 Figure 16: Tier 3 NIST Sludge Adsorption Solution Nominal lOOOppb..................52 Figure 17:Tier 3 NIST Sludge Solids Extract Nominal 5OOppb.............................. 53 LIST OF APPENDICES Appendix A: Study Protocol OOP-023-048 Adsorption and Desorption Study to Determine the Mobility and Distribution of Perfluorobutanesulfonic Acid in Soil. Protocol and SOP Deviations........................................................................... 54 Centre Analytical Laboratories. Inc. Page 8 of 74 . Study Title Centre Study No. 023-048 ADSORPTION AND DESORPTION STUDY TO DETERMINE THE MOBILITY AND DISTRIBUTION OF PERFLUOROBUTANESULFONICACID IN SOIL 1.0 SUMMARY This study was performed to estimate the adsorptioddesorption behavior of perfluorobutanesulfonic acid (PFBS) on soils, sediment and sludge to obtain a sorption value which can be used to predict partitioning under a variety of environmental conditions. The study was performed to meet the guideline requirements described in the OECD Guidelines for Testing of Chemicals 106. The three tested soils and sediment demonstrated no adsorption of PFBSr The Don Uglem loam, Kittson clay, Broeren clay loam and Goose River sediment all showed no detectable PFBS remaining with the solids following adsorption. Detection of PFBS in desorption solutions occurred in only a few scattered samples. No calculations using the Freundlich isotherm were possible for the Don Uglem loam, Kittson.clay, Broeren clay loam and Goose River sediment. The lack of sorption of PFBS to the three soils or the sediment placed PFBS in the very high *:mobility class based on ASTM El 195 (K, 0 - 50). PFBS yielded a Freundlich Kf (adsorption) value of 0.3 with a l/n value of 1.284 for activated sludge obtained from the NIST, Gaithersburg, MD 20899. The initial PFBS concentration in solution was independent of the determined sorption value. This value also placed PFBS in the very high mobility class. 2.0 INTRODUCTION This report details the results of testing the adsorption and desorption of PFBS to soils, sediment and sludge supplied by 3M Environmental Technology and Safety Services (3METSS). The study was performed over a two-month period with analysis of the generated solutions and solids performed using an ion specific method of liquid chromatography/massspectroscopy (LCMS). All solutions and soils were extracted and analyzed for PFBS using the procedures detailed in Centre Analytical Labs SOP CAL- 24FWUO; "Extraction of Wastewater Samples for Fluorochemical Analyses by LC/MS" and SOP CAL-24FLW1, "Analysis of Select Fluorochemicals by LCMS'. Centre Analytical Laboratories, Inc. Page 9 of 74 Centre Study No. 023-048 The study was initiated on October 23,2000 when the study director signed protocol number OOP-023-048. The analytical start date was December 1I, 2000, and the experimental termination date was January 9,2001. 3.0 TEST SYSTEM The test system for this study was each 50 mL plastic centrifuge tube containing soil, sediment or sludge to which PFBS fortified CaC12 solution was added. All test systems were established and maintained per the protocol and the test temperature ranged from 17.0 to 19.1"C (Tier l), 19.5 to 22.7"C (Tier 2), and 18.2 to 19.3"C (Tier 3). 4.0 TEST SOILS, SEDIMENT AND SLUDGE Soil, sediment, and sludge samples were obtained and transported to Centre by 3METSS. Source location (specified in geographical coordinates) and the depth of sampling (120 cm) were provided. Each sample was assigned a unique identification number at Centre, which was used for tracking and identification of the soillsediment during the study. The soil/sediment/sludge were stored in a temperature-monitored refrigerator maintained at 2 to 6" C. The samples were kept isolated from the test substance during storage. AGVISE Laboratories, Northwood, ND, performed characterization of the test soils and sediment. See Table 1 for soil and sediment characteristics. As specified by the OPPTS Guideline 835.1110,the activated sludge had been collected and prepared by settling, washing and centrifuging three times, lyophilization, powdering, and oven drying at 103OC for 3 hours or longer. The sludge used in this study was obtained from the National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899 and identified as Standard Reference Material 278 1. The sludge was supplied to Centre by 3METSS. Each sludge sample was assigned a unique identification number at Centre, which was used for tracking and identification of the sludge during the study. The sludge was stored in a temperature-monitored refrigerator maintained at 2 to 6" C. The samples were kept isolated from the test substance during storage. The table below summarizes the characteristics of the sludge as provided by the NIST. SRM = standard reference material (SRM #2781 used in this study) Centre Analytical Laboratories, Inc. Page 10 of 74 5.0 TEST SUBSTANCE Centre Study No. 023-048 The following analytical standard was used: Test Material Lot Number Purity (%) Expiration Date I I I I I PFBS 07/06/2001 I I 1 lBD I I TBD = to be determined, under separate study protocol. Chemical names and structures of the test substance are presented below. Chemical Name: Moleculaf Weight: perfluorobutanesulfonic acid 300 0 II Gag-S-OH II 0 Test and Reference Substance Documentation The methods of synthesis, fabrication and/or derivation of the test and reference substances are documented and retained by the Sponsor. The Sponsor, as required by US EPA FIFRA GLP Standard 40 CFR 160.105, is responsible for characterization of the test and reference substances, and the Sponsor retains these records. Archived samples of the test and reference substances are being retained by the Sponsor. The Sponsor is maintaining these records and archived samples at the 3M facilities in St. Paul, MN. The test and reference substances containers were retained beyond the duration of the study. Any emptied containers at study completion were disposed of according to standard Centre procedures. Any remaining test and/or reference substances were retained by/at Centre, or authorization was obtained from the Sponsor to return any remaining substances. Records are maintained at Centre documenting use, disposal, or return of test and/or reference substances. 6.0 ANALYTICAL METHOD All solutions and soils were extracted and analyzed for PFBS using the procedures detailed in Centre Analytical Labs SOP CAG24FWUO; "Extraction of Wastewater Samples for Fluorochemical Analyses by LCMS" and SOP CAL-24FLW1, "Analysis of Select Fluorochemicals by LCMS'. The solution extraction procedure was changed to a filtration Centre Analytical Laboratories, Inc. Page 11 of 74 Centre Study No. 023-048 of the samples through 0.45 micron filters followed by L C N S analysis. This procedure provided more consistent results than the ion extraction method. Sample/solution preparation, storage location and conditions during the study were documented in the study data. All samples and any soil/sediment extracts were identified with a unique label. Such identification was on the sample container. During analytical runs calibration standards were interspersed throughout the run. No more than 5 samples were analyzed between standards. At least 8 standards were analyzed per run with a minimum of 6 used in the calibration curve. The r2value of the calibration curves were >0.99. 7.0 EXPERIMENTAL CONDITIONS TIER 1 Preliminary Study PFBS was dissolved in methanol (JT Baker Lot T34315) at 10.09 mg/mL. A 0.1 mL aliquot of this stock was brought to 1000 mL with 0.01M CaC12 solution (well below the water solubility of the test substance) to provide fortified (0.01 M Ca"). The Don Uglem loam and the Kittson clay were used in the Tier 1 testing. The experiments were performed in individual disposable plastic 50 mL centrifuge tubes. Mixing of the soils and calcium chloride solution was accomplished using a tumbler which rotated the test tubes end-overend at 32 rpm. Three different soil to solution ratios were tested: 1/1, 1/5 and 1/25. All experiments were performed in triplicate with individual analysis of each replicate. This included the controls and blanks. The pH of the blank and fortified 0.01M CaC12 solution as well as the aqueous phases recovered after contact with the sludge were measured and recorded. The mixtures of soil and fortified 0.01M CaC12 solutions were placed on the tumbler and mixed until adsorption equilibrium was reached. Samples were collected over a 48-hour period of continuous mixing. At the specified sample intervals (4, 8, 24, and 48 hours) all test systems (centrifuge bottles with soil and solution) were centrifuged. Following this solid-liquid separation, an aliquot (1 mL) of the aqueous phase was removed for analysis. After removal of the sample, the soil was remixed with the aqueous phase and all centrifuge bottles were returned to the mixing apparatus until the subsequent sampling. Using a calibrated thermometer placed adjacent to the tumbler monitored temperature. Temperature ranged from 17.0 to 19.1"C during this phase of testing. The percent adsorption (Ati) was calculated at each time point (ti) based on the average concentration of the three control replicates (fortified solution only) and the measured concentration at the sampling time (ti). Plots of At;versus time were not generated since no apparent adsorption of PFBS was observed. The & value at 48 hours could likewise not be calculated. Based on the lack of adsorption the highest ratio was selected. The selected ratio used for all remaining work was l g soi1:l mL of solution in an attempt to obtain adsorbed values between 20% and 80% of the original amount in solution. Centre Analytical Laboratories, Inc. Page 12 of 74 Centre Study No. 023-048 Following the ratio-finding experiment and analysis of the last sample of the aqueous phase after 48 hours, the phases were separated by centrifugation.I The aqueous phase was recovered and the soil was extracted with methanol for analysis of PBSF. The concentration of PFBS in solution and soil extracts was determined by LCMS. The mass balance was performed on all three soil/solution ratios for each soil type. The mass balance was determined as the total PFBS recovered in the soil plus the total PFBS in the aqueous phase at 48 hours. The mass balance was calculated as a percent of the applied PFBS based on analysis of the fortified 0.01M CaCI2solution (no soil). TIER 2 -- Sorption Kinetics The remaining soil, river sediment and sludge were next tested at a solidsholution ratio of 1/1 for the soil and sediment and 1/5 for the sludge (soil to solution -- 20 g to 20 mL, sludge 5g to 40 mL). The concentration of the PFBS in the solution (100OpgL) was maintained based on the solubility of PFBS (>5000m a ) . Analysis of aqueous solutions was performed at 2,4,6,8a,nd 24hours of contact time. The soil, sediment and sludge were tested in triplicate with triplicate controls (test substance in 0.01M CaC12 solution with no solids) and triplicate blanks for each (solids and 0.01M CaC12 solution with no test substance). The test was performed as in the original preliminary work with tumbling of the soil, sediment and sludge with test solution, centrifugation of the samples, removal of aliquots following centrifugation, analysis of sampled aliquots, and reinitiating tumbling until the next sampling interval. The concentration of PFBS in the solutions was determined by LCMS. The percent adsorption was calculated at each time point (A,J and plotted versus time. The preliminary sorption coefficient K at equilibrium was also calculated. TIER 3 Adsorption Isotherm Five nominal test concentrations of PFBS (1000, 500, 250, 100, 50 pg/L) were used. Each test concentration was evaluated in triplicate with triplicate blanks (solids and 0.01M CaClz solution with no PFBS). The concentration values were selected to stay well above the PFBS detection limit (limit of detection was 10 p a ) . The sludge/solution ratio used for the testing was 1/5 throughout this phase of the study. Soils and sediment were tested at a ratio of 1/1. The adsorption test was performed as described under Tiers 1 and 2, except that the aqueous phase was analyzed only once at the equilibrium time determined to be 24 hours in Tier 2. The equilibrium concentrations in the solutions were determined by LC/MS. Centre Analytical Laboratories,Inc. Page 13 of 74 Centre Study No. 023-048 Desorption Isotherm Following removal of the adsorption solutions from the solids, all remaining solids were next remixed with fresh 0.01M CaC12 solution without PFBS. The same volume of solution as used for the adsorption phase was used in the desorption phase. The desorption test was performed as described under Tiers 1 and 2, except that the aqueous phase was analyzed only once at 24 hours as for the adsorption phase. The equilibrium concentrations in the solutions were determined by LC/MS. Following desorption, solid samples for which the adsorption and desorption solutions did not account for >90% of the applied PFBS were subjected to methanol extraction and LC/MS analysis. The extraction was performed using a wrist action shaker with methanol for 30 minutes followed by 30 minute sonication. Samples were centrifuged to separate the solvent and solids and the supernatant was decanted. The extraction was performed twice and both extracts were combined, concentrated, and analyzed. Mass balance was.determined for all samples for all soils, sediment and sludge. The Freundlich adsorption and desorption isotherms were calculated only for the sludge since no soil or sediment demonstrated adsorbance of PFBS. The pH of the blank and fortified 0.01M CaC12 solutions as well as the aqueous phases recovered after adsorption and desorption were measured and recorded. 8.0 CALCULATIONS Mass Balance A mass balance was performed using the following formula to ensure that the test substance was adequately accounted for: MB = {V, * C, + mE ) "100 v, * c o Where: MB = mass balance (%) mE = total mass of PFBS from solids (pg) C, = initial mass concentration of PFBS in contact with the solids (pghL) C, = equilibrium concentration of PFBS (pg/mL) V, = volume of the initial supernatant applied to the solids (I&). V,,, = volume of the supernatant recovered after the adsorption equilibrium (mL). Centre Analytical Laboratories, Inc. Page 14 of 74 - Centre Study No. 023-048 Freundlich Isotherm (Kd - The Freundlich equation was applicable to the adsorptioddesorption of PFBS at intermediate concentrations and was used to evaluate the batch equilibrium data. The equation was an empirical relationship used in the form: log Cads= l/n log C, + log& Where: Cads= the adsorbed concentration (pg/g); C, = the solution equilibrium concentration (pg/mL); Kf, n = constants. The Tier 3 data was subjected to evaluation using the Freundlich equation. For calculation purposes, the concentration of PFBS in the solids following adsorption was determined as the sum of the desorption solution values plus the amount extracted from the solids. Where possible, the sorption coefficient Kf and the constant l/n were calculated for adsorption and desorption. 9.0 RESULTS AND DISCUSSION Tables 2 to 4 and Figures 1 to 4 present the preliminary testing performed in Tier 1 to determine any adsorption of the test substance to the test vessel, the ratio of soil to solution, and the equilibrium mixing time. Tables 5 to 7 and Figures 5 to 9 present the results of the Tier 2 testing. The Tier 1 and 2 tests showed that adsorption of PFBS to the test vessel would not occur during the testing. Percent of applied material determined as percent of applied PFBS yielded recoveries of 70 to 100percent (range 71.1 to 104.1%). See Tables 4 and 7. Tier 1testing using three soil to solution ratios and two soil types (loam and clay) was performed over a 48 hour period with solution sampling at 4, 8, 24, and 48 hours (Table 2). At 48 hours the soils were collected and analyzed for PFBS concentration (Table 3). No soil to solution ratio tested demonstrated adsorption of PFBS in the range of 20 to 80%. The 1/1 ratio was chosen because it represented the highest concentration of soil to solution ratio identified in the protocol. The estimated K values from Tier 1 approximated 0.0 (Table 4). With the lack of adsorption observed in Tier 1, no plots of percent adsorption versus time were generated. Tier 2 testing (Tables 5-7) was performed over a 24 hour period with solution samplings at 2, 4 , 6 , 8, and 24 hours. At 24 hours the soil, sediment and sludge were collected and analyzed for PFBS concentration. The estimated K value (sludge only) was 0.5. The plots of percent adsorption versus time (bottom of Table 7) indicate that the equilibrium plateau was reached by 24 hours. Balance was good and averaged 102.1% for the river sediment, 100.3% for the clay loam soil, and 72.5% for the sludge. Centre Analytical Laboratories,Inc. Page 15 of 74 Centre Study No. 023-048 The Tier 3 testing was performed in triplicate at a sludge to solution ratio of 1/5, the soils and sediment were tested at a ratio of 1/1. All testing used nominal PFBS concentrations of 50, 100,250,500, and 100Opg.L Actual measured PFBS concentrations were 38,79, 196, 391, and 758 /.A&. Analysis of adsorption solution samples was performed following a 24 hour mixing period. Following removal of the adsorption solutions, fresh unfortified calcium chloride solution was added and the samples tumbled for an additional 24 hour desorption period. The temperature during the Tier 3 testing was 18.2 to 19.3"C. The analytical results are presented in Tables 8 to 10. Table 8 presents the adsorption solution values, Table 9 the desorption solutions and Table 10 the residual soil, sediment and sludge values. If an average of greater than 90% of the applied PFBS was not recovered from the adsorption and desorption solutions the residual solids were extracted with methanol. Reproducibility between the three replicates at each concentration was obtained (Table 8). Except for the sludge detectable PFBS was recovered from only a scattered few desorption solutions (Table 9). The sludge residual values for PFBS are presented in Table 