Document 6BjXBezyGZaZgpwgBbMYDjY1

BACK TO MAIN 3M Environmental Laboratory Report No. EL1132 Study Title Hydrolysis Reactionsof Perfluorooctanesulfonamide (FOSA) Data Requirement: Based on OPPTS: 835.21 10 Author Thomas L. Hatfield, Ph.D. Study CompletionDate April 3,2001 Performing Laboratory 3M Environmental Laboratory Building 2-3E-09,935 Bush Avenue St. Paul, MN 55106 Project ldentification 3M Laboratory ReportNo: ELI132 Total Number of Pages 126 Page 1 of 126 - BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 This page has been reserved for specific country requirements. Page 2 of 126 _. BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Statement of Non-Compliance StudyTitle:HydrolysisReactionsof Perfluorooctanesulfonamide(FOSA) Study Identification Number: ELI132 This study does not fully comply with the requiremoef tnhtes US EPA Good Laboratory Practices (GLP) Standards a4t 0 CFR Part 792 (TSCA). However, many GLP standards were used in the development of the analytical method (ApApe),nadnixd the quality assurance procedures followed in this study were based on the practices described in the GLP documentation. A -/&- Sponsor Representative 04$& Date Page 3 of 126 BACK TO MAIN 3M Environmental Laboratory Report No.EL.1132 Quality Assurance Statement StudyTitle:HydrolysisReactions of Perfluorooctanesulfonamide(FOSA) Study Identification Number: ELI132 The following table provides detaiolsf the audits performed by the 3M Environmental Laboratory Quality Assurance Unit (QAU). Inspection Dates Phase I 31/20-2 /O1 I RTepaobrlet s 3/2 71/0 Report Date Reported to I I I Management 3/21/01 Study Director 3/21/01 ~ ~~~~~ 3/27/0 1 3/27/0 1 Page 4 of 126 BACK TO MAIN 3M EnvironmentalLaboratory Report No. ELI 132 Table of Contents Statement of Non-Compliance ............................................................................................ 3 Quality Assurance Stateme.n..t........................................................................................... 4 List of Tables ........................................................................................................................ 6 List of Figures....................................................................................................................... 6 Study Personnel and Contribut.o..r.s................................................................................... 7 Location of Archives............................................................................................................. 7 Summary.............................................................................................................................. 8 Introduction ........................................................................................................................ 10 Summary of Kinetics Mode.l.............................................................................................. 11 Materials and Method.s...................................................................................................... 13 Chemical Characterization.s......................................................................................... 13 Sample Preparation...................................................................................................... 13 Sample Analysis............................................................................................................ 14 Deviations...................................................................................................................... 14 Results and Discussion..................................................................................................... 15 Data Quality Objectives (DQO.'.s..).............................................................................. 15 Anomalous Analytical Resu.l.t.s.................................................................................... 15 Statistical Methods and Calculatio.n..s......................................................................... 16 Data Summary and Discussi.o..n.................................................................................. 16 Conclusions........................................................................................................................ 21 References......................................................................................................................... 22 Signatures .......................................................................................................................... 23 Appendix A: Analytical Method.......................................................................................... 24 Appendix B: Kinetics Mode.l.............................................................................................. 43 Appendix C:Selected Analytical and Kinetics Results..................................................... 54 Appendix D: Selected Chromatogram..s........................................................................... 66 Page 5 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 List of Tables Table 1. Summary of Results Based on FOSA Concentratio..n..s.................................... 8 Table 2. Summary of Results Based on PFOS Limit of Quantific..a..t.i.o...n.................... 8 Table 3. Summary of Results Based on the Estimated PFOS Limit of Dete.c..t.i.o..n......9 Table 4 . Summary of Results Based on the Mean and Precision of FOSA Measurements...................................................................................................... 9 Table 5. Characterizationsof Test and Reference Substance.s..................................... 13 Table 6. Observed (50" C) Degradation Slopes for FOSA in Aqueous Buffered Solutions and at Various pH Leve..l.s................................................................................. 16 Table 7. Degradation Rate Constant oFfOSA in Aqueous Buffered Solutions Using Data Pooled Over pH Lev.e..l.s.......................................................................... 17 Table 8. Degradation Rate and Half Life of FOSA in Aqueous Buffered Solutions Based on PFOS Limit of Quantificatio..n....................................................................... 19 Table 9. Degradation Rate and Half Life of FOSinAAqueous Buffered Solutions Based on the EstimatedPFOS Limit of Detectio.n........................................................ 20 Table 10. Degradation Rate and Half Lifeof FOSA in Aqueous Buffered Solutions Based on the Concentration Mean and Standard Devia.t.i.o...n........................ 20 List of Figures Figure 1. Structures of FOSA and the Potassium Salt of PF...O....S.............................. 10 Figure 2. Observed FOSA Degradation for Various pH le..v..e..l.s................................. 17 Figure 3. Pooled FOSA Data and Slope Regress..i.o...n................................................. 18 Page 6 of 126 BACK TO MAIN 3M Environmental Laboratory Report No.E L I 132 Study Personnel and Contributors Study Director Sponsor Thomas L. Hatfield, Ph.D. 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 (651) 778-7863 3M Corporation 3M Environmental Laboratoryand Professional Services Contributing Personnel Kuruppu Dharmasiri, Ph.D Mark T. McCann Anthony E. Scales Joseph J. S. Tokos, Ph.D (Pace Analytical Services, Inc., 1700 Elm St., Minneapolis, MN 55144) Gregory Maisel Jill Maloney (Braun lntertec Corporation, 6875 Washington Ave. South, Minneapolis,MN 55439) Grant M. Plummer, Ph.D. (Rho Squared, P.O. Box 61536, Durham, NC 27715) Location of Archives The 3M Environmental Laboratory will retain the original data documents and digital copies of the original data related to this work for a1t0lyeeaasrts following the effective date of any related final ruling. Information may obtained through written inquiry addressed as follows: 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Page 7 of 126 I BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Summary We report here the results of our sotuf dthye hydrolysis oPf erfluorooctanesulfonamide (hereafter, FOSA). Our methods are described below and in Appenditxo Athis work: our results are based on the observed concentrations of FOSA and perfluorooctane sulfonate (PFOS)in buffered aqueous solutionsas a function of time. The chosen analytical technique was high performance liquid chromatography with mass spectrometry detection (HPLCIMS). Tables1 and 2 summarize the results of the study. During this study, we prepared and examined samples at six difpfeHrelenvtels from1.5 to 11.Oover a periodof 42 days. The slopesof the log-concentration ratios, calculated from observations of the FOSA concentrations pooled ovesrixthoebserved pH levels, are presentedin Table 1. Table 1. Summary of Results Based on FOSA Concentrations. Calculated slope (day'') -4.4x Calculated slope upper limit (20) (day'') 8.6 x Calculated slope lower limit (20) (day'') -8.7X We also monitored the concentrationf one of the potential hydrolysis products (perfluorooctane sulfonateP, FOS), but never observed this compound at levels above its limitof quantification (LOQ, equalto 52 ng/mL). Assuming PFOSto be the only hydrolysis product of FOSAth,is LOQ provides a second estimaotfethe minimum FOSA half-life, presented in Tabl2e. Table 2. Summary of Results Based on PFOS Limit of Quantification Maximum Possible Rate at 50" C (day'') 2.3XI o - ~ Maximum Calculated Rate at 25" C (daY-7 2.3XIO-~ Calculated Half Life at 25" C (years) 2 8.3 Page 8 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 We also failedto detect PFOS above its limit of detecti(oLnOD, with a value estimated to be below 13.0 ng/ml). ThisLOD value also provides an estimate of the minimum FOSA half-life, presented in Table 3. of Results Based on the Estimated PFOS Limit of Detection I Maximum Maximum According to the data available from this study, the half-life estimates of T2aabnleds3 represent the minimum possible half-loiffethe compound FOSA under the assumption that it hydrolyzes to formonly the compoundPFOS. A third half-life estimate (see Equations6 36 and B37) is available from the meanpand standard deviation0 of the observedFOSA concentrations, assuming that they were essentially constant over the experimental portion of the study. This estimiaste Eq. 3 where A t represents the sample incubation period. Table 4 presents the resouflthse calculation. I Table 4. Summary of Results Based on the Mean and Precision of FOSA Measurements I Maximum Half Life 1.80 X 10-3 I.80 X 10-4 2 I1 Page 9 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Introduction Three primary chemical routes of environmental degradation are hydrolysis, photolysis, and biodegradation. Studies of these routes provide information on the environmental persistence of both the "parent" compounds and their reaction products, and are ideally carried out over the range of chemical conditions pertinent to both environmental and metabolic processes. The hydrolysisof FOSA (or, more generally, its degradation in the presenocef bo)is addressed in this report. Structures of the "parent" compound FOSA and the potassium salt of its potential hydrolysis product PFOS are illustrated in Figu1re. Figure 1. Structures of FOSA and the PotassiumSalt of PFOS FOSA Potassium Saltof PFOS FFFFFFFFO II F S-0- K' I I F F F F F F F F O Page 10 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Summary of Kinetics Model A full mathematical description of the kinetics model emploiynetdhis study is presented in Appendix B. The study data allowtwo independent estimates of the hydrolytic half-life of FOSA. The first estimate(see Table 1) is based on the observed degradation of the "parent" compound FOSA in dilute, appropriately buffered aqueous solutions. Equatio1n describes the estimatedhalf-life('fli), in terms of the estimated total parent hydrolysis rate c p(see AppendixB, Equation BIO): Eq. 1 We determined the c p quantity from the experimental data as described in Appen8d.ix The data correspondingto "Day 0" (t= 0) were used to determine the relative concentration ratios (see Equations B8 anB9d). The measured concentrations of the potential hydrolysis product PFOS (also obtained during the experiments described here) provide a second estimate (see2T)aobf lethe parent half-life. Duringthe course of this study, we did not detect PFOS abovites limit of quantitation (LOQ), and related studies' show that PFOS is itself hydrolytically stable. v i ) 2 Assuming also that PFOS is the only hydrolytic product of the parent compound FOSA, these PFOS analyses provide the following estima(tTe of the minimum FOSA halflife (see Appendix B, Equations B32 and B33): Eq. 2 where [Po]= the initial FOSA molar concentration, A t = the time interval over which the study was conducte(4d2 days), and = the molar limit of quantitation for the compound PFOS. Equation 2 implies that