10. Representative chromatograms from the LC/MS analysis of PFBS during Tier 3 are presented in .Figures 10 to 17. Tables 11 to 15present the obtained mass balance from all Tier 3 testing. Each soil, sediment or sludge is presented in a single table. Overall mass balances were good with the average recovery 90.3% for Don Uglem loam (range 77.2 - lOS.l%), 105.9% for Kittson clay (range 89.5 - 126.8%), 101.7% for Broeren clay loam (range 91.5 - 116.8%), 117.4% for Goose River sediment (range 107.6 - 128.9%), and 79.1% for NIST sludge (range 68.9 93.5%). PFBS was only detected in the sludge soIids. Therefore, Freundlich isotherm calculations could only be performed for the sludge. The following Kf fit values were determined for adsorption Kf= 0.3 with l/n of 1.2840; for desorption Kf=0.001 with l/n of 2.6055. The straight-line plots of the log C, (solution equilibrium concentration n & L ) versus log x/m (concentration sorbed to the sludge ng/g) are presented at the bottom of Tables 16 and 17 for adsorption and desorption, respectively. The pH of the PFBS test solutions was approximately 6.0 at concentrations ranging from 50 to 1000pg/L. Following contact with the soils, sediment or sludge the solution pH values were measured (Tables 18 and 19). The Don Uglem loam and the sludge*increasedsolution pH to a range of approximately 6.3 to 6.5. The Kittson clay soil and Goose River sediment increased solution pH to a range of about 7.5 to 7.7. The Broeren clay loam increased the pH levels the least to approximately6.0 to 6.2. There was no apparent effect of pH on the adsorption of PFBS in the tested soils, sediment or sludge. The Don Uglem loam, Kittson clay, Broeren clay loam and Goose River sediment all showed no detectable PFBS remaining with the solids following adsorption (Kf = 0.0). The initial PFBS concentration in solution was independent of the determined sorption value. This value also placed PFBS in the very high mobility class based on ASTM E l 195 (I& 0 - 50). Centre Analytical Laboratories, Inc. Page 16 of 74 Centre Study No. 023-048 10.0 CIRCUMSTANCESTHAT MAY HAVE AFFECTED THE DATA Circumstances that may have affected the data are detailed in the SOP and Protocol deviations attached to the protocol in Appendix A. 11.0 RETENTION OF DATA AND SAMPLES When the report is final, all original paper data generated by Centre Analytical Laboratories, Inc. will be shipped to the sponsor. This does not include facility-specific raw data such as instrument logs. Exact copies of all raw data, as well as a signed copy of the final report and all original facility-specific raw data, will be retained in the Centre Analytical Laboratories, Inc. archives for the period of time specified in 40 CFR Part 160. 12.0 REFERENCES 1. US Environmental Protection Agency, January 1998, Fate, Transport and Transformation Test Guidelines, OPPTS 835.1110 "Activated Sludge Sorption Isotherm". EPA 712-C-98-298. 2. OECD GUILDELINES FOR THE TESTING OF CHEMICALS: GUIDELINE 106, "AdsorptionDesorption" Adopted 21 January 2000. 3. Organisation for Economic Co-operation and Development, OECD "Principles of Good Laboratory Practice", ENV/MC(98)17, November 26, 1997. 4. US Environmental Protection Agency, August 17, 1989. Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) Good Laboratory Practice Standards; Final Rule (40 CFR: 160), Federal Register, Vo1.54, No. 158: 34052-34074. 5. ASTM "Standard Test Method for Determining a Sorption Constant (Koc) for an I Organic Chemical in Soil and Sediments," Designation El 195, 1994.Annual Book of ASTM Standards, Vol. 11.04. Centre Analytical Laboratories, Inc. Page 17 of 74 Centre Study No. 023-048 TABLE 1: SOIL, SEDIMENT, AND SLUDGE CHARACTERIZATION Source Don Uglem Loam Broeren Clay Loam Kittson Co. Goose River Clay Sediment NIST Sludge 1 I Datecollected 1 10/19/00 I 10/19/00 I 1 I Collection depth 0-6" 0-6" i 1 1 I 1 1 TZi-1 Centre# 0010916 0010917 I 10/21/00 I 10/19/00 1 NA I4 0-6" j-0-6" NA 0010919 0010918 Texture loam clay loam clay loam NA %sand %silt 39 21 16 39 NA ~ 50 46 22 42 NA %clay 11 33 62 19 NA Organic Carbon% 4.9 2.6 2.6 1.3 NA Organic Matter % 8.4 4.4 4.5 2.3 100 pH in 0.01M CaClz 7.4 6.0 7.2 7.7 NA Total Nitrogen (%) 0.358 Cation Exchange Capacity 23.9 (meq/lOOg) Geographical Reference 0.216 24.7 0.223 54.5 0.101 17.5 4.78 NA Denver, CO Latitude 47'44' 47'42' 48'62' 47'45' NA Longitude 97'48' 97'40' 96'89' 97O37' NA Soil and sediment characterization performed by AGVISE Laboratories, Northwood. North Dakota. NA = not applicable or not performed. Organic Carbon % = organic matter % / 1.724. Centre Analytical Laboratories, Inc. Page 18 of 74 Centre Study No. 023-048 TABLE 2: SOLUTION VALUES FROM TIER 1 TESTING Ratio Analysis I I PFBS from Aqueous Solution 4 hour 8hour 24hour ] 48hour* - I 1 I I- I I Don Uglem Loam (lOOOpg/L PFBS) 20/20 1 1 I 0.282 I 0.325 I 0.250 I 0.642 2 I 0.955 I 0.893 I 0.237 I 0.616 3 0.986 0.675 0.221 0.606 Average 0.741 0.631 0.236 0.621 Avg 8 95.8 81.6 30.5 80.3 5/25 1 0.296 0.552 0.770 0.749 3 Average Avg % 1.01 5 0.853 1 10.3 0.462 0.609 78.8 0.326 0.368 47.6 0.553 0.579 74.8 5/25 1 1 0.321 I 0.483 I 0.390 I 0.751 3 Average Avg % 0.340 0.551 71.3 0.438 0.425 54.9 0.609 0.439 56.8 0.720 0.732 94.7 - 1/25 - 1 1.158 0.323 0.433 0.752 2 1.01 6 0.361 0.256 0.722 3 0.288 0.323 0.51 1 0.749 Average 0.821 0.336 0.400 0.741 ] Avg. Fortified Control I 0.305 I 0.773 I 0.675 1 0.773 I Ratio = grams of soil per mL of CaClz solution. *48 Hour samples were filtered and analyzed versus other samples which were extracted, Avg % = average percent of Fortified Control PFBS at 48 hours. Centre Analytical Laboratories, Inc. Page 19 of 74 Centre Study No. 023-048 TABLE 3: SOIL VALUES FROM TIER 1 TESTING Ratio Replicate PFBS Results From 48 (/..@TImLethanol ex tract) 20/20 I 1 2 3 Average 5/25 1 2 3 Average 1/25 1 2 3 1 Average I 3.820 3.940 3.200 3.653 2.71 0 2.81 0 2.690 2.737 0.767 0.825 0.81 4 0.802 0.00 0.00 0.00 20120 I 1 1 Average 1 3.380 3.170 2.950 2.627 I 1/25 1 2 0.909 0.964 3 Average 0.992 0.955 1 I , Ratio = grams of soil per mL of CaC12 solution. Total PFBS pg are corrected for pg in interstitial CaC12 0.00 0.00 I 0.01 I I Centre Analytical Laboratories, Inc. Page 20 of 74 Centre Study No. 023-048 TABLE 4: MASS BALANCE FROM TIER 1 TESTING I 1 I Ratio Total PFBS pg Solution Soil Total Percent of Applied Solution Soil + Don Uglem Loam (1000mgL PFBS) 11 I 1 1 I I 1 20120 12.4 0.00 12.4 80.3% 0.0% 80.3% Estimated K = 0.0 97.0% 0.0% 97.0% Estimated K = 0.0 1 1/25 I 19.9 I 0.00 I 19.9 102.7% I 0.0% 1 102.7% 1 Kittson Clay (1000mg/L PFBS) 20120 11.6 0.00 11.6 Estimated K = 0.0 5/25 18.3 0.00 18.3 Estimated K = 0.0 1/25 18.5 0.01 18.5 Estimated K = 0.0 74.8% 0.0% 74.8% 94.7% 0.0% 94.7% 95.8% 0.0% Average 95.8% 90.9% rota1 detected PFBS in control at 48 hours = 0.773pg/mL0.01M CaC12 solution Ratio = grams of soil per mL of CaC12 solution Centre Analytical Laboratories, Inc. Page 21 of 74 - Centre Study No. 023-048 II TABLE 5: SOLUTION VALUES FROM -TIER 2 TESTING 3 . Average Avg % 0.959 0.955 105.5 0.860 0.862 107.4 0.859 01858 105.1 0.797 0.778 109.1 0.796 , 0.781 102.1 Avg % = average percent of Avg. Fortified Control Ratio = grams of soil or sludge per mL of CaC12 solution i Centre Analytical Laboratories,Inc. Page 22 of 74 Centre Study No. 023-048 TABLE 6: SOIL AND SLUDGE VALUES FROM TIER 2 TESTING Ratio I Replicate PFBS Results From 24 Hours I (pg/mL methanol extract) Total PFBS Goose River Sediment (lOOOpg/L PFBS) -I 20120 1 2 I 3 1 Average 6.1 10 5.71 0 5.650 5.823 0.000 0.000 0.000 I Broeren Clay Loam (100OpgL PFBS) I 20120 1 5.1 80 0.000 2 5.000 0.000 3 Average 1 4.800 4.993 0.000 NIST Sludge (lOOO&/L PFBS) I 8/40 1 7.650 2.026 2 7.900 2.268 3 7.890 2.604 I I Average 1 7.813 I I Ratio = grams of soil or sludge per,mL of CaC12 solution. Total PFBS pg are corrected for pg in interstitial CaC12 solution (wet weight) Centre Analytical Laboratories, Inc. Page 23 of 74 Centre Study No. 023-048 TABLE 7: TIER 2 MASS BALANCE - Ratio = grams of soil or sludge per mL of CaC12solution. 50.0 C 40.0 0 -.-530.0 5: .aa 20.0 10.0 0.0 0 PFBS Tier 2 Adsomtion - I , 10 Hours 20 -+- sludge -+ sediment 30 Centre Analytical Laboratories, Inc. - Page 24 of 74 Centre Study No.023-048 TABLE 8: ADSORPTION SOLUTION VALUES (C,) FROM TIER 3 TESTING Test I ng/mL Solution From Adsorption Soil or Sludge I I I 1 I I I I Solution ng/mL Replicate UDgloenm Loam Kittson Clay River Sediment Broeren Clay loam NIST Sludge 758 1 789 932 977 852 526 2 797 937 971 885 536 3 776 961 975 884 532 391 ' 1 2 3 196 1 2 3 377 450 493 376 452 488 378 463 492 ~~ 162 20 1 222 168 198 222 165 201 229 41 6 260 41 9 257 421 254 190 115 201 113 195 113 79 1 61 75 87 75 46 2 63 76 a5 74 45 3 61 75 86 73 46 Tier 3 Ratios = all soils and sediment at 20g : 20 mL solution, sludge at 8g : 40 mL solution Centre Analytical Laboratories, Inc. Page 25 of 74 Centre Study No. 023-048 TABLE 9: DESORPTION SOLUTION VALUES (C,)FROM TIER 3 TESTING 391 ' 1 0.0 0.0 0.0 0.0 73 2 0.0 0.0 0.0 0.0 50 3 0.0 0.0 0.0 0.0 54 196 1 0.0 0.0 0.0 0.0 28 2 4.9 0.0 0.0 0.0 22 3 4.9 0.0 0.0 0.0 25 79 1 3.1 0.0 0.0 0.0 10 2 0.0 0.0 0.0 0.0 9 3 0.0 0.0 0.0 0.0 13 38 I 1 I 0.0 I o . 