when the experimental data provide an estimate of the instrumentallimitofdetection (LOD) forthecompoundPFOS ), athirdestimate (Tvi)3of the parent half-lifeis available. This estimate (Equation 3i)s identicalto that describedinEquation 2, withthesubstitution Ab:& = B38 and B39): (seeAppendix B,Equations Page 11 of 126 I BACK TO MAIN 3M Environmental Laboratory ReportNo. ELI 132 Eq. 3 All the samples used in this study were maintained at a reaction tempera5t0u"reC.of The quoted results, valid for the reaction temperature25o"f C, were approximated from our experimental results according to methods described in AppeBnd(Eixq. 840 and B41). Page 12 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Materials and Methods Details of the characteristicsof the test materials, sample preparation techniques, and analytical methods are presented in Appendix A (ETS-8-210.0, "Prepaoraf tFioOnSA, MeFOSA, or EtFOSA Hydrolysis Samples and Analysis by High Performance Liquid Chromatography with Mass Spectrometry Detection.") A summary of these iteisms provided below, as well as a description the known deviations from the procedures of Appendix A. 3M prepared and analyzed the samples included in this study between March 13 and Octobe5r , 1999. Chemical Chamcterizations Table 5 describes the sources and propertieosf the materials usedin this work. These materials were usedto prepare boththe samples and the quantitative standards used to quantify them. For this reason, and because Equation3sand 6 involve only ratios of the parent and product concentrations, the resulting rate and half-life estimaraetelasrgely independent ofthe material purity levels. - Table 5. Characterizations of Test and Reference Substances FOSA Potassium Saltof PFOS FBSA~ Source Chemical Lot Number Physical Description Molecular Weight (gm mole-') 3M Specialty Chemicals 3M Specialty Chemicals TNA-1886 TCR-99030-026 TNA-0844 Off-white waxy solid Light colored powder 499 538 3M Specialty Chemicals NB 107715-87 White powder 299 A perfluorobutanesulfonamide Sample Preparation We preparedfour 1.O-mL aqueous buffer samples(a sample, a duplicate, a triplicate, and a "matrix spike") at eaocfh six pH levels (1.53,, 5, 7,9 and 11) for analysis at seven time intervals(0, 7, 14, 21,28, 35, and 42 days). Buffered solutions containing 499 ng/mLof the analyte FOSA an2d25 ng/mL of perfluorobutanesulfonamide (FBSA), the latter serving as the internal standard for the compounds FOSA and PFOS, formed the basisof all these samples. The chosen buffer solutions are described fully in Appendix A. All the samples were prepared simultaneously, and all but the0 "sDaamyples were placed in an orbital incubatorlshaker maintainedat 50" (23") C. After at least three minutes of agitation, the "Da0ysamples were spiked (as required) with the FOSA solution, diluted 1O:l with methanol containing the internal standard PFBS, and refrigerated. After the appropriate incubation times, subseotsf the sample vials were removed from the incubator and then spiked, diluted, and stored as described Page 13 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 immediately above. Except during the relatively short periods of time requtiored prepare them, the samples were shielded from light. Five calibration standards containing FOS(5A0 to 998 ng/ml) and six standards containing PFOS (13.0to 1037 ng/ml) served as the fundamental quantitative basis of the study. All other calibration standards were prepared from these fundamental standards, atthe appropriate pH levels, using the buffer solutions described above. Sample Analysis The equipment we used for the HPLC/ITMS analysis was a Hewlett Packard model 1100 equipped with a Dionex lonPac@ NG-1 HPLC column (aqueous ammonium acetate/methanol solvent gradient) and an ALS Model G1322A degassing module. An ALS Model G1315A column heater maintained the column temperature "aCt ,4a0 quaternary pump supplied a column flow rat0e.3omf umin, and anALS Model G1313A auto-sampler provided5 FL sample injections. The detector was a Hewlett Packard MSD mass spectrometer, operatedin negative-mode electrospray ionization mode; anions of the acetate adduct of FOSA, PFOS, and FBSA were detected at the charge-to mass ratios498,499, and 298, respectively. We processed the resulting data using the computer programHP ChernSfafionforLC (Rev.A.06.0). Further analytical details, including the gradient elution program, instrument and detector parameters, and performance specifications, are presenteidn Appendix A. Deviations We failedto spike one blank sample at eacohf the pH levels 3.0,5.0, 7.0, and 9.0. In each case, the resultsof additional blank samples performed immediately before the actual sample analyses indicate that the reported data meet the pertinent data quality objectives (see below). Through either humanor mechanical error, samples 80399PFOSA-094 through 096 (pH 11.O, "Day 21") were not analyzed, and they have been excluded from the following discussion. Page 14 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 ~~ Results and Discussion ~~ ___~ Data Quality Objectives(DQO's) Below is a brief description of the data quality objectives appinliethdis study. Afull description is presentedin Appendix A. With the exceptions of the anomalous results noted below,all the DQO's were met. Appendix C presents the results for each sample set, organized bypH level. Calibrations. The minimum acceptable coefficient of determinati(oPn) for linear fits to calibration data is 0.990. The acceptance criterion for individual calibration points is that their values fall withkin25% of the linear fit value; data outside this range are excluded and the linear fit is recalculateNdo. more thantwo points may be rejected from a calibration data set. Data for the high or low calibration standardbse may rejected, though this resultisn a smaller effective calibration range. Continuing Calibration Verification(CCV). Identical calibration samples are examined at the beginning and eonfdeach sample run. Results otfhe second calibration run may not deviate by more fth2a5n% of the first run for any analyte. The average results of the calibration runs are used to calculate the analyte concentrations. Matrix Spikes. The acceptable percent spike recovery range i7s5% to 125%. Analyte specificity is demonstrated by acceptable analyte spike recoveries. Sample Duplicates. Duplicate pairs with relative percent deviation (RSD) greater than 25% may be accepted at the analyst's discretion, but must be noted. Solvent Blanks. Concentration results for solvent blanks may exceed neith5e%r of the highest calibration standard no2r5% of the lowest calibration level. System Suitability. Suitability was demonstrated by either an abbreviated mass-tocharge (m/z) check-tune or performance of a full auto-tune routine. Anomalous Analytical Results Calibrations. The PFOS calibration standards at 13.0 ng/ml failed to meet the relevant DQO, so we calculatedall the reported concentrations according to the calibration resultsfor the PFOS standard at52 nglml. However, the responsesto the 13.0 ng/ml were all non-zero, and were quite consistenst,o the instrumental limit of detection (LOD) was clearly below this value. This fact is employed below in the "Data Summary and Discussion" section. Spike Recoveries. As discussed above, the samples 80399PFOSA-094 through 096 failedto meet the relatedDQO, so we have excluded the "Day 21" data for pH = 11. Other Detected Peaks: Some pH = 9.0 data indicate the presence of peaks at the value mlz = 616, correspondingto the compound 2-(N-ethylperfluorooctanesulfonamido). No explanation for the appearance of these peakissapparent. In addition, a very consistent response was noted at m=/4Z99 in all the standards and samples. This responseis possibly dueto various 13Cforms of FOSA. Because the response is consistenti,t does not compromise the reported results for the dominant 12CFOSA isotopomer amt /z = 498. Page 15 of 126 BACK TO MAIN 3M EnvironmentalLaboratory Report No. ELI 132 Statistical Methods and Calculations Using functions provided in Microsoft@ Excel@ software, we calculated means, standard deviations, and first-order rate constants (see Appendix B, Equation B8) for various subsets ofthe acquired data. Our linear regressions included the determinatioonf constant terms, that is, the regression fits were not forced to pass through the origin. As describedin Appendix B (Equations840 and B41), rates measured a5t 0C were extrapolatedto 25C by dividing by a factor oIfO;this approximationis valid for reactions with Arrhenius heats of activation near 18 Kcal/mole.* Data Summary and Discussion The LOQ is defined as the concentration of the lowest (accepted) stanidnatrhde calibration set for whicthe known concentration exceeds 400% of the indicated solvent blank level (see Appendix A). During this study, the LOQ's for FOSA and PFOS were 50 ng/mL and52 ng/mL, respectively. Results forthe internal standard compound (PFBS) were reasonably consistent throughout the study. The percent relative standard deviatioonfsthe measured values, calculated for each pH level, ranged fro1m.8% to 17%. Table 6 presentsthe results of the slope determinations (see Appendix B, Equa8ti8o)n at sixpH levels and 50C. ~ ~~~ ~~~~ ~~~ ~ Table 6. Observed (50" C) Degradation Slopes for FOSA in Aqueous Buffered Solutions and at Various pH Levels. PH Observed Slope (day") Percent (20) Slope Uncertainty (day') 1.5 -0.0013 3.0 -0.0009 5.0 -0.0003 7.0 +0.0001 9.0 +0.0012 11 +0.0011 98 261 622 1145 71 115 These slopes are generally only poorly determined; their percent rel2a0tiv(e95% confidence) uncertainties range from 7%1 to 1145%. The data do not indicate any degradation of FOSA. A regression of the slopes vs. pH yields a line with welldetermined slope; however, considering the near-zero valuoefsthe slopes, their generally large uncertainties, and the lack of physical meaning of the positive this trend is not meaningful. We conclude that the data indicate no relationship the degradation of FOSA and the sample pH level. slopes, between Page 16 of 126 BACK TO MAIN 3M EnvironmentalLaboratory Report No. EL1132 In the absenceof a clear relationship between the FOSA degradation rate and the sample pH,it is appropriate to "pool" the data over pH level and determine the degradation rate using the entire dasteat. Figure 3 illustrates the resultsof this pooled analysis according to Equatio1n, and Table7 summarizes the resultsof the analysis. Table 7. Degradation Rate Constant of FOSA in Aqueous Buffered Solutions Using Data Pooled OverpH Levels. Observed Rate Constant The uncertaintyin the rate constant presented in Tab7l,ewhich is based on direct observations of the compound's concentration in aqueous solution, indicates that FOSA is hydrolytically stableto within the experimental limitationosf this study. Fiaure 2. Observed FOSA Dearadation for Various DH levels. 0.08 0.06 4 0.04 0.02 0.00 -0.02 -0,04 -0.06 -0.08 -0.10 -0.12 -0.14 0 - - - - _-pH 1.5 pH 3.0 - - - pH 5.0 - - - pH 7.0 pH 9.0 - I - . pH 11 10 20 30 40 50 Time (days) Page 17 of 126 BACK TO MAIN 3M Environmental LaboratoryReport No. ELI132 Figure 3. Pooled FOSA Data and Slope Regression. I 0 Q -0.13 - Solid Line: y = -4.425E-06~- 1.997E-02 R2= 2.751E-06 0 Dashed Lines: 20 Uncertainties (slope and intercept) -0.18 I I I I 0 10 20 50 30 40 time (days) We also monitored the concentratioonf the potential hydrolysis produc(tPFOS), but never observed this compound at levels above itsoflimquitantification (LOQ,equal to 52 ng/mL). The initial FOSA concentration (499 ng/ml) and thPeFOS LOQ provide an estimate of the FOSA half-life (see in Appendix B, Equations B32 and 833). The maximum degradation rateis given by Equation 3: and the minimum half-life is givbeynEquation 4 A t [pol In(2) 2 Ab 2 S Eq. 3 Eq. 4 Page 18 of 126 BACK TO MAIN 3M Environmental Laboratory ReportNo. E L I 132 We note thatin both Equations 3 and 4, the initial FOSA concentra(tiPoon)and the PFOS LOQ ( calculations. aremolarquantities.Table8presentstheresultsoftherelated I Table 8. At (days) 42 Degradation Rate Bonased and HalfLife of FOSAin Aqueous PFOS LQimuiat notfification Buffered Solutions I 1 Maximum Maximum Calculated ObservedRateat Calculated Half Life [Po A;% 50" C at 25" C Rate at 25" C (nmlml) .o (nmlml) 0.097 1 2.3 x10" (day") (day-') (years) 2.3 x104 2 8.3 Appendix C lists the analytical results foar number of calibration standards containing PFOS at 13.0 ng/ml (e.g. sample 99039-135-02, analyzed just before the initial calibration standard set foprH 1.5). These results failed to meet the relevant data quality objectives for calibration standardss, o the test analyte results presentiendthis report are based on the results for the PFOS standards at 51.9 ng.ml; these latter standards establish the LOQ of 52 ng/ml for PFOS. Using the accepted calibration regressions for PFOS, the instrumental respotnostehse 13.0 ng/ml standards had an average valoufe16 ng/ml and a standard deviation of 4.4 ng/ml. Although these results did fail to meet the relevant data quality objectives for calibration standards, they do firmly establish the fact that the instrumental LOD for PFOS (A;:&) was below 13 ng/ml. The initial FOSA concentration (499 ng/ml) and the PFOS LOD provide an estimate of the FOSA half-life (see in Appe6n,dEixquations 638 and 639). The maximum degradation rate is given by Equat5io: n k, 5 (kp),,,w= --CI AYN Po A t m=l and the minimum half-life is givbeyn Equation6 (T'/2Pl2 2 A t [pol Q2) AI;% Eq. 5 Eq. 6 Page 19 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 We note that in both Equation5sand 6, the initial FOSA concentratio(nPo)and the PFOS LOD (Ai:&) are molar quantities. Table9 presents the results of the related calculations. ~ ~ ~~ ~ -~~- Table 9. Degradation Rateand Half Life ofFOSA in Aqueous Buffered Solutions Based on the Estimated PFOS Limit of Detection At (days) 42 [Po 1 (nm/ml) 1.o AES (nm/ml) 0.024 Maximum Observed Rate at 50" C (day'') 5.7 x1O4 Maximum Calc-lated Rate at 55" C (day- 1 5.7 xlo-s Calculated Half Life at 25" C (years) 2 33 The mean and standard deviation of the FOSA concentrations also provide a useful estimate of its half-life. Details of the related calculations are presenteindbelow (see Appendix 6,Equations 836 and B37). The maximum degradation rateis given in Equation 7: and the minimum half-lifeis given in Equation4 Eq. 7 Eq. 8 We note that in both Equations 7 a8n, tdhe mean FOSA concentration(pp)and standard deviation( 0,)can be either molar or mass quantities. Tab1le0 presents the results of the calculation. Table 10. Degradation Rate and Half Life ofFOSA in Aqueous Buffered Solutions Based on the Concentration Meanand Standard Deviation At c1P (days) (years) ((dnagy-W 42 455 (ng/ml) 17.2 Maximum ObservedRateat 50" C (day -') X 10-3 Maximum Rate at 55" C ) 1.80 x 10-4 1.80 Calculated Half Life at 25" C 2 11 Calculated Page 20 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Conclusions We have performed a studoyf the aqueous hydrolytic degradation of perfluorooctanesulfonamide (FOSA). Six different pH levels were included in the study, which were carried out at 50C and extrapolatedto 25C. Our results, based on direct observations of the FOSA concentration and a model of the related first-order kinetics, indicate no hydrolytic degradation of FOSA. We also monitored the concentration of the compound PFOS, a potential hydrolytic product of FOSA. Throughout the study, the PFOS concentration remained below both our limit of quantification (52 ng/mL) and our limiot f detection (13.0 ng/ml). Using the LOQ for PFOS and the initial FOSA concentration(499 nglml), and assuming PFOS is the only hydrolytic product of FOSA, we estimate that the hydrolytic half-life of FOSA at 25C is greater than toor equal 8.3 years. Using the LOD for PFOS and the same initial FOSA concentration, and assuming PFOS is the only hydrolytic producotf FOSA, we estimate that the hydrolytic half-life of FOSA at 25C is greater thanor equal to33 years. Finally, using the mean and standard deviation of the observed FOSA concentrations, we estimate that the hydrolytic half-life of FOSA at 25C is greater than or equal 1to1years. Page 21 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 References ' "Fate, Transport and Transformation Test Guidelines: 835.I2O1: Hydrolysis as a Function ofpH," U.S. EPA Officeof Prevention, Pesticides and Toxic Substances, publication number 712-(2-98-057, January 1998. 2 "Experimental Physical Chemistry"F,. Daniels, et al., McGraw Hill BooCkO. (New York), p. 131, 1962. Page 22 of 126 Signatures BACK TO MAIN 3M Environmental Laboratory Report No. E L I 132 %ate Page 23 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Appendix A: Analytical Method ETS - 8-210.0, "Preparation of FOSA, MeFOSA, or EtFOSA Hydrolysis Samples and Analysis by High Performance Liquid Chromatography with Mass Spectrometry Detection." This Appendix presents the analytical method employed in this study. Page 24 of 126 BACK TO MAIN 3 M Environmental Laboratory Report No. ELI 132 I. 3M ENVIRONMENTLAALBORATORY METHOD PREPARATION OF FOSA, MEFOSAO, R ETFOSAHYDROLYSIS SAMPLES AND h l L Y S 1 S BY HIGHPERFORMANCE LIQUIDCHROMATOGRAPFIYWITH MASS SPECTROMETRY DETECTION Method Number: ETS-8-210.0 Adoption DPte: Revision Effective Date: Approved by: ETS-8-210.0 Page 1 of 18 Preparationof FOSA, MeFOSA, or EtFOSA Hydrolysis Samples and Analysis by HPLC/MS Page 25 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. E L I 132 I . .. . 1.0 SCOPEAND APPLICATION 1.1 This procedure defines commonsteps for sample preparation, hydrolysis, andanalysis of perfluorooctanesulfonamide(FOSA, C&17S02NHzs,ometimes referredto as PFOSA), Nmethylperfluorooctanesulfonamide(MeFOSA, C~l,SOzNHCH,,sometimes referred to as FOSMA or PFOSMA)o, r N-ethylperfluorooctanesulfonamide (EtFOSA, C$,,S02NHC,H,, sometimes referred to as FOSEA or PFOSEA). Hydrolysis products are identified and quantified by high performance liquid chromatography (HPLwCi)th mass spectrometry (MS) detection. Each test analyte (FOSA, MeFOSoAr E, tFOSA) is studied separately using common, multi-component spike and intesrtnaanldard solutions. The method is based on EPA OPPTS: 835.21 10 (Reference 18.1). FOSiAs quantified using FBSA (perfluorobutanesulfonamide,C4F9S02NH2, sometimes called PFBSAas) an internal standard. MeFOSA and EtFOSAmay be quantified usingeitherNmethylperfluorobutanesulfonamide(N-MeFBSA, C.,FF,SO,NHCH,,sometimescalled PFBSMA or MePFBSA) orTHPFOS (the anionof 3,3,4,4, 5,5,6,6,7,7, 8, 8, 8tridecafluorooctane sulfonic acid)as internal standard. Perfluorooctanesulfonate(PFOS anion, a potential hydrolysis product) mabye quantified usingeither FBSA or THPFOS as internal standard. External standard quantificatioins permitted for all chemical species with appropriate technical justification. Representative structureasre shown in Attachment A. 1.2 Compatibleanalytes. FOSA,MeFOSA,EtFOSA,FBSA,N-MeFBSA, THPFOS, and PFOS. 1.3 Acceptable matrices for analysis. Aqueous solutions at various buffered pH levels. 1.4 This is a performance-based method. Refer to Section 10 for the quality control parameters to be analyzedby this method. Refer to Section14 for the quality assurance .evaluationcriteriafor this method.. 2.0 SUMMARY OF METHOD 2.1 Aliquots of FOSA, MeFOSA, or EtFOSA test-analyte stock solution are added to vials that contain buffers at pH levels 1.5,3.0,5.0,7.0,9.0, and 11.0. The vials are then placed in anorbital incubatorhhaker set at 50k 3 "C. Sets of vials (sample,duplicate,triplicate, spike, and blank) are removed at designated intervals and the date and time recorded. An aliquot of mixed spike solution (containing PFOSF,OSA, MeFOSA, and EtFOSA) is added to the "spike" samples, andall vials are diluted1:10 with methanol (MeOH) containing an internal standard mixture (e.Tg.HPFOS, FBSA, and N-MeFBSA). Samples are separated on a reverse phase Dionex IonPac" NG-1 HcPoLluCmn using an ammonium acetate/MeOH solvent gradient, with detection by electrospriaoynization mass spectrometry inthe negative mode. 3.0 DEFINITIONS 3.1 Solvent Blank. A sample of analyte-free medium (e.g, MeOHt)hat is not taken through the sample preparation process.This blank is used to evaluate instrumentcontamination. ETS-8-210.0 Page 2 of 18 PreparationofFOSA, MeFOSA,or EtFOSA HydrolysisSamples and Analysis by HPLClMS Page 26 of 126 I ,' BACK TO MAIN 3M Environmental Laboratory Report No. E L I 132 . . . ., . . ... .- -., ,._. ., .. . 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3.10 3.11 Buffer Blank. A sample of each buffer usedin the hydrolysis incubationsthat is not taken through the sample preparation process. Laboratory Control Sample(LCS). In this method, asample of each bufferthat is spiked withspiking solution and internal standard solutionT.his sample does not undergo hydrolysis and is prepared pritoranalysis. Continuing Calibration Blank(CCB). A sample of analyte-free mediumthat matches the matrix of the standards used to calibrate the instrument isanrdunin tandem with the Continuing Calibration Verification (CCV)T. he CCB is used to evaluate carryover from the standardsand instrument baseline, anids run periodically throughouthe analytical run(see Section10 for frequency). CalibrationStandard. A stock, intermediate or purchased standadrdiluted appropriately to achieve standard solutionosf test analytein a concentrationrange of interest. ContinuingCalibration Verification(CCV). Standards analyzedduring an analytical m to verify the continued accuracyof the calibration curve.This solution may be prepared from a different sourocrelot number than the calibration curve standards. Internal Standard:A known amount of a compound similar in analyticablehavior to the compound(s) of interest, added to all samples and standaarndds,carried through the entire measurement process. It provides a reference for evaluating caonndtrollingthe precision and bias otfhe applied analytical method. Matrix Spike( M S ) . Prepared by adding a known mass of target analytteo a specified amount of a sample matrix exposed to hydrolytic conditfioornws hich an independent estimate of target analyte concentratioins available. Matrixspikes are used to determine the effect of the matrix on the method's recovery efficiency. Sample Triplicates. Three samplestaken from and representativeof the same sample source and carried through all steopfsthe sampling, treatment and analyticparlocedures in an identical manner. Sample triplicates are used to assess varianctheeotfotal method, including sampling, treatment and analysis. Dilution. A step in the hydrolysis study procedurien which asolvent (e.g. MeOH)is added to the test analytehuffer solution to prepareit for instrumental analysis. This step occurs after the vials are removed from incubation and beforthee samples are analyzed. IS(s) may be incorporated into the diluting solvent, if desired. Limit of Quantitation (LOQ). The lowest concentrationthat can be reliably measured within specified limits of accuracy during routine laboratory operaticnognditions. The LOQ is generally 5 to 10times the minimumconcentration witha 99% confidence limit that the concentration is greater than zero. However,it may be nominallychosen within these guidelines to simplify data reporting. For many analyteths,e LOQ is selected as the lowest non-zero standardin the calibration curve thiast greater than 4 times the level of the solvent blanks. Sample LOQs are highly matrix-dependent. 4.0 WARNINGS AND CAUTIONS 4.1 Healthandsafetywarnings ETS-8-210.0 Page 3 of 18 Preparation of FOSA, MeFOSA, or EtFOSA Hydrolysis Samples and Analysisby HPLCMS Page 27 of 126 BACK TO MAIN 3M Environmental LaboratoryReport No. ELI 132 I 4.1.1 Wear the proper lab attire for all parts of this procedure. Wear gloves and proper eyewear aatll times. 4.1.2 Handle all solvents in a hood for all parotsf the described sample preparation procedure. 4.1.3 For potential hazardsof each chemical used, referto material safety data sheets, packing materials, and3M Environmental Laboratories Chemical Hazard Review. 4.2 Cautions 4.2.1 All glassware in which standards are prepared should be triple-rinsed with 1:1 acetoneMeOH to reduce the possibility of accidental contamination. 4.2.2 Ensure thatthe mobile phase eluents are freshly prepared and that thereis sufficient quantity to complete rthuen. Do not allowthe pump torun dry. 4.2.3 Ensure that before starting therun sequence thereis ample harddisk space on the computer to save arluln data. 4.2.4 Ensure that thereis enough nitrogen in the supplytankto complete sequence rUnS. 5.0 INTERFERENCE 5.1 Contaminantsin solvents, reagents, glassware, and other sample processing or analysis hardware may cause interference. Use the routine analyosfislaboratory method blanks to demonstrate that theries no such interference. 5.2 Contamination from columns,HPLC tubing, and detector components may cause interference atlow detection levels. The routine analysis of solvent blanks must be used . to demonstrate that there is no such interference. 