0 1 0.0 I 0.0 I 3.2 I 2 0.0 0.0 0.0 0.2 2.8 3 0.0 0.0 0.0 0.8 1.9 I I Blank 1 0.0 0.0 0.0 0.0 0.0 2 0.0 0.0 0.0 0.0 0.0 3 0.0 0.0 0.0 0.0 0.0 Tier 3 Ratios = all soils and sediment at 20g : 20 mL solution, sludge at 8g : 40 mL solution All soils, sediment and sludge desorbed using CaC12solution. Centre Analytical Laboratories, Inc. Page 26 of 74 Centre Study No. 023-048 TABLE 10: SOIL A N D SLUDGE VALUES (dm) FROM TIER 3 TESTING Initial Solution 758 Replicate I 1 2 3 I I 1 ng/g Solids From Soil or Sludge Extraction UDdoenm Kittson River Broeren NIST Loam I Clay I ~~ Sediment I Clayloam I Sludd NA NA NA NA NA NA NA NA NA NA 248 NA 191 NA 278 ! 1 391 . 1 NA NA NA 2 NA NA NA 3 NA NA NA NA 91 NA 103 NA 102 1 196 I 1 I NA I NA I NA I NA 1 4.9 1 I 1 2 1 NA I NA 1 NA 1 NA I 2.2 1 r I ~ 1 3 I NA 1 NA 1 NA 1 NA 1 0.0 I I I I I I I -1 79 1 NA NA NA NA 0.0 - 2 NA NA NA NA I 0_ .0_ 3 NA NA NA NA 0.0 I 38 Blank I 1 1 NA NA 2 NA NA 1 3 NA NA 1 1 NA NA 2 NA NA 3 1 NA 1 NA 1 NA NA NA NA NA NA 1 NA 0.0 NA 3.1 NA 0.0 I NA 0.0 NA 0.0 NA I 0.0 1 Tier 3 Ratios = all soils and sediment at 20g : 20 mL solution, sludge at 8g : 40 mL solution NA = not analyzed, adsorption and desorption solutions were >90% of applied overall. Centre Analytical Laboratories, Inc. Page 27 of 74 Centre Study No. 023-048 TABLE 11: MASS BALANCE FOR DON UGLEM LOAM - TIER 3 TESTING Soil : solution ratio 1:l (20g soil : 20 mL fortified 0.01M CaC12 solution) Ads = adsorption Des = desorption NA = not analyzed, adsorption and desorption solutions were >75% of applied, >90% overall, Centre Analytical Laboratories, Inc. Page 28 of 74 -~~ ~ Centre Study No. 023-048 It TABLE 12: MASS BALANCE FOR KITTSON CLAY - TIER 3 TESTING Initial Rep ng PFBS Solution 1 Total Percent of Applied I Solution I I Total I Ads I Des I Soil I I 18740 18740 391 1 9000 0.0 2 9040 0.0 3 9260 0.0 NA 9000 NA 9040 9260 115.1yo 1 15.6% 1 18.4% 196 1 1 4020 0.0 1 NA 4020 102.6% 0.0% 1 02.6% 2 3960 0.0 NA 3960 101.0% 0.0% 101.O% 3 4020 0.0 NA 4020 102.6% 0.0% 102.6% Avera e 102.0% 1520 1520 I Overall Average 105.9% Soil : solution ratio 1:l (20g soil : 20 mL fortified 0.01M CaC12 solution) Ads = adsorption Des = desorption NA = not analyzed, adsorption and desorption solutions were >90% of applied. Centre Analytical Laboratories, Inc. Page 29 of 74 Centre Study No. 023-048 TABLE 13: MASS BALANCE FOR BROEREN CLAY LOAM - TIER 3 TESTING Soil : solution ratio I: 1 (20g soil : 20 mL fortified 0.01M CaC12 solution) Ads = adsorption Des = desorption NA = not analyzed, adsorption and desorption solutions were >90% of applied. > Centre Analytical Laboratories, Inc. Page 30 of 74 Centre Study No. 023-048 TABLE 14: MASS BALANCE RIVER SEDIMENT - TIER 3 TESTING Sediment : solution ratio 1:1 (20g sediment : 20 mL fortified 0.01M CaC12 solution) Ads = adsorption Des = desorption Sed = sediment NA = not analyzed, adsorption and desorption solutions were >90% of applied. i Centre Analytical Laboratories, Inc. Page 31 of 74 ~ Centre Study No.023-048 I TABLE 15: MASS BALANCE NIST SLUDGE - TIER 3 TESTING I 111 I1 ng- PF'BS Solution Total Ill ! 1 1 758 1 21040 I 4666.0 1 1984.7 27691 2 21440 5357.1 1539.9 28337 3 21280 3512.7 2228.6 27021 II l l 391 1 10400 2920.3 739.2 14060 2 10280 1993.0 834.7 13108 3 10160 2166.4 822.5 13149 1 1 I Solution Ads Des 1 Total Sludge* 1 1 1 1 1 79 i:li 430758.12 1840 514.6 I 2355 1 38 1 920 128.0 0.0 1048 2 960 110.0 25.4 1095 3 1240 77.1 0.0 1317 I Overall Average Sludge : solution ratio 1:5 (8g sludge : 40 mL fortified 0.01M CaC12 solution) Ads = adsorption Des = desorption *Sludge extracted with methanol. 79.1yo Centre Analytical Laboratories, Inc. Page 32 of 74 Centre Study No. 023-048 TABLE 16: FREUNDLICH ADSORPTION ISOTHERM NIST Sludge 1/5 ratio (Sg sludgd40 mL CaC12) Correlation = 0.9790 Slope (lh)= 1.2840 Intercept = -0.5470 Linear Regression Analysis n = 0.779 Kf = 0.3 a PFBS Adsorption Isotherm- sludge 4.0 0.0 0.0 1.0 2.0 3.0 4.0 log Ce (ng/mL) Centre Analytical Laboratories. Inc. Page 33 of 74 Centre Study No.023-048 TABLE 17: FREUNDLICH DESORPTION ISOTHERM ~ ~~ NIST Sludge 1/5ratio (8g sludgd40 mL CaC12) Sludge CaC12 Solution K I 3 I 277.84 1 2.444 1 87.82 1.944 I 3.2 I Correlation = 0.9198 Slope (lh)= 2.6055 Intercept = -2.8621 Linear Regression Analysis n = 0.3838 Kf = 0.001 PFBS Desorption Isotherm- sludge 3.0 1 I 0.0 4 I 0.0 1 .o 2.0 3.0 log Ce (ng/mL) I Centre Study No. 023-048 TABLE 18: pH READINGS DURING TIER 1 and 2 TESTING pH at Ratio 1 1 I Rep 1:l 15 1:25 I I Don Uglem Loam (lOOOpg/L PFBS) I Blank I I 1 I 1 6.25 I 6.03 I 5.99 6.62 2 6.24 6.01 5.99 6.60 3 6.31 6.01 5.98 6.68 ~~ `KittsonClay (100OpgL PFBS) I 1 1 I 1 I 7.57 1 6.95 I 7.00 I 7.70 I 1 2 1 7.50 6.91 7.00 7.70 3 7.50 6.93 7.00 7.65 Control (no soil) 5.99 5.85 5.89 PFBS fortified CaCl, 6.19 TIER 2 Broeren River NIST I I Rep I ClayLoam I Sediment 1 Sludge I PFBS 1 2 3 6.1 9 6.16 6.21 7.68 7.68 7.69 6.50 6.50 6.49 Blank 1 6.13 7.70 6.44 2 6.1 7 7.71 6.44 3 6.1 8 7.70 6.46 Control 6.10 6.00 5.75 PFBS fortified CaCI2 5.80 1 Blank contains soil, sediment or sludge with non-fortified CaC12 solution. Control contains fortified CaC12 solution with no soil, sediment or sludge. PFBS nominal fortification = 1000 p g L . Centre Analytical Laboratories, Inc. Page 35 of 74 Centre Study No. 023-048 TABLE 19: pH READINGS DURING TIER 3 TESTING 1 Initial I Solution Rep Don Uglem Loam 24 Hour Solution pH IQttson Clay River Sediment Broeren Clay loam NIST Sludge 758 1 6.31 7.48 7.58 6.20 6.45 ( 2 1 6.37 7.56 7.59 6.1 3 6.46 1 -3 1 6.31 7.58 7.56 6.10 6.47 39 1 1 6.27 7.57 7.66 5.99 6.48 2 6.29 7.64 7.58 5.98 6.48 3 6.30 7.75 7.64 5.96 6.47 L 196 . 1 6.39 7.77 7.64 6.09 6.46 I I 2 I 6.35 1 7.65 I 7.67 1 6.13 I 6.45 I I 1 3 1 6.26 I 7.74 I 7.57 1 6.06 I 6.46 I I 79 I 1 I 6.21 I 7.61 I 7.62 I 6.07 I 6.46 I I 1 2 I 6.29 1 7.63 I 7.66 I 6.02 I 6.46 I I I 3 I 6.24 I 7.64 I 7.66 I 6.05 I 6.45 I 38 1 6.34 7.71 7.70 6.1 7 6.48 2 6.34 7.70 7.66 6.18 6.47 3 6.30 7.72 7.70 6.1 7 6.48 0.0 1 6.26 7.69 7.65 6.10 6.50 2 6.29 7.66 7.65 6.07 6.50 I I 3 I 6.30 I 7.71 I 7.67 1 6.10 I 6.47 1 Centre Analytical Laboratories, Inc. Page 36 of 74 Centre Study No. 023-048 FIGURE 1: REPRESENTATIVE STANDARD OF PFBS AT 500ppb Centre Analytical Laboratories, Inc. Page 37 of 74 Centre Study No. 023-048 FIGURE 2: KITTSON CLAY 48 HOUR CaC12 SOLUTION AT THE l/1 RATIO TIER 1 1' " b ' . ' b ' . .d I Centre Analytical Laboratories, Inc. Page 38 of 74 Centre Study No. 023-048 FIGURE 3: DON UGLEM LOAM 48 HOUR SOIL EXTRACT -- 1/1 RATIO TIER 1 Centre Analytical Laboratories, Inc. Page 39 of 74 Centre Study No. 023-048 FIGURE 4: KITTSON CLAY BLANK SOLUTION AT 24 HOURS 111 RATIO TIER 1 -i- U M .. Compound Name Amount R.T. Sienrl Centre Analytical Laboratories, Inc. Page 40 of 74 Centre Study No. 023-048 FIGURE 5: FORTIFIED CONTROL FROM TIER 2 TESTING NOMINAL lOOOppb I 1 Centre Analytical Laboratories,Inc. Page 41 of 74 Centre Study No.023-048 -- FIGURE 6 BROEREN CLAY LOAM 24 HOUR CACLz SOLUTION 1/1 RATIO TIER 2 MSDI 299, ElC=288.7:288.7(122200UM000010.D) API-ES NogaUva 1sOOOO 160000 140000 12oOao 100000 I 0. 1. Compound Name PFBS I 2 Amount 142.3 I 4 R.T. 7.71 I 6 Area 1890871 I I ml Bignrl M S D l 299, EIC-298.7:29 Centre Analytical Laboratories, Inc. Page 42 of 74 Centre Study No. 023-048 FIGURE 7: GOOSE RIVER SEDIMENT 24 HOUR CACL2 SOLUTION -- 111 RATIO TIER 2 .I 18ooM)1WM)- - 14oooO 120000- - 1OoOw Centre Analytical Laboratories,Inc. Page 43 of 74 Centre Study No. 023-048 FIGURE 8: NIST SLUDGE 24 HOUR CACLz SOLUTION -- 1/5 RATIO TIER 2 0 Compound Nam I 2 Amount I 4 R.T. 1 4 Area nl I 8 Slmul. Centre Analytical Laboratories, Lnc. Page 44 of 74 Centre Study No. 023-048 FIGURE 9: NIST SLUDGE 24 HOUR SOLIDS EXTRACT -- 1/5 RATIO TIER 2 MSDl 298. EIC1288.7:209.7(1222OOUMOOw34.0) API-ES Nogatlvr 0" - Centre Analytical Laboratories, Inc. Page 45 of 74 Centre Study No. 023-048 FIGURE 10: TIER 3 KITTSON CLAY ADSORPTION SOLUTION NOMINAL lOOOppb j 200000- - 175000 1SOOOO125oOo100000- Centre Analytical Laboratories, Inc. Page 46 of 74 Centre Study No. 023-048 FIGURE 11: TIER 3 BROEREN CLAY LOAM ADSORPTION SOLUTION NOMINAL 500ppb Centre Analytical Laboratories, Inc. Page 47 of 74 Centre Study No. 023-048 FIGURE 12: TIER 3 DON UGLEM LOAM ADSORPTION SOLUTION NOMINAL 250ppb roowm- m- Centre Analytical Laboratories, Inc. Page 48 of 74 Centre Study No. 023-048 FIGURE 13: TIER 3 GOOSE RIVER SEDIMENT ADSORPTION SOLUTION NOMINAL lOOppb -1 zoo,4 . . . .. . w 2oooO- 13900- 1oooO- Centre Analytical Laboratories, Inc. Page 49 of 74 Centre Study No. 023-048 FIGURE 14: TIER 3 BROEREN CLAY LOAM DESORPTION SOLUTION NOMINAL 50ppb Centre Analytical Laboratories, Inc. Page 50 of 74 Centre Study No. 023-048 FIGURE 15: TIER 3 GOOSE RIVER SEDIMENT DESORPTION SOLUTION NOMINAL lOOOppb "1 I Compound Namr I 2 Amount I 4 R.T. 1 6 Armr I 8 ld Slanrl Centre Analytical Laboratories, Inc. Page 51 of 74 Centre Study No. 023-048 FIGURE 16: TIER 3 NIST SLUDGE ADSORPTION SOLUTION NOMINAL lOOOppb Compound blame 2 AJWunt 4 R.T. 6. Are. b Sb-1 Centre Analytical Laboratories, Inc. Page 52 of 74 Centre Study No. 023-048 FIGURE 17: TIER 3-NISTSLUDGE SOLIDS EXTRACT NOMINAL SOOppb Centre Analytical Laboratories, Inc. Page 53 of 74 Centre Study No. 023-048 APPENDIX A Study Protocol 0013-023-048 Adsorption and Desorption Study to Determine the Mobility and Distribution of PerfluorobutanesulfonicAcid in Soil Protocol and SOP Deviations Centre Analytical Laboratories, Inc. Page 54 of 74 Centre Study No. 023-048 ! Centre Protocol No. OOP-n?3-048 STUDY PROTOCOL STUDY TITLE ADSORPTION AND DESORPTION STUDY TO DETERMINE THE MOBILITY A N D DISTRIBUTION OF PERFLUOROBUTANESULFONICACID IN SOIL. SPONSOR 3M Environmental Technology and Safety Services Building 2-3E-09 PO Box 3333 1 St. Paul, MN 55133-3331 1 DATA REQUIREMENTS OECD Guideline for Testing of Chemicals, 106 OECD Guidelines for the Testing of Chemicals Proposal for Updating Guideline 106 TESTING LABORATORY Centre Analytical Laboratories, Inc. (Centre) ..... 