6.0 EQUIPMENT 6.1 Analyticalbalancesensitiveto0.1 mg 6.2 Shaker, incubator capabloef maintaining temperatureat 50 f3 OC 6.3 Hewlett-PackardTM (HP) 1100 HPLC system, or equivalent 6.3.1 Pump, quaternary, Model G131lA, or equivalent 6.3.2 Solventdegasser,Model G1322A orequivalent 6.3.3 Autosampler,ALSModelG1313A,variableinjectionvolumecapable 6.3.4 Columnheater,Model GI316A 6.4 Dionex IonPac@NG-l,35mm x 4.0 mm, 10 pm packing, or equivalent 6.5 Mass spectrometer, Hewlett-PackaLrdCMSD, or equivalent, capableof operating in the selected-ion-monitoring mode 6.6 Clock, digital 6.7 Centrifuge capableof maintaining 3000 rpm for 5 minutes 6.8 pH meter,Comingm Model 308 pWTemperature Meterwith 3-in-1 gel-filled combination electrode(pWreference/temperature),or equivalent 6.9 Refrigerator, capable of maintaini4ngf3 "C ETS-8-210.0 Page 4 of 18 Preparation of FOSA, MeFOSA, or EtFOSA Hydrolysis Samples and Analysis by HPLC/MS Page 28 of 126 BACK TO MAIN 3M EnvironmentalLaboratory Report No.ELI 132 6.10 Data system, a personal computer capabloef controllingthe HPLC systemas well as - recording and processing signaflrsom the detector 6.11 Data analysis s o h a r e : Hewlett-Packard ChemStation", Version A.6.03 or later 7.0 SUPPLIESAND MATEFUALS 7.1 VOA (volatile organic analysis) via4ls0,mL, I-CHEM or equivalent 7.2 Crimp cap autovials, 1.5mL 7.3 Labels 7.4 Graduated pipets, glass, disposable1,mL-10 mL 7.5 Pasteur pipets, glass, disposable 7.6 Hamilton Gastight@ syringes (precisfion1% of total volume), 10pL-1000 pL 7.7 Volumetric flasks, various sizes 7.8 Beakers, glass, various sizes 7.9 Automatic pipettor, capabloef dispensing 10-5000 pL 8.0 REAGENTS AND STANDARDS 8.1 Methanol (Meow: HPLC/SPEC/GCgradefromEMScience,or equivalent 8.2 Acetone: HPLC/SPEC/GCgradefrom EM Science,orequivalent 8.3 18.0 MR water. Water with resistance < 18.0 MQ must not be used. 8.4 Calibrationandstandardstock solutions 8.5 All weights should be recorded to the nearest 0.0001 g 8.5.1 FOSA prepared in MeOH. (ExampleA:n FOSA stock solutionis prepared at a concentration of approximately 14,350 pg/mbyLweighing approximately 0.143 5 gof FOSA in a 10-mL volumetric flask and bringtiongthe mark with MeOH. This solution is dihted to make additional, appropriate standards.) 8.5.2 MeFOSA preparedin MeOH. (Example: A MeFOSA stocskolution is prepared at a concentrationof approximately 19,900&mL by weighing approximately 0.1990 gof MeFOSA in a 10-mCvolumetricflask and bringingto the mark with MeOH. This solution is diluted to make additional, appropriatsetandards.) 8.5.3 EtFOSA preparedin MeOH. (Example:An EtFOSA stocksolution is prepared at a concentrationof approximately 56,580 pg/mL by weighing approximately 0.5658 gof EtFOSA in a10-mL volumetric flask and bringintgo the mark with MeOH. This solutionis diluted to make additional, appropriate standards.) 8.5.4 PFOS prepared in MeOH. (Example: A PFOS stock solutioins prepared at a concentrationof approximately 30,520 pg/mL by weighing approximately 0.3052 gof PFOS in a10-mL volumetric flask and bringintgo the mark with acetone. This solutionis diluted to make additional, appropriate standards.) 8.5.5 Ammonium acetate buffer, approximately 2 mMT. his is chromatographic eluent A. See Section 12.3.1. (Example:An acceptable buffersolutionis made by weighing out approximately 0.16 g of ammonium acetate into a weigh boat and then quantitatively transferring ato1-L volumetric flask. Add ETS-8-210.0 Page 5 of 18 Preparation of FOSA, MeFOSA,or EtFOSA Hydrolysis Samples and Analysis by HPLCMS Page 29 of 126 BACK TO MAIN 3M Environmental LaboratoryReport No. ELI132 1 : approximately500 mL of 18.0MSZ water and10mL of MeOH as a preservative. Diluteto the mark with 18.0MR water and mix thoroughly.) 8I.n6ternsatal ndards 8.6.1 THPFOS prepared in MeOH. (Example: A THPFOS stock solution is prepared at a concentrationof approximately 2,000&mL by weighing approximately 0.0200 g of THPFOS in a 10-mL.volumetric flask &d bringing ttohe mark with MeOH. This solution is diluted to make additional, appropriate standards.) ,8.6.2 FBSA prepared inMeOH., (Example: An FBSA stock solutionis prepared at a concentrationof approximately 2,000pg/mL by weighing approximately 0.0200 g of FBSA in a 10-mL volumetric flask and bringintgo the mark with MeOH. This solution is diluted to make additional, appropriate standards.) 8.6.3 N-MeFBSA prepared in MeOH. (Example: An N-MEFBSA stock solution is prepared at a concentrationof approximately 2,000 pg/mL by weighing approximately 0.0200 gof N-MEFBSA in aIO-mL volumetric flask and bringing to the mark with MeOH. This solutionis diluted to make additional, appropriate standards.) 8.7 Buffers for calibration of pH meter Purchased pH calibration standarodfspH 4.0,7.0, and 10.0 (suppliers vary). 8.8 Buffer solutions for hydrolysisstudy Prepare pH5.0 buffer solution using guidelines froFmate, Transport and Transformation Test Guidelines(Reference 18.1). Prepare buffersolutions'ofpH = 1.5, 3.0,7.0,9.0, and 11.Oat ambient room temperature using guidelinferosm the CRC Handbook of Chemistry andPhysics (Reference 18.2). Prepartehe buffer solutionsin l-L quantities. Calibrate a portabplewtemperature meter using purchased pH calibration standards of pH 4.0,7.0, and.lO.0,and measure thepH of all buffer solutions. The concentrations are presented below. Recfoirndal pH measurementsof all buffers.Store buffers in sealed glass containers. . 8.8.1 pH 1.5 8.8.1.1 207 mL of 0.2 M HCl 8.8.1.2 250 mL of 0.2 M KC1 8.8.1.3 Adjust pH to 1.5 with additional 1N HC1 8.8.1.4 Bring to a final volume of 1L with 18.0 M a water 8.8.2 pH 3.0 8.8.2.1 500 mL of 0.1 M Potassium Hydrogen Phthalate 8.8.2.2 223 mL of 0.1 M HCL 8.8.3 pH 5.0 8.8.3.1 3.8777 g ammonium acetate added to 250mL 18.0 MR water 8.8.3.2 Add 250 mL 0.052 M acetic acid 8.8.3.3 Add 18.0 M a water to approximately900mL 8.8.3.4 Adjust to pH 5.0 with glacial aceticacid (approximately0.5 mL) 8.8.3.5 Bring to a final volumeof 1 L with 18.0 MR water 8.8p.H4 7.0 8.8.4.1 500 mL 0.1 M KH,PO, buffer 8.8.4.2 291 mL 0.1 N NaOH ETS-8-210.0 Page 6 of 18 Reparation of FOSA, MeFOSA,or EtFOSA Hydrolysis Sampleasnd Analysis by HPLCIMS Page 30 of 126 BACK TO MAIN 3M EnvironmentalLaboratory Report No. ELI132 8.8.4.3 Adjust pH to7.0 with either 1 N HColr 1 N NaOH 8.8.4.4 Bring to a final volumeof 1 Lwith 18.0 MSZ water. 8.8.5 pH 9.0 8.8.5.1 46 mL of 0.1 N HC1 8.8.5.2 500 mL of 0.1 M borax (NqBO,-H,O) 8.8.5.3 Adjust pH to 9.0 with either 1 N HCl or 1 N NaOH 8.8.5.4 Bring to a final volume of 1 Lwith 18.0 MSZ water. 8.8.6 pH 11.0 8.8.6.1 500 mL. 0.05M NaHCO, 8.8.6.2 227 mL 0.1NNaOH 8.8.6.3 Add water to 950 mL 8.8.6.4 Adjust pH to1 1.0 with 1 N NaOH 8.8.6.5 Bring to a final volumeof 1 L with 18.0MSZ water 8.9 TestAnalyte,Spike, and Dilutingsolutions: 8.9.1 FOSA test analyte sol&ion.'Example: Approximately 150 pL of solution 8.5.1 is diluted in 10mL MeOH, yielding a concentratioonf approximately 215 p g / d FOSA. A 10-pL aliquot of this solution is then addedto 1.O mL of buffer before hydrolysis testing. After hydrolysis, dilution with 9.0 mL MeOH containing internal standards (step performiendSection 12.1.12)results in concentrations before analysoisf approximately 215n g l d FOSA. 8.9.2 MeFOSA test analyte solution.Follow the proceduresin Section 8.9.1, but use the MeFOSA test analyte solution prepareind Section 8.5.2. 8.9.3 EtFOSA test analyte solutionF. ollow the procedures in Section 8.9.1, but use the EtFOSA test analyte solution prepared in Section 8.5.3. 8.9.4 Spiking solution. [Example: A common post-hydrolysisspiking solution is used for the analysisof FOSA, MeFOSA or EtFOSA hydrolysis sampleTs.his solution contains approximatel5y0 pg/mL FOSA, 50 pg/mL MeFOSA,50 pg/mL EtFOSA, and50 p g h L PFOS in MeOH. It is made by first preparing intermediate solutionsof approximately 500 pg/mLof each compound by MeOH dilutionof the solutions prepareidn Sections 8.5.1, 8.5.2,8.5.3, and 8.5.4, respectively. The combined50 pg/mL FOSA, 50 pg/mL MeFOSA,50 pg/mL EtFOSA, and50 pg/mL PFOS solutionis made by adding .1O-mL. aliquots ofeach of the intermediate solutionsto a IO-& volumetric flask and diluted to the mark with MeOH. After the hydrolysis periodis complete, 50 pL of the mixed solutionis added to eachof the "spike" samples.After dilution with 9.0 mL MeOH solution containing internal standard (step performeind Section 12.1.12), thefinakoncentrations ofthe added spikes in the sample are approximately250 ng/nL FOSA, MeFOSA, EtFOSA and PFOS]. 8.9.5 Diluting Solution ContainingTHPFOS,FBSA, and N-MeFBSAInternal Standards. A common, mixed-stock solution isfirst prepared in MeOH. This solution is used for the analysiosf FOSA, MeFOSA,or EtFOSA hydrolysis samples. Example: A solution containing approximatel2y50 &mL each THPFOS, FBSA, and N-MeFBSAis prepared by adding appropriate volumeosf THPFOS stock (Section 8.6.1), FBSA stock (Section 8.6.a2n)d, MeFBSA stock ETS-8-210.0 Page 7 of 18 Preparation of FOSA, MeFOSA, or EtFOSA HydrolysisSamplesand Analysis by HPLCMS Page 31 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 1; (Section 8.6.3) to a 10-mL volumetric flask and diluting to the mark with MeOH. A working dilution solution is prepared by addi2ngmL of the 250 pg/mL mixedTHPFOS, FBSA, and N-MeFBSA stock solutionto a 2 L volumetric and dilutintgo the mark with MeOH(fmalconcentration of 250 ng/mL, of each compound). After the hydrolysis perioids complete, 9 mL of the working solutionis added to the sample. Thefinal concentrations of the added internal standardsin the sample are approximately 225 ng/mTLHPFOS, 225 ng/mL FBSA, and 225n g / d N-MeFBSA]. 9.0 SAMPLHEANDLING 9.1 Handle samples and standards in a well-ventilated area. Wear gloves and eyewear whenever handlingany solutions. 9.2 Record times of initial preparation and quenching additions on the fluorochemical degradation (hydrolysis) Analysis Sample Preparation Data Sheet (AttachBm).ent 9.3 Once the 9.0 mL of final diluting solvent has been added, analyze the samples. Alternatively, aliquotsof the methanol-diluted samples should be refrigerateadt 4 k 3 "C or frozen until analysis can be performed. 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 QUALITCYONTROL (F'REQUENCY OF PERFORMANCE) Solvent Blank. Solvent blanks should berunbefore and after every calibration curve, before and after everCyCV (whereit is called a CCB), and aftenro more than 20 sample injections. Buffer Blank A buffer blank should be analyzed once preurn (30 samples or less). Laboratory Control Sample (LCS).An LCS should be analyzed once perrun(30 samples or less). ContinuingCalibration Blank (CCB). A CCB (solvent blank)is run before and after 'every CCV. Continuing Calibration Verification(CCV). A mid-range CCV standard, flanked by solvent blanks (CCBs)i,s run after every 20 samples (or less) to verify the calibration stability. This solution may be prepared fiom a different sourcelotonr umber thanthe calibration curve standards. Internal Standards. IS(s) are added in a constant concentrationto all standards, samples, and matrix spikesI.n this method, internal standards are addetdo the diluting solvent (Section8.9.5). Matrix Spikes. Prepare a post-hydrolysis matrix spike solution along with eacshet of triplicate samplesat each of the pH levels used in the study (refer to Secti8o.n9.4). Concentrations of the spikeshouldbe approximately equatlo the mid-range calibration standard. Triplicate Samples. All samples are prepared in triplicate incubation mixtufroesr each pH and time point. 11.0 CALIBRATIOANND STANDARDIZATION ETS-8-210.0 Page 8 of 18 Preparationof FOSA, MeFOSA, or EtFOSAHydrolysis Samples and Analysis by HPLC/MS Page 32 of 126 BACK TO MAIN 3M Environmental Laboratory ReportNo. E L I 132 I 11.1 `Standardpreparation. Prepare six calibration standardsof FOSA, MeFOSA or EtFOSA in MeOH, dependingon the choice of test andykefor the analysis.Standards from approximately10-1 000 ng/mL are suggested. This solution shouldalso contain appropriate concentrationsof the internal standard. 11.2 Calibration standards. Analyzethe calibration standardsat the beginning and end of the run. Use the data reduction software program for linear regrescsiaolcnulationsto relate the analyte peak area ratio versus the amount ratio thfreoimnternal standard. External standard calibration may be used if data review shows a prwoibtlhemthe internal standard analysis. Consult with the group leader for directiotno pperrioforrming the external calibration methodology. Notoen the standard curve andin the report why a decisionwas made to perform external standard calibration the raw data. 12.0 PROCEDURES 12.1 Sample and spike preparation 12.1.i Before spiking with anoyf the stock standards, transfer approximate1lymL of the solutionto an autovial and cap it. Utsheis smaller volume fosrpiking to minimize the effects of evaporation from stock solutions. 12.1.2 Determinethe number of time pointsthat will be analyzedE.ach time point will have four vials for eachpH, multiplied by the number of pH levels analyzed. One vial at each level will be labaesle"dsample", "duplicate", "triplicate"o,r "spike." 12.1.3 Obtain the appropriate numberof 40-mL I-CHEM vials with caps and cardboard boxes. Prepare appropriate sample preparation worksheetscarenadte labels and affix to the vials. The labels should includthee sample number, pHt,ime point, and initials otfhe analyst. Record thepH of each buffer solution. 12.1.4 Remove the cap of the I-Chem vial and addm1L of the appropriate buffer solution to alolf the prelabeled vials. Always replace tchaep immediately after any additionto minimize evaporation. 12.1.5 To all of the vials, add 1p0L of the appropriate FOSA, MeFOSAor, EtFOSA test analyte solution (prepareidn Section 8.9.1, 8.9.2,or 8.9.3) with a 1O-pL Gastight' syringe. Recordthe time of addition for each vial. 12.1.6 For "Time Zero" samples only, proceetdo section 12.1.11. For all other samples, continue on to section 12.1.7. 12.1.7 Make sure that the cap has beenfirmly tightened and plactehe samplesback-in the cardboard case. 12.1.8 Place the case into a pre-warmed incubatodshafkoerrthe appropriate time. Record the time, temperature, and ratoef shaking. The temperatureis determined bythe conditions of the experiment. Contintouemonitor the incubator temperature daily duritnhge entire incubation. Recortdhe temperature on the sample preparation sheet. 12.1.9 Remove the case from the incubaatot rthe designated preset time. ETS-8-210.0 Page 9 of 18 Preparationof FOSA, MeFOSA, or EtFOSAHydrolysis Samples and AnaIysis by HPLCMS Page 33 of 126 li - . BACK TO MAIN 3M Environmental Laboratory Report No.ELI 132 . ., 1 - . . . . . . I 12.1.10 Remove the vials from the case and placein racks. Allowthe vials to cool for 15minutes to room temperature. Alternatively, freetzhee vials if solutions are to be diluted and analyzeadt a later date. 12.1.11 Using a 10-pLgas tight syringe, add10 yL of mixed-spike solution (Section 8.9.4) to the "spike" vials. Invert each vial severtaiml es to mix the contents. 12.1.12 Using a 10-mL graduated pipet, add9.0 mL of the MeOH diluting solution prepared in Section8.9.5 to eachvial. Invert each vial several times to mix the contents. 12.1.13 Aliquot approximately1 mL of each sampleto the appropriately labeled autovial. Cap the vials and mark the bootftothme meniscus. 12.1.14 Place the vials in the HPLC autosampler. 12.2 Instrument setup 12.2.1 Check thatthe appropriate HPLC column isthine instrument for each analysis. 12.2.2 Check that the correct eluent solutiaornesin bottles to be used andthat enough is available to completethe sequence run, 12.2.3 Place the samples in the autosampler tray and construct a sequetnacbele with appropriate calibration standards, calibration check standards saonldvent blanks. 12.2.4 Verify that all samples and standards are positioned correctly. sEeqnuteernce information: (sample or standarIDd , method name) useone injectionper sample. 12.2.5 Save sequenceas analysis date (e.g.on March 14,1999, save sequencetable as 03 1499s). Save all datato a subdirectory labeled with analysis date (e.g., 03 1499). 12.2.6 Set post-sequence command mactrooshut down system (Example: "STANDBY" on HP systems). 12.3 HPLC set up: 12.3.1 Analysis of FOSA, MeFOSA, or EtFOSA sainples from pHlevels 1.5,3.0,5.0, 7.0,9.0, and 11.O: Install the column: DionexIonPac"NG-l,4.0 x 35mm, 10-pmpacking, or equivalent. Solvent A: 2 mM ammonium acetate including1%MeOH Solvent B: MeOH Solvent Gradient (may vary slightly from studtoystudy: ~~ ~ TIME(MIN) 0.0 %A %B FLOWRATE 60 40 0.5 mUmin 0.5 60 40 0.5 mUmin 2.5 5 95 0.5 mUmin - I I 6.0 7.0 1 5 1 95 0.5 mUmin 1 1 I I I I ETS-8-210.0 Page 10 of 18 Preparation of FOSA, MeFOSA, or EtFOSA Hydrolysis Samples and Analysis by HPLC/MS Page 34 of 126 I.. I . BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 - Posttime: 2.0 3.0 minutes; cofumn temperature:40T. 12.4 'RecommendedMass Spectrometersetup:' 12.4.1 Analysis of FOSA, MeFOSA, or EtFOSAatpH 1.5,3.0, 5.0,7.0,9.0,and 11.O: I I AcquisitionMode Selected ion (SIM) I IonMizoadtieon I Electrospray I I Polarity I Negative I Drying Gas Flow 8 Umin Nebulizer Pressure Drying Gas Temp 30 psig 300" C Identifiable ions: 'Example conditions an applicableto Hewletf PackardH P I 100equipmentonly. MeFOSA (M-H') 512.00 2.0 70 EtFOSA (M-H+) 526.00 N-MeFOSE-OH (M-H+) 616.00 2.0 70 N-EBOSE-OH (M-H+) 630.00 2.0 70 '"Quant'' ion for FOSA ** ''Quent" ion for PFOS 97 97 70 2.0 97 97 12.5 Autosamplesret-up* AUTOSAMPLER: ,.I ALS Model G1313A AUTOSAMPLER PROGRAM: [ None I INJECTION VOLUME: '1 5.0 pL I *Example conditionsare applicableto Hewlett PackardHP1100 equipment only. 12.S6amplaenalysis 12.6.1 Enter the standard, sample and QC information into the sequence table. Analyze solvent blanks and calibration standards first, then utop20 sample injections, followed by solvenbtlanks and calibration standards.If more than 20 sample ETS-8-210.0 Page 1 1 of 18 Preparation of FOSA, MeFOSA, or EtFOSA HydrolysisSamplesand Analysis by HPLCMS Page 35 of 126 BACK TO MAIN 3M Environmental Laboratory Report No.ELI 132 I 12.6.2 12.6.3 12.6.4 12.6.5 injections are to breun,analyze a continuing calibration standar(dCCV) after every 20 andrun the calibration standards agaaitnthe end of the sequenceR. un solvent blanks before and after esatcahndard curve, before and aftetrhe CCV, and afterthe set of sampletso check for any analyte carryover. Identifjr the electronic acquisition files wiatnh appropriate prefix.Do not exceed five. characters if the sequence contains more thlaines9.9 Place the standards, samples, anQdC (matrix spikes and sample blankisn)to the autosampler tray accordintgo the order they are listeindthe sequence. Savethe sequence tablewith a name corresponding to today's date. (e.g. if today is December 1,1998, save the sequence as 120198,s) Start the sequence. 13.0 DATAANALYSIS AND CALCULATIONS 13.1 Peak evaluation: Peaks must be symmetricin shape and identifiedby extracting compound specific ions. Peaks considered for calibration must have peak heights greater than 5 (five) times the baseline noise for that regitohne cohfromatogram. Peak integration is from baseline to baseline through a peak using autoomr mataicnual integration. Compounds with isomers presaesnat shoulderor as a discrete second peak should be integrated with the parent compound unless otherwise noted. Quantidtatiaon are calculated usingTHPFOS,FBSA,or N-MEFBSA as the internal standardsa,s appropriate. However, external standard calibration may be acceptablesawmhpenle integrity is intact. Consult with the team leader for direction prior to perfotrhmeing externalcalibration methodology. Document changien raw data and finalreport. 13.2 Calculation of k Calculate theFOSA,MeFOSA, or EtFOSA concentrationisn each of the pH matrices usingthe curves obtainedfiom the calibrations and the internal standard. Assuming first-order kinetics, a rate constant (k) can be determined bythpelotting natural logarithmof the ratio (concentrationof FOSA at any given tim/einitial concentrationof FOSA)versus the time (-t). Thselope of the resultant line is k. Half-life of the test analyte(tin, in the units oft) is obtained from the relation: Ln 2.0k = 0.693k. ' 13.3 Matrix spikes. Calculate the percent recoverfyor each of the matrix spikes. Usintghe observed matrix spike recoveries, calculate the average spike recovery. Catlhceulate matrix spike percent recoveries using ftohlelowingequation: % Recovery = (observed spiked sample resul-t average sample result)x 100 actual amount spiked 13.4 Sample triplicates. Calculate the relative standard deviatio(nRSD) for thetriplicate samples. STDEV {A, B>C) x 100% .AVERAGE{A, B,C} ETS-8-210.0 Page 12 of 18 PreparationofFOSA, MeFOSA, or EtFOSA Hydrolysis Samples and Analysis by HPLC/MS Page 36 of 126 BACK TO MAIN Where:A =the concentrationmeasured in thesample,and B = the concentration measuredin the duplicate, and C= the concentration measured itnhe triplicate 14.0 METHODPERFORMANCE 14.1 Solvent Blanks, Buffer Blanks, and Continuing CalibrationBlanks. The measured value for these blanks shoulbde less than25% ofthe limit of quantitation (LOQ) of the method. Solvent blanks shouldshow no more than a5% carry over from a high standard or calibration check standard. sIof, two solvent blanks mabye necessary to rule out instrumental contamination. If peaks with greater 5th0a%n of the peaakrea of a low standard value are observeind sequential solvent blanks, thme n should be stopped.This is indicative of instrument contamination. The instrument shall be brought into compliance by thoroughly cleaning the electrospray source, and repolraclienagning columns, tubing, etc. 14.2 CoeScient of Determination (3).The coefficient of determinatio(n8)for linear calibration curves should b0e.990 or greater. The curves should be examincedlosely for linearity and intercept, particularly for accuorafcqyuantitation athe low andhigh ends of the curve. On occasionit may be necessary to utilize exponential or quadrfaitiscof the data, usually when broad range curves (gretahtaexri 3 orders of magnitude between the low and high concentration standards) are used. Recionrtdhe raw data the reasons for using quadratic equations, and get apprforvoaml QAU. If a point is i 20 % of the nominal value the poinits used for quantitation. If the value exceedfs 20 %, the curve is out of range and the curvisererun until all points patshse criteria. 14.3 Continuing Calibration Verification (CCV)I.f the relative percent difference ftohre amount of measured analyte is> 15% of the true value, relativtoe the initial standard curve, stop the run. Only those samples analyzed befothre last acceptableCCV will be used. Appropriate steps musbte taken to correctthe problem before analysisis allowed to proceed (consult the project lead for guidance). Reanalythze remaining sampleswith a new calibration curve. 14.4 Internal Standards. Peak-area ratios of samples (relative tthoe IS) are used for quantification. The %RSD ofthe internalstandards in calibrationcurves should be < 10 YO,or the projectlead should be consulted. The area responseof an IS in a samplemust be between50% and 150%of the mean area responsoef the IS in an acceptable calibration curve. Samples having area response outside this range should be reanalyzed or prepared again,at the discretionof the project lead. - 14.5 Matrix Spikes. The analyst shall accept percent spike recovearluyes of 100f 25%. Spike recoveries of 70 - 75% or 125 130% of nominal may be useadt the discretion of the project lead. Spike recoverie<s 70% or > 130%piace the analysisout of control. .Appropriate steps(e.g. cleaning, blank tests, install a new column) must be taktoen correct the problem befotrhee analysisis allowed to proceed. 14.6 Sample Triplicates. The analyst shall accepRtF'D values of <25%. FWDvalues > 25% place the analysis out of control. Appropriate steps must be taken to cotrhrecptroblem before analysis is allowetod proceed; consulthe group leaderfor direction. ETS-8-210.0 Page 13 of 18 Preparation of FOSA, MeFOSA, or EtFOSA HydrolysisSamples and Analysis by HPLCiMS Page 37 of 126 BACK TO MAIN 3M EnvironmentalLaboratory Report No. ELI 132 14.7 Limit of Qusntitation (LOQ). The limit of quantitationis equal tothe lowest standard in the calibration curve that <is5 times the blank level othr e S / N , whichever is greater. 14.8 System Suitability. System suitability is demonstratedby acceptable instrumental checks (e.g. abbreviatedd z check-tune, or full auto-tune routines). Acceptablechecks should be documentedin instrument runlogs. 15.0 POLLUTIONPREVENTION AND WASTE MANAGEMENT 15.1 Dispose of sample wasteby placing in'highor low BTU containersas appropriate. Use broken glass containertso dispose of glass pipettes. 15.2 Collect HF'LC solvent waste in the satellite accumulation can. Empty itnhteo flammable storage drumin the hazardous waste collection aroenathe 2nd floor. 15.3 Use smaller bore columns when possiblteo minimize waste generation. 16.0 RECORDS 16.1 Print out hard copiesof all graphics and data analysis summaries for archiving. 16.2 Sign and date all graphics and label with instruImDe. nt 16.3 Fill out the hydroiysis sample preparation worksheet complemtealyk,ing sure to include all initials and dates. 16.4 Print out the sample sequence table, photocopayreduced-size duplicate, andtapethe photocopy to the instrument log. Keetphe original copy fotrhe raw datafiles package. 16.5 Print chromatograms and internal standard reports for all analyses. 16.6 Print Calibration tables and curve information and isntotrhee raw data file. 16.7 Store hydrolysis sample preparation worksheientsthe raw datafile. 16.8 Enter all standard preparation information in the standards preparation logbook. Make a photocopy of the logbook page and includthee copy in the raw data file. 16.9 Archive electronicdatato appropriate media when necessary. 17.0 ATTACHMENTS 17.1 Attachment A: RepresentativeChemical structures 17.2 Attachment B: HydrolysisSampleLogsheet 18.0 BIBLIOGRAPHY 18.1 Fate, Transport and Transformation Test Guidelines Office of PreventioPne,sticidesand Toxic Substances(OPPTS) 835.2110Hydrolysis as a Functionof pH, EPA 712-C-98057, January 1998. 