3048 Research Drive State College, PA 16801 Phone 814-231-8032 PROTOCOL IDENTIFICATION hUMBER OOP-013-04s Centre Analyiical Laboratories, Inc. .. - Centre Analytical Laboratories, Inc. Page 1 of 16 Page 55 of 74 Centre Study . No 023-048 Centre Protocol No.OOP-023-048 TABLE OF CONTENTS Page STUDYTITLE PAGE ................................................................................................................................. 1 1. PURPOSE ............................................................................................................................................. 3 2. JUSTIFICATION FOR THE SELECTION OF THE TEST SYSTEM.......................................... 3 3. SUMhlARY........................................................................................................................................... 3 4. SPONSOR............................................................................................................................................. 4 5. TESTING FACILITY AND PERFORMING LABORATORY ...................................................... 4 6. PROPOSED EXPERIMENTALTIME-FRAhfE............................................................................. 4 7. TEST SUBST.4NCE ............................................................................................................................. 5 8. _SOIU...S...E..D....I.h..I..E...N...T.../.S..L...U...D...G....E...R...E...C...E..I..P..T......P..R...O...C...E...S..S...I.N...G.......S..T...O....R...A...G...E...A...N...D....I..D...E...N...T...I.F...I.C...A...T..ION6 9. BIASICONTAMINANTS.................................................................................................................... 6 10. SILYLATIONOF GLASSWARE.................................................................................................. 7 11. ANALYTICAL METHOD..........................................................................................................7.... .. 12. EXPERIMENTALDESIGN ........................................................................................................... 7 TIER TIER 1 2 -.PARDESLOIRMPITNIAOKRSNITYUNDEYT.I...C...S............................................................................................................................................. 7 9 TIER 3 ...................................................................... .................................................. 9 13. CALCULATIONS.......................................................................................................................... 10 14. STATISTICAL METHODS TO BE USED ................................................................................. 11 15. PROTOCOL DEVUTIONS ANJl AXlENDhIENTS................................................................. 11 16. RECORDS ...................................................................................................................................... 12 17. QUALITY ASSURkNCE.............................................................................................................. 12 IS. DATA AND REPORT.................................................................................................................... 13 19. ARCHIVE STATEMENT ............................................................................................................. 13 20. REFERENCES............................................................................................................................... 14 21. PROTOCOL REYIEW/APPROVAL........................................................................................... 15 PFEIGRUCREENT1:ARGEELSAOTFIOANDSSHOIRPBBEEDTTWEESETNSUSOBSILTATNOCSEO..L...U....T...I.O....K....R...A....T...I.O....S...A....N...D....K....D....A...T...V...A....RIOUS16 Centre Analytical Laboratories. Inc. Page 3- of 16 Centre Analytical Laboratories. Inc. Page 56 of 74 Centre Study No. 023-048 Centre Protocol No. OOP-023-048 Studv Title Adsorption and Desorption Study to Determine the Mobility and Distribution of Perfluorobutanesulfonic Acid in Soil 1. PURPOSE The purpose of this study is to estimate the adsorptioddesorption behavior of perfluorobutanesulfonic acid on soils to obtain a sorption value which can be used to predict partitioning under a variety of environmental conditions. The study will be performed to meet the guideline requirements described in the OECD Guidelines for Testing of Chemicals 106 and the Proposal for Updating Guideline 106. Sorption studies estimate the availability of a chemical for: degradation; transformation and uptake by organisms; leaching through soil; volatility from soil; and run-off into natural waters. This study is designed on three tiers: Tier 1. a determination of soiVsolution ratio, equilibration time for adsorption, potential for adsorption on the surfaces of the test vessels and stability of the test substance(s) during the test period; Tier 2, screening varied soil types at a single concentration; and Tier 3, determination of Freundlich isotherms. 2. JUSTIFICATION FOR THE SELECTION OF THE TEST SYSTEM Chemical residues may move through the soil profile by leaching or be transported to aquatic environments by movement in surface water. This study is designed to predict the potential for leaching and movement of chemicals in terrestrial and aquatic systems by the use of the batch equilibrium technique with three soil types, one sediment, and one sludge. The test systems (soils, sediment, and sludge) were chosen as recommended in the "OECD Guideline For Testing of ... Chemicals 106". As specified by the OECD Guidelines (106 and Proposal forupdating Guideline 106), soil types will be selected such that they will vary significantly in cation exchange capacity, clay content, organic matter content, exchangeable cations and PH. 3. SIDIMARY Perfluorobutanesulfonic acid (PFBS)will be evaluated in each matrix for adsorption/desorption isotherms. Perfluorobutanesulfonic acid prepared in aqueous 0.01M calcium chloride (CaC12) solution is mixed with representative soils, sediment and sludge and allowed to equilibrate at a constant temperature between 70 and 75C. The soil/test solution phases are separated by centrifugation and the concentration of perfluorobutanesulfonic acid in solution is determined. The adsorbed concentration is determined by difference or extraction and analysis. In Tier 1 two soil types and three soil/solution ratios are used. The Centre Analytical Laboratories. Inc. Page 3 of 16 Centre Analytical Laboratories, Inc. Page 57 of 74 SANI l lZED Centre Study No. 023-048 DEC 0 9 2003 Centre Protocol No. OOP-023-048 solution concentrations are determined at selected intervals over a 48-hour mixing period (for example 4, 8, 24,48 hours). By analyzing the control samples, adsorption to the test vessels and stability of the test substance will be evaluated. Data are reduced and the appropriate soil/solution ratio and equilibration time determined for use in Tier 2. Tier 2 screening uses all soils, sediment, and sludge samples except those from Tier 1. The solution values of peffluorobutanesulfonic acid are determined after 2 , 4 , 6 , 8 , and 24 hour contact times. The advanced test, Tier 3, is performed to determine Freundlich isotherms. All soils and sediment are evaluated using five concentrations of perfluorobutanesulfonic acid covering two orders of magnitude (if possible). The soil/solution ratio and the equilibrium time determined in Tiers 1 and 2 are used in performing Tier 3 testing. The adsorption test is performed once, the equilibrium concentrations in the solution are determined and the amount adsorbed is calculated from the depletion of the test substance. Desorption is next performed by replacing the volume of solution with an equal volume Qf 0.01M CaClz without test substance. Desorption continues until equilibrium is reached. Data are evaluated for percent desorption, the percent desorption @ti> and adsorption (A,J ycTsus time are plotted, and the Freundlich adsorption and desorption isotherms are determined. 4. SPONSOR 3M Environmental Technology and Safety Services Building 2-3E-09 PO Box 33331 St. Paul, MN 55133-333I SPONSOR STUDY MONTTOR: 5. TESTING FACILITY Ah' PERFORMING LABORATORY Centre Analytical Laboratories, Inc. (Centre) 3038 Research Drive State College, PA 16801 STUDY DLRECTOR: Kevin Lloyd, Centre TELEPHONE: 8 14-23 1-SO32 FAX NUMBER: 814-231-1253 6. PROPOSED EXPERIMENTAL TIME-FRAME Experimental Start Date Experimental Termination Date Report. Issued October 23,2000 December 31,2000 January 3 1,2001 Centre Analytical Laboratories, Inc. Page 4 of 16 Centre Analytical Laboratories, Inc. Page 58 of 74 SANITIZED Centre Study No.023-048 7. TEST SUBSTANCE *OQ3 Centre Protocol No. 03P-023-045 Test Material PFBS Lot Number Purity (5%) TBD Expiration Date Oct 2001 TBD = to be determined. Chemical names and structures of the test substance are presented below. Chemical Name: Molecular Weight: peffluorobutanesulfonic acid 300 0 It C39- S -OH I 0 From time to time the following reference compounds will be used to calibrate the method. These reference compounds will be naphthalene (providing I& values from 1000-30,000), 2,4-dichlorophenoxy acetic acid (providing values from 100-400), and p-chloroaniline (providing K, values <loo). A record of test and reference substance receipt, storage conditions, and a record of use will be maintained at Centre Analytical Laboratories, Inc. Forms documenting chain-of-custody and shipping records for tracking of the test substances will be included as part of the raw data package. All standardshest substances and any prepared solutions will be identified with a unique label or number on the container or cross-referenced to the container. All samples submitted for analysis are identified using a unique designation. Hazard Information A current MSDS for the chemical(s) used in this study will be maintained at the testing facility. Test and Reference Substance Documentation The methods of synthesis. fabrication andlor derivatization of the test and reference substances are documented and retained by the Sponsor. The Sponsor, as required by US EPA FIFRA GLP Standard 40 CFR 160.105,conducted characterization of the test and reference substances, and the Sponsor retains these records. Archived samples of the test and reference substances are being retained by the Sponsor. The Sponsor is maintaining these records and archived samples a[ the 3M facilities in St. Paul, MN. Centre Analytical Laboratories. Inc. Page 5 of 16 Centre Analytical Laboratories, Inc. Page 59 of 74 Centre Study No. 023-048 Centre Protocol No. 00P-023-048 The test and reference substances containers will be retained for at least the duration of the study. If the containers are emptied, and the study is completed, discontinued, or terminated. the containers will be disposed of according to standard Centre procedures, Any remaining test and/or reference substances will be retained by/at Centre, or authorization will be obtained from the Sponsor to return any remaining substances. Records will be maintained at Centre documenting use and disposal, if any, of test andlor reference substances. 8. SOIL/SEDIrvIENT/SLUDGERECEIPT, PROCESSING, STORAGE AND IDENTIFICATION Soil, sediment, and sludge samples will be obtained and transported so as not to alter their initial properties. Source location (specified in geographical coordinates), depth of sampling (120cm), amount and type of vegetation cover, treatment(s) with chemical pesticides or fertilizers andor biological additions, and/or accidental contamination will be documented for each soil sample. Each sample will be assigned a unique identification number at Centre, which will be used for tracking and identification of the soilhediment during analysis. The soil/sediment/sludge will be stored in a temperature-monitored refrigerator maintained at 1 to 6" C. The samples will be kept isolated from the test substance during storage. The sludge sample was obtained from the US NIST Laboratories in Gaithersburg, MD and has been fully characterized. Soil and sediment will be collected, sieved (retaining the fraction 5 2 mm). homogenized, and characterized by 3M Environmental Technology and Safety Services. Soil/sediment will be analyzed for percent sandlsiitlclay content, bulk density (disturbed), field moisture capacity (FMC) at 113 bar, pH value in 0.01MCaClz (1:l soil:solution), organic carbon content, organic matter content (%OM), nitrogen content, C/N ratio, cation exchange capacity and extractable cations (meq1100g of Ca, M g . Na. K, H). carbonate as CaC03, and clay fraction mineralogy. 9. BIAS/CONTAR.IINANTS No experimental bias is expected in this study. Measures to control bias will include the use of replicate test systems with separate analysis and arbitrary sampling of the replicates. No contaminants are expected during the studies that are known to be capable of interfering with the purpose and conduct of the study. Centre Analytical Laboratories. Inc. Centre Analytical Laboratories, Inc. Page 6 of 16 Page 60 of 74 Centre Study No. 023-048 ! ! Centre Protocol No. OOP-023-043 10. SILYLATION OF GLASSWARE All glassware used in this study (e+, volumetric flasks, graduated cylinders, pipettes, W L C vials, centrifuge tubes, etc.) will be silylated before use according to the pertinent Centre standard operating procedure. 11. ANALYTICAL METHOD All solutions and soils will be extracted and analyzed for PFBS using the procedures detailed in Centre Analytical Labs SOP CAL-24FWUO; "Extraction of Wastewater Samples for Fluorochemical Analyses by LCIMS" and SOP CAL24FLW1, "Analysis of Select Fluorochemicals by LCMS'. Sampldsolution preparation, storage location and conditions during the study will be documented. All samples and any soil/sediment extracts will be identified with a unique label or sample number. Such identification will be either on the container or cross-referenced to the container. During analytical runs calibration standards will be interspersed throughout the run. No more than 5 samples will be analyzed between standards. At least 8 standards will be analyzed per run with a minimum of 6 used in the calibration curve (up to 2 may be rejected). The r2value of the calibration curve will be >0.99. The run is acceptable with the final acceptable standard, provided that sufficient standards have been analyzed to create a calibration curve. 12. EXPERIMENTAL DESIGN TIER 1- Preliminary Study The test substance is dissolved in 0.01M CaClZ in deionized water (CAL Type 1); the CaC12 solution is used to improve centrifugation and minimize cation exchange. The concentration of the stock solution will be three orders of magnitude (if possible) higher than the detection limit of the analytical method. Additionally, the stock solution concentration will be below the water solubility of the test substance. If the stock solution is stored, it will be held in the dark under refrigeration at -4C. If the test substance is poorly soluble in water, an organic co-solvent may be used at no more than 0.1% by volume of the aqueous phase. Two soil types and three soiVsolution ratios are used. One soil will be the highest i n organic carbon with low clay content and the second soil will be the highest in clay content with low organic carbon content. The following soil (dry weight basis) to solution ratios will be used: 20 g soil and 20 mL aqueous solution of the test substance (1/1 ratio), Centre Analytical Laboratories, Inc. Page 7 of 1G Centre Analytical Laboratories, Inc. Page 61 of 74 Centre Study No.023-048 Centre Protocol No. OOP-023-048 - 5 g soil and 25 mL aqueous solution of the test substance (115 ratio), 1 g soil and 25 mL aqueous solution of the test substance (1125 ratio). All experiments are performed in triplicate. This includes the controls and blanks as described below. In order to check for stability and adsorption to the test vessel, controls (triplicates) with only the test substance in 0.OlM CaCI? solution (no soil) are subjected to the same steps as the test systems. Triplicate blanks per soil type will be run at 10 g soil and 10 mL0.OIM CaClz solution (without test substance) to serve as a background control to detect any interfering compounds or contaminated soils. If soil samples have been air-dried, the soil will be equilibrated with 0.01M CaC12 solution overnight (12 hours) the day prior to the test. The minimum volume of 0.01M CaClz solution will be lOmL for 1 , s or 10 g of soil. Following overnight mixing the samples will be centrifuged and the aqueous phase decanted. The weight of the hydrated soils will be recorded. The pH of the blank and fortified 0.01M CaCIz solution as well as the aqueous phases recovered after contact with the soil will be measured and recorded. The mixtures of soil and fortified 0.01M CaClt solutions are mixed until adsorption equilibrium is reached. The equilibrium time depends on the chemical and the soil and will vary considerably from one study to the next. Samples will be collected over a 48-hour period of mixing. At the specified sample interval (approximately, 4, 8, 24, and 48 hours) all test systems (centrifuge tubes with soil and solution) will be centrifuged and an aliquot (1 mL)of the aqueous phase removed for analysis. The