18.2 CRC Handbook of Chemistryand Physics, ISt Student Edition,"Buffer Solutions Operational Definitionsof pH," Robert C . Weast, Ph.D.,1988,p. D-87. ETS-8-210.0 Page 14 of 18 Preparation of FOSA, MeFOSA, or EtFOSA Hydrolysis Samples and Analysis by HpLC/MS Page 38 of 126 ~~ ~~ ~~ BACK TO MAIN 3M Environmental LaboratoryReport No. ELI132 19.0 AFFECTED DOCUMENTS None. 20.0 REVISIONS Revision Number Reason for revision - Date ETS-8-210.0 Page 15 of 18 Preparation of FOSA, MeFOSA, or EtFOSA Hydrolysis Samples and Analysis by HPLCMS Page 39 of 126 BACK TO MAIN I , 3M Environmental Laboratory ReportNo. EL1132 Attachment A: Representative Chemical Structures FOSA (MW = 499) FFFFFFFFO MeFOSA (MW = 513) FFFFFFFFO F EtFOSA (MW = 527) FFFFFFO PFOS (MW of anion = 499) THPFOS (MW of anion = 427) FFFFFFHHO ETS-8-210.0 Prep. of FOSA, MeFOSA, or EtFOSA Hydrolysis Samples and Analysis by HPLCMS Page 16 of 18 Page 40 of 126 FBSA ( M W = 299) BACK TO MAIN I . 3M Environmental Laboratory Report No. ELI 132 FFFFO N-MeFBSA ( M W = 3 13) ETS-8-210.0 Prep. of FOSA, MeFOSA, or EtFOSA Hydrolysis Samples and Analysis by HPLCMS Page 17 of 18 Page 41 of 126 Quenching BACK TO MAIN 3M Environmental Laboratory ReportNo. ELI132 Attachment B:Hydrolysis Sample Logsheet TEST ANALYTE HOURS: Sample No. - - - - - - - - Fluorochemical Degradation (Hydrolysis) Analysis Description Sample Duplicate Spike 0 Tm i of Initial PW Sample Duplicate Spike 0 Sample Duplicate Spike 0 Sample Duplicate Spike 0 Buffer pH 1.5 1.5 1.5 BufFer Volume (dl 1 .o 1 .o 1 .o Test Analyte Solution (& 5 1.0 5 I.o 5 1.0 7 1 .o 7 1 .o 7 1 .o 9 1 .o 9 1 .o 9 1 .o ISm Solution (llL) Spike Solution (&) lime of Quenching Quenching Solvent(ml) - Sample - Duplicate - Spike 0 Dateof InitialPrep: 11 I.o 11 1.0 11 1.0 Date of Quenching: Analyte Test Cnt,,t;nn StandardFraceabililyNo. Component Concentration (WrnL) ISSToDlution Spike Solution sn~,,tion NA Temperatureof Incubator CC): IncubationStart (Date andTme): Incubation Stop (Date and Tme): Total Incubationlime: Buffer Addition by: ISTO Addition by: Test Analyte Addition by: Quenching by: Spike Addition by: Autovial Aliquotingby: YeCsentrifugation I No Centrifuge: RPM: Time: I min By: Filtration: Yes I No BY: Size: Pore urn, Brand: Reviewed by: ETS-8-210.0 Preparation of FOSA, MeFOSA,orEtFOSA Hydrolysis Samplesand Analysis by HPLCMS Page 18 of 18 Page 42 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 ~ Appendix B: Kinetics Model This Appendix includes a mathematical descriptioonf the kinetics model employed in the study. Page 43 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Kinetics Model BI. Reaction Components and Rates The arguments below are based on the following idealized set of reactions representing the hydrolysisof a parent compoundP and its hydrolysis productsA,, which number N. The actual hydrolysis reactions that occur under neutral, acidic, and basic conditions are subsumed in these equations, and are assumed to proceed with pseudo-first order rates k,, (for the parent) andk,, (for the parent's hydrolysis products). P + H20 kP, e n, A, +Y, (m= 1toN) 031) A, + H,O e k h Ym2 (m= 1toN) where the general symbolsY,, and Ym2represent all the other hydrolysis products. B2. Parent Compound Concentrations Equation B1 indicates that the pseudo-first order differential chaningethe parent concentration P is given by which is equivalent to the separable differential equation Equation 64 may be directly integrated to obtain the general solution ln[P]= [-xn, k,, t ]+C With the initial conditionP(t = 0) E Po,the specific solution to EquationB4 is P = Po exp [-gn, k,, 1). Poe-kpt using the additional definitioonf the total parent hydrolysis rate Page 44 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 N k, E n, k,, . Equation B6 canbe re-written in a form that allows a least-squares estimatethoef total parent hydrolysis rate: k,t =-In [i] Using the initia(tl =0) measured value of the parent concentratioPnoand later values P measured at later timest , one can calculate and plot the (linear) quantity [- In (P/Po)] versus time and obtaina least -squares estimate of the slope of the line. The resulting slope is the least-squares estimaitepof the total parent hydrolysis rate. Equation B6 indicates that over a period of TtiIm'; e(the parent hydrolysis half-lifet)he parent concentrationP is reduced through hydrolysis by a factortwoof , where A least squares estimate of the parent hydrolysis half-life is therefore available from 63. Product Compound Concentrations The pseudo-first order differential changiensthe product concentrations4, (using Equations 82 and B6) are dA, = ( n,kp,P - k,,A,)dt = ( nmkPmPeO-kp - k,,A,)dt (Bll) and the (first order, non-separable) differential equation governing the product concentrations is - dAm+ k,A, = nmkPmPeO-kpt. dt The "standard form" of Equation B12 is Page 45 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 A i + S (t) A, = Q(t) where the "function"S(t)is actually a constant: and Q(t) =nmkPmPeO-kpt. The general solutionA, to Equation B12 is contained in (815) where and ~ Q ( t ) e ~ s h .d)td t+' C = n,k,,Po~ ekht e-kptd+t C There aretwo cases of Equation B18 to consider. In the circumstance thatk,, = k, , which occurs only when the hydrolysis oraf ttehe mthproduct is identicatlo the total parent hydrolysis rate, the general solution to Equation B18 is (for k, = k , ) A, + ekp=t nmkpmPtO C and, using the initial conditioAn,(t = 0) = A, , the specific solutionto Equation18 is (for k, = k,) A, = (nmkPmPt O+ A , ) e-kp . We note that whenk, = k , = 0 (that is, when both the parent and potential product are hydrolytically stable), EquatioBn7 requires (also) thatk,, =0 , so Equation B20 becomes Page 46 of 126 BACK TO MAIN 3M Environmental Laboratory ReportNo. ELI 132 indicating, as required, that the product concentration does not change with time. The circumstance k, = k, is highly improbable, and is neglected in the remainder of this discussion. However, the reader should bear in mind that the expressions derived below do not hold when the parent hydrolysis rkapteand the product hydrolysis ratek, approach each other. In the more probable case, for whickh,,,, # kp (i.e. that the hydrolysis rate of themth product is different from the total parent hydrolysis rate), the general solutotion Equation B18 is and the specific solutionto Equation B18 with the initial conditionA,(t = 0) = A,, is Of greatest interest here is the caisnewhich the product compounds are knowton be hydrolytically stable, that is, whenk, = 0 for all m. In this case, Equation823 becomes (for hydrolytically stable products) + ( A,,, = A m O n,k PmP 1- l - C k p f ). B4. Relationships Between the Parentand Compound Concentrations Equations 87 and B24 can be combined to obtain (for hydrolytically stable products) Page 47 of 126 so that or ~ BACK TO MAIN 3M Environmental Laboratory Report No. E L I 132 (for hydrolytically stable products) (for hydrolytically stable products) If the changesin the product concentrations are all small compared to the original parent concentration, that is,if we may use the expression (valid for -1 5 X I1 ) In(l+X)=X- -1x2 + -1 x 3 - 1- x 4 +..... 2 3 4 and EquationB23 becomes (for hydrolytically stableproductsand ICAm- A m o << Po) Page 48 of 126 ~ -~~~ ~~~~~ ~ ~ ~~ ~~ BACK TO MAIN 3M EnvironmentalLaboratory Report No. ELI132 or (for hydrolytically stable products and I Z A , -A , l << Po) 85. Parent Half-Life EstimatesBased on Limits of Quantification of the Products In every experimental determination okf, , there is some set of valueAs r Q (the "limits of quantitation") below which the product concentrationAs, cannot be reliably measured. If during an experiment carried out over the periofdtimeA t all the product concentrations A, remain below their limits of quantitation, then the maximum possible value of the ratek, is obtained by assuming (for all the products) tha1t ) A,, = 0 and 2) at time t= A t ,the product concentrations have increasetdo the values A,,,= A F Q . With these assumptions, the experimental data indicate that the reaction rka,teis less than some maximum value(kp),, as follows: (for hydrolytically stable products at concentrations below the limits of quantitation) 1 N k, 5 (kp),= = Po A t m=l Under the same circumstances and assumptions, the experimental data indicate that the parent half-lifeTI'; (see EquationB9)is greater than the value(Tvi) , as follows: mm (for hydrolytically stable products at concentrations below the limits of quantitation) The reader should note that Equations B32 and B33 are valid only when1)bthoeth products are hydrolytically stable an2d) the concentrations oaf ll the potential products are measured. Otherwise, the quantity (kp)- in Equation B32 may not actually represent the maximum possible value of the rate conkst,a,natnd the related resuiltn Equation B33 for (T") . is also questionable. mln Page 49 of 126 BACK TO MAIN 3M Environmental Laboratory Report No.E L I 132 B6. Parent Half-Life Estimates Based oLnimits of Quantification and Experimental Precision of Product Concentrations In certain experiments, some hydrolysis products are present at quantifiable but essentially constant concentrations over the tim(eA t ) of the experiment. In this casei,t is the experimental precision of the measured product concentrations, rather than the limits of quantitation, which contributtoethe estimate of the maximum value of the parent hydrolysis ratek, . If the set of concentrations measured for tmhethproduct have the mean valuep, and standard deviation(3 ,,the data do not exclude the possibility that the product concentration increased from the initial v0a,lue-p,,,to the value ( 3 +,p, at time t= A t . Taking this possibility to be the actual case for the measured products, the maximum valuoef the quantity (A, -Amo) is 20,. This reasoning suggests that the following estimate of the maximum parent hydrolysisisrate appropriate: (for hydrolytically stable products at either1) constant measured concentrations with standard deviation om or k, I (k,),= 2) = -1 c concentrations below the limitsof quantitation) r 1 1 A Y Q + c20,j. 0` A Below LOQ Cons tan t Under these circumstances and assumptions, the experimental data indicate that the parent half-life TI'; is greater than the value (Tvi) . as follows: mm (for hydrolytically stable products at eitherI)constant measured concentrations with standard deviationom or 2) concentrations below the limits of quantitation) The reader should note that Equations634 and 635 are valid only when both1) the products are hydrolytically stable an2d) the concentrationsof all the potential products are measured. B6. Parent Half-Life Estimates Based on the Experimental Precision of Parent Concentrations In certain experiments, the hydrolytic parent remains at an essentially constant concentration over the time( A t ) of the experiment. In this case,it is the experimental precision of the measured parent concentrations that determines the maximum value of the parent hydrolysis ratek, . If the setof concentrations measured for the parent have the mean valuep, and standard deviationCJ,,the data do not exclude the possibility Page 50 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 (3, that the product concentration increased from the initial valpupe- to the value CY, pp + at time t= A t . This reasoning suggests that the following estimate of the maximum parent hydrolysis rate is appropriate: (for essentially constant parent concentrations with mean valupe pand standard deviation0,) Under these circumstances and assumptions, the experimental data indicate that the parent half-life T1'; is greater than the value(Tyi) . as follows: mm (3, (for essentially constant parent concentrations with mean valueppand standard deviation ) B5. Parent Half-Life Estimates Based on Limits of Detection of the Products In every experimental determination okf p, there is some set of valuesA': (the "limits of detection") below which the product concentratioAn,s,,cannot be reliably detected. If during an experiment carried out over the period of timt eaAll the product concentrations A, remain below their limits of detection, then the maximum possible value of the ratek, is obtained by assuming (for all the products) t1h)aAt ,, = 0 and 2) at time t= A t ,the product concentrations have increasetdo the values A,,,= A;'". With these assumptions, the experimental data indicate that the reaction rka,teis less than some maximum value(k,), as follows: (for hydrolytically stable productsat concentrations below the limits of detection) 1 N k, I (kp),, = - E A ? . Po A t m=l Page 51 of 126 BACK TO MAIN 3M Environmental Laboratory Report No.E L I 132 Under the same circumstances and assumptions, the experimental data indicateththeat parent half-lifeT1/i(see Equation B9) is greater than the valu(eTb/t). as follows: mm (for hydrolytically stable products at concentrations below the limitsof detection) The reader should note that Equations B38 and B39 are valid only when1)btohteh products are hydrolytically stable an2d) the concentrations oaf ll the potential products are measured. Otherwise, the quantity(kp),, in Equation B38 may not actually represent the maximum possible value of the rate conskt,a,nat nd the related resulitn Equation B39 for (Tyi) . is also questionable. rnm B9. Temperature Dependence of the Reaction Rateand Half-Life In order to increase the speed of the reactions of interest, we conducted this experimental study using samples maintained at the temperature 5=03C23 K. Of greater interestare the corresponding results for the environmentally important temperature 25C = 298 K. When the Arrhenius activation energy for a reactiiosnAH,, Equation 838 B1 provides the following relationship between the hydrolysis r(aktleasnd k2) for that reaction tawt o different absolute temperature(sTl and T2): where R = 1.99 x lo3 Kcal mole-' K-lis the ideal gas constant. Using the valueB2 AHa=18 KcaVmole, therate ratiok , / k , at the corresponding temperaturesTl=298 K and T,=323 K is 5= exp{ 18 [L- k2 1 . 