same quantity of fresh 0.OlM CaCll solution is added to the mixture to maintain the soil to solution ratio. After removal of the sample the soil is remixed with the aqueous phase and all centrifuge tubes returned to the mixing apparatus until the subsequent sampling. The percentage adsorption (A,) is calculated at each time point (tJ on the basis of the nominal initial concentration and the measured concentration at the sampling time ( t J . Plots of A,, versus time are generated to estimate the equilibrium plateau. The & value at equilibrium is also calculated. Based on this &value, appropriate soil/solution ratios are selected from Figure 1 (from ENV/EPOC(99)24), so that adsorption is >?O%c80%. The mass balance is performed on both soils and for one soillsolution ratio per soil that gives a depletion above 20% and preferably > 50% at equilibrium. Following the ratio-finding experiment and analysis of the last sample of the aqueous phase after 48 hours, the phases are separated by centrifugation. The aqueous phase is recovered and a suitable extraction solvent added to the soil to extract the test substance. At least two successive extractions are performed. The amount of test substance in the soil and test vessel extracts is determined and the Centre Analytical Laboratories, Inc. Page 8 of 16 Centre Analytical Laboratories, Inc. Page 62 of 74 Centre Study No. 023-048 mass balance is calculated (see calculations). If balance is Irsy 1ti:in W%, [he test substance is considered unstable in the time scale of the test. It the study is continued this instability will be considered and both phases (aqueous and soil) analyzed in the main study. TIER 2 -Adsorption Kinetics All soils, sediment, and sludge selected for the study (except those used in Tier 1) will be tested in Tier 2. The equilibrium time, soillsolution ratio. weight of soil sample, the volume of the aqueous phase, and the concentration of the test substance in the solution are chosen based on the Tier 1 resulis. Analysis of aqueous solutions will be done at approximately 3,4,6,8, and ?4 hours of contact time. The same quantity of fresh 0.01MCaClz solution is added to the mixture to maintain the soil to solution ratio and the agitation continues until the next time interval. The mixing time may be extended to a maximum of 48 hours if the test substance requires longer equilibration time with respect to ratio-finding results. Each soiYsediment/sludge is tested in triplicate at one concentration with triplicate controls (sample of test substance with no soil) and triplicate blanks (soil uiid 0.01M CaC12 solution with no test chemical). The test is performed as in Tier 1 with mixing of soillsediment with test solution, centrifugation, remixing until the next sampling interval. The percent adsorption is calculated at each time point (Ati) and plotted versus time. The distribution coefficient & at equilibrium, as well as organic carbon normalized adsorption coefficient K, are also calculated. TJER 3 Adsomtion Isotherms Five test substance concentrations are used covering two orders of magnitude, if possible. All soils,sediment,and sludge selected for the study will be tested in Tier 3. The same soillsolution ratio per soillsediment will be used throughout the study. The adsorption test is performcd as described under Tier 1 except that the aqueous phase is analyzed only once at the equilibrium time as determined in Tier 2. The equilibrium concentrations in the solution are determined and the amount ad:,o:.bi:d is calculated either directly (no desorption to be performed) or by difference (desorption isotherm to be determined). The adsorbrd mass per unit mass of soil/sediment/sludge is plotted as a function of the equilibrium concentration of the test substance. The Freundlich isotherm is calculated (see calculations below). Desorotion Kinetics Using the remaining samples from the adsorption kinetics determination (Tier 2). the aqueous phase of the centrifuged test systems is removed as much as possible. The volume of aqueous solution removed is replaced with an equal volume of O.01M CaCI?solution with no test substance. The new mixture is mixed until the Centre Analytical Laboratories, Inc. Page 9 of 16 Centre Analytical Laboratories,Inc. .._.-. ... - Page 63 of 74 Centre Study No. 023-048 Centre Protocol No. OOl'-013-048 desorption equilibrium is reached. During this time period, at defined time intervals (such as 2 , 4 , 6 , 8, and 24 hours), the centrifuge tubes are centrifuged to separate the phases. A small aliquot of the aqueous phase is immediately analyzed for the test substance. If possible, the volume of each aliquot should be c 1% of the total volume. The same quantity of fresh 0.01M CaCl2 solution is added to the mixture to maintain the soil to solution ratio and the agitation continues until the next time interval. The percent desorption is calculated at each time point (Do)and is plotted versus time. The desorption coefficient as bcart equilibrium is also calculated. See Calculations. Desomtion Isotherms Freundlich desorption isotherms are determined on the soils used for the adsorption isotherm determination. The desorption test is performed as described above under 'desorption kinetics' except that the aqueous phase is analyzed only once, at desorption equilibrium. The amount of test substance desorbed is calculated. The content of test substance remaining adsorbed on soil at desorption equilibrium is determined directly (extraction) and plotted as a function of the equilibrium concentration of the test substance in solution. 13. CALCULATIONS Moss Balance Determination of the mass balance over time: Study must have reached adsorption equilibrium. v, c, = 1Vr-r * Cnddeq) + mF ) *loo * Where: MB = mass balance (To) mE = total mass of test chemical extracted from soil and walls of test vessel (pg) C, = initial mass concentration of test chemical in contact with the soil ( ~ cmg ") Cadr= equilibrium concentration of test chemical (pg ~ m . ~ ) V, = volume of the initial supernatant applied to the soil (cm3). ,V, = volume of the supematant recovered after the adsorption equilibrium (cm3). AdsorvtionDesorption Freundlich Isotherms The Freundlich equation is applicable to the adsorption/desorption of chemicals at intermediate concentrations and is commonly used to evaluate batch equilibrium data. The equation is an empirical relationship which may be expressed as: Centre Analytical Laboratories. Inc. Page 10 of IG Centre Analytical Laboratories, Xnc. Page 64 of 74 -... _. Centre Study No. 023-048 Centre Protocol No. OOP-023-04s Cab= KCc"O Where: Cadr = the adsorbed concentration (pg); C, = the solution equilibrium concentration (p$n?i); K,n = constants. Another relationship that assumes that n equals one is the simple proportionality: x / m = KdC, Where: x/m = the adsorbed concentration (pJ~g); C, = the solution equilibrium concentration (pdrnL); & = the sorption constant. Both adsorption and desorption are subjected to evaluation using the Freundlich equation. The adsorption coefficient I;d and the constant l/n are calculated for each soil type. Additionally, & (sorption coefficient based on organic carbon) is determined from the following equation: Where: K, = (Kd * 100) / %OC %OC = 8 organic carbon = % organic matter / 1.724. 14. STATISTICALhlETHODS TO BE USED Mathematical methods of linear regression, means, sums, and logs will be used for data reduction. Standard (linear) curves used to determine the concentration of the compound being analyzed will be constructed from a minimum of five concentrations. Correlation coefficients of the standard curve will be determined. Other than these descriptive statistics, no other statistical methods will be used during the course of this study. If necessary, a standard test for outliers, e.g., Dixon's test will apply. If an outlier exists, then i t may be excluded from the statistical analysis. 15. PROTOCOLDEVIATIONS Ah?) .GvIENDhlENTS Any deviatioiis from the protocol or from the analytical method as provided will be documented and reported promptly to the Sponsor Representative. Planned changes to this protocol or to the analytical method will be made in writing as an amendment or modification, and approved by the Study Director and the Sponsor Centre Analytical Laboratories, Inc. .. . . Centre Analytical Laboratories, Inc. Page 11 of 16 ... Page 65 of 74 Centre Study No. 023-048 Representative. Any amendments will be appended to this protocol and included in the final report. 1. Protocol amendments: Planned changes to the approved protocol shall be documented by amendments that clearly describe the change, justification for the change. and impact on the study. Amendn~entsw i l l be signed and dated by the Study Director and Sponsor Representative. Copies of amendments will be sent to the quality assurance unit. 2. Protocol deviations: Protocol deviations, which are one time and unplanned deviations from the protocol, shall be documeirted in l!ic study I L C ~ n~oti.ng the nature of the deviation. potential effect or impact on the study, and corrective action if required. Protocol deviations are signed or initialed by the Study Director and Sponsor Representative. 