9 9 ~ 12098-3~23 L]} = exp(-2.35) = 0.095 Equation B39 indicates that the hydrolysis reactions of interest proceed approximately ten times more slowly a2t5C than at the chosen experimental temperature of 50C. Accordingly, the rate reactions reported here for the temperature 25Cteanretimes lower than those measured 5a0tC, and the hydrolysis half-life estimates reported here Page 52 of 126 ~~~ BACK TO MAIN 3M Environmental Laboratory Report No.ELI 132 for 25C samples are ten times longer than those calculated from the 50C experimental data. References to Appendix B: I. N Levine, "Physical Chemistry," McGraw-Hill (New York), pp. 498-5(109178). 82 F. Daniels, et al., "Experimental Physical Chemistry", McGraw Hill (New York), p.131 (1962). Page 53 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Appendix C: Selected Analytical and Kinetics Results This Appendix includes selected sample data and their related kinetics results. Page 54 of 126 -0.057 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 FOSA Buffer Hydrolysis Studyat 50" C. 7 14 28 35 42 1.5 1.5 1.5 1.5 1.5 L 1.5 -0.024 464 443 -0.20154 450 441 458 441 -0.069 -0.075 -0.036 -0.073 I FOSA @ 50 C v pH 1.5, Rate constant graph 0.05 I:?---"' *. _3 y = -1.27E-03x - 2.078-02 R' =4.54E-01 ......................................... 1- 0 10 20 30 40 50 Time (days) pH Time (Days) Conc. In([P]ti[P]o) 3.0 0 484 0.000 3.0 7 48 1 -0.006 -0.057 3.O457 14 3.0 -0.12211 429 451 28 3.0 -0.035 4673.0 35 42 3.0 466 -0.037 SUMMARY OUTPUT Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.67379 0.45399 0.34479 0.02299 7 ANOVA Regression Residual Total df 1 5 6 ss 0.00220 0.00264 0.00484 lnterceot X Variable 1 Coefficients -0.02072 -0.00127 StanEdarrrodr 0.01567 0.00062 % 20 Slope Uncertainty 98% SUMMARY OUTPUT Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.32433 0.10519 -0.07377 0.04187 7 ANOVA Regression Residual Total df 1 5 6 ss 0.00103 0.00877 0.00980 InterceDt X Variable 1 Coefficients -0.02664 -0.00087 StanEdarrrodr 0.02853 ~~ 0.001 13 % 20 Slope Uncertainty 261% Page 55 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 FOSA Buffer Hydrolysis Study at 50" C. All concentrations in ng/ml. pH Time (Days) 5.0 0 Conc. 470 5.0 442 5.0 46 1 5.0 42 457 ln([P]ti[P]o) 0.000 -0.032 -0.066 -0.076 -0.061 -0.019 -0.027 -FOSA @ 50 C pH 5.0 Rate constant graph 0.05 IT-"""" 7 2-s -0.10 -0.15 -0.20 y = -2.64E-04x- 3.478-02 R' = 2.038-02 SUMMARY OUTPUT Regression Multiple R R Square Adjusted R Square Standard Error Observations Statistics 0.14235 0.02026 -0.17568 0.03036 7 ANOVA Regression Residual Total df 1 5 6 ss 0.00010 0.00461 0.00470 Intercept 0.02069 X Variable 1 Coefficients -0.03470 0.000-802.00026 StanEdarrrodr % 20 Slope Uncertainty 622% 465 14 pH Time (Days) Conc. ln([P]t/[P]o) 7.0 0 48 1 0.000 7.0 7 414 -0.015 7.0 -0.034 7.0 21 484 0.007 7.0 28 456 -0.055 7.0 35 488 0.014 7.0 42 419 -0.004 SUMMARY OUTPUT Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.07787 0.00606 9-207.21 0.02653 7 ~~ ~ ~~~ FOSA @ 50 C pH 7.0 -Rate constant graph 5 -0.05 -0.20 -0.25 I 0 y = 1.25E-04x-1.51E-02 R' = 6.068-03 ~~ IO ~ . . .. j I ~~~ -~ T - ~ 7-1 20 30 40 50 Time (days) - ___ ANOVA Regression Residual Total Intercept X Variable 1 % 20 Slope Uncertainty 1145% df 1 5 6 ss 0.00002 0.00352 0.00354 Coefficients -0.01505 0.000720.00013 StanEdarrrodr 0.01807 Page 56 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 FOSA Buffer Hydrolysis Study at50" C. \It concentrations in ng/ml. pH Time (Days) 9.0 0 9.0 I 9.0 14 9.0 21 9.0 28 9.0 35 9.0 42 Conc. 429 430 431 438 428 45 1 452 In([P]t/[P]o) 0.000 0.003 0.018 0.022 -0.002 0.050 Error 0.052 SUMMARY OUTPUT Regression statistics Multiple R R Square Adjusted R Square Standard Observations 0.78210 0.61 167 0.53401 0.01555 7 FOSA @?50 C ANOVA , pH 7.0 -Rate constant graph 0.10 , j - - Regression Residual 4- -0.10 1 -0.20 / ' ~~~- y = I.IBE-03x-4.10E-03 R2= 6 12E-01 ,-_ .. .I .. 2 , ~~~~ ~ .,...... Total Intercept X Variable 1 0 10 20 30 40 Time (days) % 20 Slope Uncertainty 71 % s s - df ~~ 1 0.00190 5 0.00121 6 0.0031 1 Coefficients -0.00410 0.001 18 StanEdarrrodr 0.01060 0.00042 pH 11.0 11.0 11.0 43911.0 11.0 11.0 11.0 Time (Days) 21 0 I 14 28 35 42 Conc. 445 446 445 438 463 466 In([P]t/[P]o) 0.000 -0.001 -0.017 -0.018 0.038 0.044 SUMMARY OUTPUT Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.65519 0.42927 0.28659 0.02276 6 ANOVA Regression Residual df 1 4 ss 0.00156 0.00207 4 -0.05 -0.15 y = 1.07E-03x- 1.47E-02 R z = 4 29E-01 Intercept X Variable 1 % 20 Slope Uncertainty 115% Data in italics excluded on the basis of data quality objectives: see text. Coefficients -0.01467 0.00107 StanEdarrrodr 0.01590 0.00061 Page 57 of 126 FOSA (Perfluorooctanesulfonamide) Hydrolysis Study 5OC; pH 1.5 AII concentrations i n ng/ml. AII areas x 10' DSA MeOH Blank 99039-135-02 99039-135-03 99039-135-04 99039-135-05 99039-13566 PFOSAW1.D PFOSAO05.D PF0SAOOG.D PFOSA007.D PFOSAO08.D PFOSAW9.D let Time 4.5 4.5 4.5 4.5 4.5 4.5 Area - COnC. c 12.5 200 412 1060 2091 3951 53 101 252 513 1018 Y-Standard or %RSD 106% 102% 101% 103% 102% 'h SDike Recovery MeOH Blank MeOH Blank PFOSA014.D PFOSA015.D 4.5 c 12.5 4.5 c 12.5 80399PFOSA-001 PFOSAO16.D Day 0 4.5 1958 474 1% 80399PFOSA-002 PFOSA017.D Day 0 4.5 2005 48 1 80399PFOSA-003 PFOSA018.D Day 0 4.5 1949 469 80399PFOSA-004 PFOSAO19.D Day 0 4.5 2789 689 80399PFOSA-025 PFOSA020.D Day 7 4.5 1915 459 156 80399PFOSA-026 PFOSA021.D Day 7 4.5 1940 465 80399PFOSA-027 PFOSA022.D Day 7 4.5 1945 467 80399PFOSA-028 PFOSA023.D Day 7 4.5 291 1 703 80399PFOSA-049 PFOSA024.D Day 14 4.5 1885 447 1 % 80399PFOSA-050 PFOSA025.D Day 14 4.5 1881 438 80399PFOSA-051 PFOSA026.D Day 14 4.5 1957 443 80399PFOSA-052 PFOSA027.D Day 14 4.5 2850 684 80399PFOSA-073 PFOSA028.D Day 21 4.5 1864 439 3% 80399PFOSA-074 PFOSA029.D Day 21 4.5 1931 447 80399PFOSA-075 PFOSA030.D Day 21 4.5 1976 463 80399PFOSA-076 PFOSA031.D Day 21 4.5 2810 652 86% 96% 97% 81 % MeOH Blank MeOH Blank PFOSAO35.D PFOSA036.D 4.5 C 12.5 4.5 < 12.5 80399PFOSA-097 PFOSA037.D Day 28 4.5 1850 437 1% 80399PFOSA-098 PFOSA038.D Day 28 4.5 1840 44 1 80399PFOSA-099 PFOSA039.D Day 28 4.5 1914 444 80399PFOSA-100 PFOSA040.D Day 28 4.5 2905 699 80399PFOSA-I21 PFOSA041.D Day 35 4.5 1898 448 2% 80399PFOSA-122 PFOSA042.D Day 35 4.5 1896 455 80399PFOSA-123 PFOSAM3.D Day 35 4.5 1974 470 80399PFOSA-124 PFOSA044.D Day 35 4.5 2682 651 80399PFOSA-I45 PFOSA045.D Day 42 4.5 1927 451 2% 80399PFOSA-146 PFOSA046.D Day 42 4.5 1871 434 80399PFOSA-147 PFOSA047.D Day 42 4.5 1854 439 80399PFOSA-148 PFOSA048.D Day 42 4.5 2898 700 104% 77% 103% MeOH Blank PFOSA049.D MeOH Blank 99039-135-01 PFOSA050.D PFOSA051.D 99039-135-02 PFOSA052.D 99039-135-03 9903913504 99039-135-05 PFOSA053.D PFOSA054.D PFOSA055.D P9F9O0S39A-015365.-D06 Method ID: 0309-15A.M __ (A) The relative standard deviation (RSDis) not define 4.5 < 12.5 4.5 < 12.5 4.5 195 50 4.5 405 96 4.5 1037 243 4.5 2067 489 4.5 3935 979 101% 96% 97% 98% 98% Internal Standard quant: 8-0.999 Curve Averaged, Quadratic,Orlgm ignored Cal. range mm. amnadx = 49.9 998 Original cow.= 499.4 Sptke conc.= 249.7 hen the mean concentratlon IS zero. BACK TO MAIN 3M Environmental Laboratory Report No.ELI132 'FOS Ret Time 37 3.7 3.7 3.7 3.7 3.7 3.7 Area 25 119 238 61 1 1173 2154 Conc. < 13.0 15 54 104 264 531 1050 %Standard or %RSD %Spike Recovery 3.7 < 13.0 3.7 < 13.0 0 0 3.7 0 0 3.7 0 0 3.7 0 0 3.7 593 255 3.7 0 0 3.7 0 0 3.7 0 0 3.7 596 250 3.7 0 0 3.7 0 0 3.7 0 0 3.7 590 246 3.7 0 0 3.7 0 0 3.7 0 0 3.7 597 242 98% 96% 95% 97% 3.1 < 13.0 3.7 < 13.0 3.7 0 0 3.7 0 0 3.7 0 0 3.7 589 246 3.7 0 0 3.7 0 0 3.7 0 0 3.7 587 249 3.7 0 0 3.7 0 0 3.7 0 0 3.7 592 248 95% 96% 96% 3.7 < 13.0 3.7 < 13.0 3.7 28 16 3.7 115 51 3.7 240 101 3.7 604 257 3.7 1160 506 3.7 2177 1026 99% Internal Standard quant: ?=0.999 CurveAveraged, Quadratic. Ongin ignored Cranl.mgein. and max = 51.9 1038 Spike conc.= 259.40 BSA tet Time 3.8 3.8 3.8 3.8 3.8 3.8 Area 0 1008 1012 1022 1012 1029 3.8 1021 3.8 1031 3.8 1027 3.8 1026 3.8 1029 3.8 1032 3.8 1030 3.8 1051 3.8 1039 3.8 1058 3.8 1088 3.8 1056 3.8 1044 3.8 1065 3.8 1055 3.8 1088 3.8 1043 3.8 1028 3.8 1063 3.8 1054 3.8 1044 3.8 1027 3.8 1038 3.8 1039 3.8 1055 3.8 1060 3.8 1040 3.8 1051 3.8 3.8 3.8 3.8 3.8 Conc. mean S.D. %S.D. 1038 1053 1036 1046 1059 225 1042 I8 1.8% Page 58 of 126 FOSA (Perfluorooctanesulfonamide)Hydrolysis Study 5OC; pH 3.0 All concentrations in nglml. All areas x IO-' OSA 99039-13641 99039-13642 99039-13603 99039-136-04 99039-13665 99039-13606 PFOSA059.D PFOSA060.0 PFOSA061.D PFOSA062.D PFOSA063.D PFOSA064.D ZetTime 4.5 4.5 4.5 4.5 4.5 4.5 Area 195 403 1059 2041 3909 Conc. < 12.5 48 99 262 516 1022 %Standard or %RSD 95% 99% 105% 103% 102% % Spike Recovery MeOH Blank MeOH Blank PFOSA069.D PFOSA070.D 4.5 0 c 12.5 4.5 0 c 12.5 80399PFOSA-005 PFOSA071.D Day 0 4.5 1972 484 1% 80399PFOSA-006 PFOSA072.D Day 0 4.5 1971 481 80399PFOSA-007 PFOSA073.D Day 0 4.5 1984 486 80399PFOSA-008 PFOSA074.D Day 0 4.5 2931 734 80399PFOSA-029 PFOSA075.D Day 7 4.5 1919 484 1% 80399PFOSA-030 PFOSA076.D Day 7 4.5 1917 476 80399PFOSA-031 PFOSA077.D Day 7 4.5 1981 482 80399PFOSA-032 PFOSA078.D Day 7 4.5 2953 732 80399PFOSA-053 PFOSA079.D Day 14 4.5 1908 448 2% 80399PFOSA-054 PFOSA080.D Day 14 4.5 1952 468 80399PFOSA-055 PFOSA081.D Day 14 4.5 1890 455 80399PFOSA-056 PFOSA082.D Day 14 4.5 3050 72 1 80399PFOSA-077 PFOSA083.D Day 21 4.5 3565 421 3% 80399PFOSA-078 PFOSA084.D Day 21 4.5 1880 446 80399PFOSA-079 PFOSA08S.D Day 21 4.5 1805 419 80399PFOSA-080 PFOSA086.D Day 21 4.5 2874 690 100% 100% 106% 105% MeOH Blank MeOH Blank PFOSA0SO.D PFOSA091.D 4.5 < 12.5 4.5 < 12.5 80399PFOSA-101 PFOSA092.D Day 28 4.5 1871 458 0% 80399PFOSA-102 PFOSA093.D Day 28 4.5 1857 455 80399PFOSA-I03 PFOSA094.D Day 28 4.5 1883 458 80399PFOSA-I04 PFOSA095.D Day 28 4.5 2873 700 80399PFOSA-125 PFOSA096.D Day 35 4.5 1933 467 1% 80399PFOSA-126 PFOSA097.D Day 35 4.5 1953 471 80399PFOSA-I27 PFOSA098.D Day 35 4.5 1898 464 80399PFOSA-128 PFOSA099.D Day 35 4.5 2962 730 80399PFOSA-149 PFOSA1OO.D Day 42 4.5 1958 471 3% 80399PFOSA-150 PFOSA1OI.D Day 42 4.5 1984 479 80399PFOSA-151 PFOSA102.D Day 42 4.5 1867 448 80399PFOSA-152 PFOSA103.D Day 42 4.5 2911900 695 98% 105% 92% MeOH Blank MeOH Blank 99039-13601 99039-13602 99039-136-03 99039-136-04 99039-13605 99039-136-06 Method ID: PFOSA104.D PFOSA105.D PFOSA106.D PFOSA107.D PFOSAIO8.D PFOSA1OS.D PFOSA1lO.D PFOSAlll.D 0309-15A.M (A) The relativepercent deviatlon (RPD) isnot define( 4.5 < 12.5 4.5 < 12.5 4.5 201 48 4.5 41 1 98 4.5 1056 254 4.5 2108 472 4.5 3986 977 96% 98% 102% 94% 98% InternalStandard quant: 8=0.999 CuNe Averaged, Quadratlc. Origln ignored Cal. range min. and rnax= 49.9 998 Oriainala m . = 499.4 Spike ~ m .2=49.7 en the mean concentrationis zero. BACK TO MAIN 3M Environmental Laboratory ReportNo. ELI 132 FOS Zet Time 3.7 3.7 3.7 3.7 3.7 3.7 3.7 Area 25 117 232 614 1171 2160 Conc. < 13.0 11 51 101 273 540 1064 %Standard or %RSD % Spike Recovery 3.7 0 < 13.0 3.7 0 < 13.0 3.7 0 0 3.7 0 0 3.7 0 0 3.7 593 256 3.7 0 0 3.7 0 0 3.7 0 0 3.7 593 253 3.7 0 0 3.7 0 0 3.7 0 0 3.7 62 1 253 3.7 0 0 3.7 0 0 3.7 0 0 3.7 585 242 99% 98% 98% 97% 3.7 < 13.0 3.7 < 13.0 3.7 0 0 3.7 0 0 3.7 0 0 3.7 589 248 3.7 0 0 3.7 0 0 3.7 0 0 3.7 601 255 3.7 0 0 3.7 0 0 3.7 0 0 3.7 598 246 96% 98% 95% 3.7 < 13.0 3.7 c 13.0 0.0 27 12 3.7 115 49 3.7 239 101 3.7 615 265 3.7 1191 484 3.7 2205 1014 93% 98% InternalStandard quant: ?=0.999 Curve Averaged, Quadratic, Origin ignored Cal. range min.and max = 51.9 1038 Spike conc.