16. RECORDS Records to be maintained include the following (as appropriate): 1. Sample tracking she&) 2. Sample records*, storage history, and chains of custody 3. History and preparation of standards (stock, fortification, calibration) 4. Description of any modifications to the method 5. Instrument run sheets, bench-sheets or logs 6. Analytical data tables 7. All chromatographic and instrumental conditions 8. Sample analysis dates 9. A complete listing of study personnel, signatures and initials 10. Chronological presentation of all study correspondence 11. Any other data necessary for the reconstmction of the study * Sample records will include soil characterization as specified in OECD Guideline 106. 17. QUALITY ASSURANCE The Quality Assurance Unit of Centre Analytical Laboratories, Inc. (QAU) will audit the study for compliance with OECD GLP's and EPA FIFRA Good Laboratory Practice standards 40 CFR Part 160. The QAU will review the protocol; audit the study conduct and the study documentation (including raw data and final report) IO ascertain that all QNGLP procedures are adhered to. Centre QAU will inspect the study at intervals adequate to assure compliance to GLP's, and will report the findings of the audits to the Study Director, Centre Management, and the Sponsor Representative. Centre Analytical Laboratories, Inc. Page 12 of 16 Centre Analytical Laboratories, Inc. Page 66 of 74 Centre Study No. 023-048 Centre Protocol No. OOP-023-04s 18. DATA AND REPORT All raw data and the original signed protocol will be maintained in the study file. This data includes (as appropriate) the protocol amendments, protocol deviations, laboratory notebooks, analytical standard solution preparation, sample chain of custody sheets, sample work sheets, chromatograms, calibration curves, and any other appropriate data generated. Raw data not used will be stored in the study file. The reason for exclusion will be documented. A final report following the guidelines of United States Environmental Protection Agency PR Notice 86-5, approved and signed by the Study Director and sufficient for submission to EPA, will be prepared. Centre.wil1 send a copy of the draft report to the Sponsor Representative, who will return the report with comments. Centre Analytical will make revisions and finalize the report with the approval of the Sponsor Representative. The Centre QAU will conduct an audit of the final draft report and data files to assure accuracy and GLP compliance. Prior to signature, the Sponsor Representative must approve the final report and copies of the raw data. A QAU statement of inspections and a GLP statement of compliance by the Study Director will be included in the final report. Any corrections or additions to the final report shall be in the form of an amendment by the Study Director. The amendment shall clearly identify the part of the final report that is being corrected and the justification for correction. The amendment shall be signed and dated by the Study Director and the Sponsor Representative. REPORT DISTRIBUTION:Original to Sponsor Representative, Copy to Centre Archives. 19. ARCHIVE STATEMENT When the final report is complete, all original paper data generated by Centre Analytical Laboratories, Inc. will be shipped to the sponsor. This does not include facility-specific raw data such as instrument logs, however exact copies of temperature logs will be submitted. Exact copies of all raw data, as well as a signed copy of the final analytical report and all original facility-specific raw data, will be retained in the Centre Analytical Laboratories, Inc. archives for the period of time specified in 40 CFR Part 160. Retained samples of reference substances are archived by the sponsor. Upon completion of the study (acceptance of the final report by 3M), all remaining samples and unused soil. sediment, and sludge will be returned to 3M Environmental Technology and Safety Services. 3M will be responsible for the archiving or disposal of all samples and unused soil/sediment/sludge. Centre Analytical Laboratories. Inc. Page 13 of 16 Centre Analytical Laboratories, Inc. Page 67 of 74 Centre Study No. 023-048 Ccntre.Pr?tn;ol KO.OOP-023-04S 20. REFERENCES 1. OECD GUILDELINES FOR THE TESTING OF CHEMICALS: GUIDELINE 106,"Adsorption/Desorption" Adopted 12 May 1981. 2. OECD GUILDELINES FOR THE TESTING OF CHEMlCALS: "PROPOSAL FOR UPDATING GUIDELINE 106" ENV/EPOC(99)24 3. US Environmental Protection Agency. August 17, 1989. Federal Insecticide, Fungicide, and Rodenticide Act (RFRA) Good Laboratory Practice Standards; Final Rule (40 CFR: 160), Federal Register, Vo1.54, No. 158: 34052-34074. 4. The OECD Principles of Good Laboratory Practice, Environment Monograph No. 45,OECD/GD(92)32, Paris 1992. Centre Analytical Laboratories, Inc. Centre Analytical Laboratories, Inc. Page 14 of 16 - _... Page 68 of 74 SANITIZED Centre Study No. 023-048 1012o/oo DEC 0 9 2003 Centre Protocol No. OOP-023-048 21. PROTOCOL REVIEW/APPROVAL The Quality Assurance Unit of Centre Analytical Laboratories, Inc, reviewed this protocol. REVIEW L i s M m n g , I Centre L' ! . . Quality Assurance Officer APPROVAL Centre $.-p evin OY , tu Y irector Vice Presihent - n,t331N3 - L m F Z # klaherty, k acility Mabagernent bate roupfleam Leader - Operations .... / A T i w , Richard President Facility iVlanagcment bate 3M - Centre Analytical Laboratories, Inc. . . . . . .- ... .. . . .. . . .. . . . .... . . .. . Centre Analytical Laboratories, Inc. Page 15 of 16 Page 69 of 74 Centre Study No. 023-048 Centre Protocol No. OOP-023-04S FIGURE 1: RELATIONSHIPBETWEES SOIL TO SOLUTION RATIOS AND & AT VARIOUS PERCENTAGES OF ADSORBED TEST SUBSTANCE 1 0.1 0.01 1 IO 100 IO00 Distribution coefficient Kd (cm3 g*) Centre Analytical Laboratories, Inc. - . -._-- Centre Analytical Laboratories, Inc. Page 16 of 16 Page 70 of 74 SANIT1ZED Centre Study No.023-048 DEC 0 9 2003 tor CEntrE Analytical Labora ks. Inc. 3048 Research Drive State College, PA 16801 w.centrelab corn (814) 231-8032 Fax: (814) 231-1253 or (814) 231-1580 PROTOCOL DEVIATION Deviation Number: -I Date of Occurrence: 12/26-27/00 - - Centre Study Number: -023-048 Sponsor Stud) Number: -OOP-G23-OJS- DESCRIPTION OF DEVIATION Tier 3 testing did not meet the protocol specified temperature range of20-2j"C but \vas 18.0 to 19.3T. Deviation issued. ACTIONS TAKEN Le.. amendment issued. SOP revision. etc... Recorded Bymate: I l/LYyh W IMPACT ON THE STUDY Yo known impact on the study. /I Jnnuar) 5,200 1/j Centre Analytical Laboratories, Inc. . .... - - . . . .- -. ~ . . . .. . . . ~ .... _ _ . _ Page 71 of 74 c I j I Page 1 . I PROTOCOL DEVIATION 5 cviation issued. .. I ' .cI.' i .r ? .. .. I ' i Centre Analytical Laboratories, Inc. .. Page 72 of 74 Centre Study No. 023-048 CEntrE Analytical Laboratsrks. Inc. 3048 Research Drive State College, PA 16801 w.centrelab.com (814) 231-8032 Fax: (814) 231-1253 or (814) 231-1580 Pngc -lof 1- SOP DEVIATION Deviation Number: -1 Date of Occurrence: -1 7!27.75/00 3AL Study Number: 013-048 Sponsor Study Number: -0OP-023-04S- DESCRIPTION OF DEVIATION P SOP CAL-I 1P/8 Section 3.0 requires that the pH meter be calibrated prior to dail!. use. On the rollowing dates the calibration \vas not perfomied prior to use: Dec. 27,2000 Dec. 28,2000 SOP deviation issued. ACTIONS TAKEN Le.. amendment issued. SOP rrvision. e t ... iecorded Bymate: I I IhlPACT ON THE STUDY Vo negative impact on the study. The instrument successfully calibrated on Dcc 2 2 . 2000 and Inn. 2 , 200 1. e Study-Director $ifnature Date Centre Analytical Laboratories, Inc. ...-~ .__... ...- .... . ... - . . ... . Page 73 of 74 Centre Study No.023-048 Inc. Labora C Etr~E Analytical torks, 3048 Research Drive State College, PA 16801 www centrelab.com (814)231-8032 Fax: (814)231-1253or (814)231-1580 CAL Study Number: SOP DEVI-ATION Deviation Number: -3 Date of Occurrence: -entire study 023-048 Sponsor Study Suniber: -0OP-023-048- DESCRIPTION OF DEVIATION 1. SOP CAL-24FLM describes the use of an internal standard in sample analysis. No internal standard was used in this study 2 . SOP CAL-24FWL ion paired extraction procedure \vas not used in the stiidg. :. Several solutions from Tier 1 testing (4 hr clay1:1-2 and clay1 25-3; 8 hr clay 1 :1-2, control 2, loam1 :5-3 and loam1 2 5 - 2 ; 24 hr control 1) had LC responses greater than the highest standard and should have been diluted and reinjected per SOP CAL24FLWl-9.3. Id. SOP deviation issued. Recorded Bymate: ACTIONS T.XEN Le.. amendment issued. SOP revision. etc... IhlPACT ON THE STUDY No negative impact on the study. 1. An internal standard \vas not necessary for anal!,sis of PFBS. 2. The selected method of filtration prior to analysis rather than ion paired extraction yielded niorc reporducible results. 3. The over curve responses \vere only from the range finding u w k in Tier 1 testing and had no impact on the final results from Tier 3 testing. i Study Director Signature Date . - .. . Centre Analytical Laboratories, Inc. .--- . .. Page 74 of 74