= 259.40 BSA 3et Time 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 Area 0 0 1041 1041 1044 1045 1054 0 0 3.8 1073 3.8 1080 3.8 1076 3.8 1075 3.8 1045 3.8 1060 3.8 1082 3.8 1086 3.8 1118 3.8 1098 3.8 1092 3.8 1137 3.8 2222 3.8 1108 3.8 1128 3.8 1116 3.8 0 3.8 0 3.8 1074 3.8 1074 3.8 1081 3.8 1101 3.8 1089 3.8 1091 3.8 1077 3.8 1091 3.8 1095 3.8 1091 3.8 1094 3.8 1123 3.8 0 3.8 0 3.8 3.8 3.8 3.8 3.8 Conc. mean S.D. 96S.D. 1067 1072 1076 1176 1120 225 1116 186 16.7% Page 59 of 126 FOSA (Pefluorooctanesulfonarnide)Hydrdyois Study 50C: pH 5.0 AHconcentrations in nglrnl. AII areas x O=I 99039-13701 99039-137-02 99039-13763 99039-13764 99039-13765 99039-13746 PFOSA004.D PFOSAO05.D PFOSA0DG.D PFOSA007.0 PFOSAOO8.0 PFOSAO09.D Letlime 4.5 4.5 4.5 4.5 4.5 4.5 Area 194 419 1026 2059 4043 Conc. c 12.5 51 101 246 495 986 %Standar%doSrpike %RSD Recovety 102% 101% 98% 99% 99% MeOH Blank MeOH Blank PFOSA014.D PFOSA015.D 4.5 < 12.5 4.5 < 12.5 80399PFOSA-009 PFOSAO16.D Day 0 4.5 2010 472 0% 80399PFOSA-010 PFOSA017.D Day 0 4.5 2039 470 80399PFOSA-011 PFOSA018.D Day 0 4.5 2003 468 80399PFOSA-012 PFOSA019.D Day 0 4.5 3010 705 80399PFOSA-033 PFOSA020.D Day 7 4.5 1934 446 2% 80399PFOSA-034 PFOSA021.0 Day 7 4.5 1956 461 80399PFOSA-035 PFOSA022.0 Day 7 4.5 1935 458 80399PFOSA-036 PFOSA023.D Day 7 4.5 3030 716 80399PFOSA-057 PFOSA024.D Day 14 4.5 2285 436 1% 80399PFOSA-058 PFOSA025.D Day 14 4.5 1964 44 1 80399PFOSA-059 PFOSA026.D Day 14 4.5 1942 443 80399PFOSA-060 PFOSA027.D Day 14 4.5 3055 684 80399PFOSA-081 PFOSA028.D Day 2 1 4.5 1966 443 5% 80399PFOSA-082 PFOSAO29.0 Day 21 4.5 1980 450 80399PFOSA-083 PFOSA030.D Day 21 4.5 1853 413 80399PFOSA-084 PFOSA031.D Day 21 4.5 2945 703 94% 96% 97% 81 % MeOH Blank MeOH Blank PFOSAO35.0 PFOSAO36.D 4.5 < 12.5 4.5 < 12.5 80399PFOSA-105 PFOSA037.0 Day 28 4.5 1873 444 1% 80399PFOSA-106 PFOSAO38.D Day 26 4.5 1888 446 80399PFOSA-107 PFOSA039.D Day 28 4.5 1869 437 80399PFOSA-108 PFOSA040.D Day 28 4.5 2863 692 80399PFOSA-129 PFOSA041.D Day 35 4.5 1949 461 2% 80399PFOSA-130 PFOSA042.D Day 35 4.5 1926 453 80399PFOSA-131 PFOSA043.D Day 35 4.5 2007 468 80399PFOSA-132 PFOSA044.D Day 35 4.5 2957 705 80399PFOSA-I53 PFOSA045.D Day 42 4.5 1926 459 1% 80399PFOSA-154 PFOSAC46.D Day 42 4.5 1947 461 80399PFOSA-155 PFOSA047.D Day 42 4.5 1887 452 80399PFOSA-156 PFOSA048.D Day 42 4.5 2963 705 104% 77% 103% MeOH Blank MeOH Blank 99039-137-01 99039-13702 99039-137-03 99039-13704 99039-13705 99039-137-06 Method ID PFOSA049.D PFOSA050.D PFOSA051.D PFOSAO52.D PFOSAO53.0 PFOSAO54.D PFOSAO55.D PFOSAO56.D 0309-156.M __ (A) The relabve percent deviation (RPD) niso1 definec 4.5 < 12.5 4.5 C 12.5 4.5 197 52 103% 4.5 404 100 100% 4.5 1015 246 98% 4.5 2083 510 102% 4.5 4003 1011 101% InternalStandard quant: 8-0.999 Curve Averaged, Quadratic, Origin ignored Cal. range min. and max = 49.9 998 Originalmnc.= 499.4 Spike conc.= 249.7 en the mean concentratlonis zero. BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 'FOS RetTirne 37 3.7 3.7 3.7 3.7 3.7 3.7 Area 26 118 236 579 1171 221 8 Conc. < 13.0 I5 54 103 254 523 1028 %Standard or %RSD X Spike Recovery BSA letlime 3.8 3.8 3.8 3.8 3.8 3.8 3.7 0 < 13.0 3.8 3.7 0 < 13.0 3.8 3.1 0 0 3.7 0 0 3.7 0 0 3.7 596 249 3.7 0 0 3.7 0 0 3.7 0 0 3.7 598 252 3.7 0 0 3.7 0 0 3.7 0 0 3.7 634 253 3.7 0 0 3.7 0 0 3.7 0 0 3.7 598 254 96% 3.8 3.8 3.8 3.8 97% 3.8 3.8 3.8 3.8 98% 3.8 3.8 3.8 3.8 102% 3.8 3.8 3.8 3.8 3.7 < 13.0 3.8 3.7 < 13.0 3.8 3.7 0 0 3.7 0 0 3.7 0 0 3.7 575 248 3.7 0 0 3.7 0 0 3.7 0 0 3.7 571 243 3.7 0 0 3.7 0 0 3.7 0 0 3.7 592 251 95% 3.8 3.8 3.8 3.8 94% 3.8 3.8 3.8 3.8 97% 3.8 3.8 3.8 3.8 3.7 < 13.0 3.7 < 13.0 3.7 26 15 3.7 118 54 3.7 236 105 3 .l 57 6 255 3.7 1147 52 1 3.7 2179 1046 101% InternalStandard quant: ?-0.999 Curve Averaged. Quadratlc. Origin ignored Craln.mgein. and max = 51.0938 Spike conc.= 259.40 3.8 3.8 3.8 3.8 3.8 3.8 3.8 225 Conc. mean 49 S.D. %S.D. Area 0 1054 1075 1062 1070 1099 0 0 1092 1113 1098 1115 1110 1087 1082 1106 1341 1141 1124 1165 1137 1127 1147 1094 0 0 1081 1086 1095 I081 1083 I088 1100 1095 1076 1082 1070 1098 0 0 1050 1054 1051 1051 1063 1099 4.5% Page 60 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 FQSA (PeAuorooctanesulfonamideH) ydrolysis Study 5OC; pH 7.0 AII concentrations in nglml. AII areas x IO^ OSA SetTime 4.5 Area Conc. c 12.5 %Standardor Y.RSD X Spike Recovery 99039-13802 99039-138-03 99039-138-04 99039-13505 99039-138-06 PFOSAO6O.D PFOSA061.D PFOSA062.D PFOSA063.D PFOSA064.D 4.5 203 48 4.5 412 97 4.5 1050 258 4.5 2035 496 4.5 3978 1003 97% 97% 103% 99% 100% MeOH Blank MeOH Blank PFOSA069.D PFOSA070.D 4.5 < 12.5 4.5 c 12.5 80399PFOSA-013 PFOSA071.D Day 0 4.5 1974 486 1% 80399PFOSA-014 PFOSA072.D Day 0 4.5 1992 476 80399PFOSA-015 PFOSA073.D Day 0 4.5 1977 482 80399PFOSA-016 PFOSA074.D Day 0 4.5 2979 733 80399PFOSA-037 PFOSAO75.D Day 7 4.5 1936 469 1% 80399PFOSA-038 PFOSA076.D Day 7 4.5 1899 474 80399PFOSA-039 PFOSA077.D Day 7 4.5 1968 480 80399PFOSA-040 PFOSA078.D Day 7 4.5 3004 737 80399PFOSA-061 PFOSA079.D Day 14 4.5 2006 457 2% 80399PFOSA-062 PFOSA080.D Day 14 4.5 1921 469 80399PFOSA-063 PFOSA081.D Day 14 4.5 2131 470 80399PFOSA-064 PFOSA082.D Day 14 4.5 2955 710 80399PFOSA-085 PFOSA083.D Day 2 1 4.5 1943 479 1% 80399PFOSA-086 PFOSA084.D Day 21 4.5 2000 484 80399PFOSA-087 PFOSA085.D Day 21 4.5 2109 490 80399PFOSA-088 PFOSA086.D Day 21 4.5 3153 738 101% 105% 98% 101% MeOH Blank MeOH Blank PFOSAR90.D PFOSA091.D 4.5 < 12.5 4.5 < 12.5 80399PFOSA-110 PFOSA092.D Day 28 4.5 1813 446 2% 80399PFOSA-111 PFOSAO93.D Day 28 4.5 1884 458 80399PFOSA-112 PFOSA094.D Day 28 4.5 1878 463 80399PFOSA-113 PFOSA095.D Day 28 4.5 2876 71 1 80399PFOSA-133 PFOSA096.D Day 35 4.5 1935 474 3% 80399PFOSA-134 PFOSA097.D Day 35 4.5 2089 497 80399PFOSA-135 PFOSA098.D Day 35 4.5 2009 493 80399PFOSA-136 PFOSA099.D Day 35 4.5 2918 721 80399PFOSA-I57 PFOSA100.D Day 42 4.5 1993 487 2% 80399PFOSA-158 PFOSAIO1.D Day 42 4.5 1939 480 80399PFOSA-159 PFOSA1OZ.D Day 42 4.5 1932 471 80399PFOSA-180 PFOSAI03.D Day 42 4.5 2980 723 102% 93% 98% MeOH Blank MeQH Blank 99039-138-01 99039-138-02 99039-138-03 99039-13844 99039-138-05 99039-13866 Method ID PFOSA104.D PFOSA1OS.D PFOSA106.D PFOSA107.D PFOSAIO8.D PFOSAIO9.D PFOSAIIO.D PFOSAI1I.D 0309-15B.M ___ (A) The relativepercent deviation(RPD) is not defined 4.5 < 12.5 4.5 < 12.5 4.5 200 49 97% 4.5 413 101 101% 4.5 1023 253 4.5 2017 496 101% 99% 4.5 3998 996 100% _ _ InternalStandard quant: +0.999 CurveAveraoed. Quadratic.Onain ianored GI. range min. and max= 49.9 998 Origlnalcone.= 499.4 Spike conc.= 249.7 en the meanconcentrationis zero. ___ FOS 1etTime 3.7 3.7 3.7 3.7 3.7 3.7 3.7 Area 26 122 238 597 1155 2162 Conc. < 13.0 11 52 101 264 516 1044 %Standard o r %RSD % Spike Recovery 3.7 < 13.0 3.7 < 13.0 3.7 0 0 3.7 0 0 3.7 0 0 3.7 583 252 3.7 0 0 3.7 0 0 3.7 0 0 3.7 593 256 3.7 0 0 3.7 0 0 3.7 0 0 3.7 603 255 3.7 0 0 3.7 0 0 3.7 0 0 3.7 613 252 97% 98% 98% 101% 3.7 C 13.0 3.7 C 13.0 3.7 0 0 96% 3.7 0 0 3.7 0 0 3.7 574 250 3.7 0 0 98% 3.7 0 0 3.7 0 0 3.7 583 253 3.7 0 0 96% 3.7 0 0 3.7 0 0 3.7 585 250 3.7 4 13.0 3.7 < 13.0 3.7 26 12 3.7 116 51 3.7 237 103 3.7 589 262 3.7 1144 51 7 _3.7_ 2166 1032 99% InternalStandard quant: ?-0.999 Curve Averaged, Quadratic. Orlgin Cal. range min. and max= 51.9 ignored 1038 Spike conc.= 259.40 BSA tetlime 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 Area 0 0 1043 1060 1030 1050 1040 0 0 3.8 1039 3.8 1070 3.8 1048 3.8 1051 3.8 1055 3.8 1025 3.8 1048 3.8 1056 3.8 1121 3.8 1046 3.8 1159 3.8 1076 3.8 1037 3.8 1056 3.8 1100 3.8 1106 3.8 0 3.8 0 3.8 1038 3.8 1050 3.8 1037 3.8 1045 3.8 1044 3.8 1075 3.8 1043 3.8 1047 3.8 1047 3.8 1032 3.8 1049 3.8 1066 3.8 0 3.8 0 3.8 3.8 3.8 3.8 3.8 Conc. mean S.D. %S.D. 1023 1026 1023 1040 1052 225 1054 28 2.6% Page 61 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 FOSA (Perfluorooctanesulfonarnide)Hydrolysis Study 50C; pH 9.0 All concentrationsin nglml. All areas x IO' OSA PFBMOlaeSnOkAHO03.D 99039-139-01 99039-139-02 99039-139-03 99039-1 39-04 99039-139-05 99039-13906 PFOSA004.D PFOSAO05.D PFOSAO08.D PFOSAO07.D PFOSAO08.D PFOSA009.D letTim 4.5 4.5 4.5 4.5 4.5 4.5 Area XRSCOonc. C 12.5 196 56 420 98 1056 229 2258 498 3943 953 %Standard or 111% 98% 92 % 100% 95% % Spike Recovery MeOH Blank MeOH Blank PFOSA014.D PFOSA015.D 4.5 c 12.5 4.5 c 12.5 80399PFOSA-017 PFOSA016.D Day 0 4.5 1948 434 1% 80399PFOSA-018 PFOSA017.D Day 0 4.5 1921 425 80399PFOSA-019 PFOSA018.D Day 0 4.5 1948 427 80399PFOSA-020 PFOSA019.D Day 0 4.5 2936 683 80399PFOSAd41 PFOSA020.D Day 7 4.5 1947 431 1% 80399PFOSA-042 PFOSA021.D Day 7 4.5 1945 435 80399PFOSA-043 PFOSA022.D Day 7 4.5 1894 423 80399PFOSA-044 PFOSA023.D Day 7 4.5 2760 628 80399PFOSA-065 PFOSA024.D Day 14 4.5 2054 435 1% 80399PFOSA-066 PFOSA025.D Day 14 4.5 1931 431 80399PFOSA-067 PFOSA026.D Day 14 4.5 1982 443 80399PFOSA-068 PFOSA027.D Day 14 4.5 2872 669 80399PFOSA-089 PFOSAO28.D Day 21 4.5 1893 430 2% 80399PFOSA-090 PFOSA029.D Day 21 4.5 1970 440 80399PFOSA-091 PFOSA030.D Day 21 4.5 1985 444 80399PFOSA-092 PFOSA031.D Day 21 4.5 2960 691 102% 79% 93% 101% MeOH Blank MeOH Blank PFOSA035.D PFOSAO36.D 4.5 < 12.5 4.5 < 12.5 80399PFOSA-113 PFOSA037.D Day 28 4.5 1883 43 1 1% 80399PFOSA-114 PFOSAO38.D Day 28 4.5 1849 422 80399PFOSA-115 PFOSA039.D Day 28 4.5 1850 430 80399PFOSA-116 PFOSA040.D Day 28 4.5 2813 686 80399PFOSA-I37 PFOSA041.D Day 35 4.5 1948 450 0% 80399PFOSA-138 PFOSA042.D Day 35 4.5 1936 452 80399PFOSA-I39 PFOSA043.D Day 35 4.5 1917 450 80399PFOSA-140 PFOSA044.D Day 35 4.5 2933 71 1 80399PFOSA-161 PFOSA045.D Day 42 4.5 1872 444 2% 80399PFOSA-162 PFOSA046.D Day 42 4.5 1929 452 80399PFOSA-163 PFOSA047.D Day 42 4.5 1951 459 80399PFOSA-164 PFOSA048.D Day 42 4.5 2831 697 103% 104% 98% MeOH Blank PFOSA049.D 4.5 c 12.5 MeOH Blank PFOSA050.D 4.5 C 12.5 99039-139-01 PFOSA051.D 99039-139-02 PFOSA052.D 4.5 190 57 113% 99039-139-03 PFOSA053.D 4.5 408 99 100% 99039-1 39-04 PFOSA054.D 4.5 1050 245 98% 99039-139-05 PFOSA055.D 4.5 2165 52 1 104% P99F0O3S9A-103596-.0D6 104% 4.15042 3835 1089 0309-1ID5M:Ce.tMhod InternalStandard quant: ?=0.999 Cuwe Averaged, Quadralic, Origin ignored Cal. ranmgaeimn.dax = 499.998 Original COK.= 499.4 Spike conc.= 249.7 (A) The relative percent deviation (RPD) is not define( hen the mean concentration is zero. 2127 FOS let Tkne 3.7 3.7 3.7 3.7 3.7 3.7 3.7 ha 26 114 248 612 1232 2172 Conc. < 13.0 22 55 102 244 505 985 %Standaorrd XRSD % Spike Recovery BSA tetlime 3.8 3.8 3.8 3.8 3.8 3.8 3.7 < 13.0 3.8 3.7 < 13.0 3.8 3.7 0 0 3.7 0 0 3.7 0 0 3.7 572 230 3.7 0 0 3.7 0 0 3.7 0 0 3.7 577 230 3.7 0 0 3.7 0 0 3.7 0 0 3.7 581 235 3.7 0 0 3.7 0 0 3.7 0 0 3.7 584 235 89% 3.8 3.8 3.8 3.8 89% 3.8 3.8 3.8 3.8 90% 3.8 3.8 3.8 3.8 94% 3.8 3.8 3.8 3.8 3.7 < 13.0 3.8 3.7 13.0 3.8 3.7 0 0 3.7 0 0 3.7 0 0 3.7 557 235 3.7 0 0 3.7 0 0 3.7 0 0 3.7 579 241 3.7 0 0 3.7 0 0 3.7 0 0 3.7 559 237 90% 3.8 3.8 3.8 3.8 93% 3.8 3.8 3.8 3.8 91 % 3.8 3.8 3.8 3.8 3.7 =z 13.0 3.7 c 13.0 3.7 26 23 3.7 112 57 3.7 242 105 3.7 597 256 3.7 1218 547 3.7 105% InternalStandard quant: +=0.999 Cuwe Averaged, Quadratic. Origin ignored Craln.mgaeimn.dax = 510.938 Spike conc.= 259.40 3.8 3.8 3.8 3.8 3.8 3.8 946 3.8 225 Conc. mean S.D. %S.D. Area 0 997 1029 1016 1022 1038 0 0 1002 1008 1016 1007 1006 997 996 1018 1052 1000 998 1003 98 1 999 998 1005 0 0 974 975 958 962 968 958 953 974 941 955 952 955 0 0 941 981 942 942 986 30 3.0% Page 62 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 FOSA (Pefluomoctanesulfonamide) Hydrolysis Study 50C; pH 11 All concentrationsin nglrnl. All areas x 16' 'OSA 99039-14041 99039-14042 99039-14043 99039-14044 99039-14065 99039-14046 PFOSAO59.D PFOSAO6O.D PFOSAffi1.D PFOSA062.D PFOSA063.D PFOSA064.D Retlimr 4.5 4.5 4.5 4.5 4.5 4.5 Area 196 393 1031 1995 3844 Conc. C 12.5 53 96 242 475 996 %Standard or %RSD 107% 96% 97% 95% 100% % Spike Recovery 'FOS 3etTime 1.7 3.7 3.7 3.7 3.7 3.7 3.7 Area 27 115 227 596 1126 2139 Conc. < 13.0 20 54 99 255 491 1026 Y-Standard or %RSD % Spike Recovery MeOH Blank MeOH Blank PFOSA069.D PFOSA070.D 4.5 C 12.5 4.5 C 12.5 3.7 < 13.0 3.7 < 13.0 80399PFOSA-021 PFOSA071.D Day 0 4.5 1906 105% 447 1% 80399PFOSA-022 PFOSA072.D Day 0 4.5 1884 450 80399PFOSA-023 PFOSA073.D Day 0 4.5 1856 440 80399PFOSA-024 PFOSA074.D Day 0 4.5 2893 707 80399PFOSA-045 PFOSA075.D Day 7 4.5 185299% 437 2% 80399PFOSA-046 PFOSA076.D Day 7 4.5 1884 446 80399PFOSA-047 PFOSA077.D Day 7 4.5 1906 453 80399PFOSA-048 PFOSA078.D Day 7 4.5 2810 692 80399PFOSA-069 PFOSA079.D Day 14 4.5 1933 101% 459 4% 80399PFOSA-070 PFOSA080.D Day 14 4.5 1782 427 80399PFOSA-071 PFOSA061.D Day 14 4.5 1855 430 80399PFOSA-072 PFOSA082.D Day 14 4.5 2845 692 80399PFOSA-093 PFOSA083.D Day 21 4.5 1871 446 80399PFOSA-094 PFOSA084.D Day 21 4.5 445 80399PFOSA-095 PFOSA085.D Day 21 4.5 445 80399PFOSA-096 PFOSA086.D Day 21 4.5 1913 445 3.7 0 0 3.7 0 0 3.7 0 0 3.7 568 236 3.7 0 0 3.7 0 0 3.7 0 0 3.7 570 239 3.7 0 0 3.7 0 0 3.7 0 0 3.7 584 242 3.7 0 0 3.7 0 0 3.7 0 0 3.7 0 0 91% 92% 93% 0% MeOH Blank MeOH Blank PFOSA0SO.D PFOSA091.D 4.5 < 12.5 4.5 c 12.5 3.7 < 13.0 3.7 < 13.0 80399PFOSA-117 PFOSA092.D Day 28 4.5 1829 104% 435 1% 80399PFOSA-118 PFOSA093.D Day 28 4.5 1886 436 80399PFOSA-119 PFOSA094.D Day 26 4.5 1853 444 80399PFOSA-120 PFOSA095.D Day 28 4.5 2800 697 80399PFOSA-141 PFOSAO96.D Day 35 4.5 1949 461 0% 80399PFOSA-142 PFOSA097.D Day 35 4.5 1921 464 80399PFOSA-143 PFOSA098.D Day 35 4.5 1911 464 80399PFOSA-144 PFOSA099.D Day 35 4.5 2819 704 80399PFOSA-165 PFOSA100.D Day 42 4.5 195595% 473 4% 50399PFOSA-166 PFOSAIOl.D Day 42 4.5 1831 444 30399PFOSA-167 PFOSA1OZ.D Day 42 4.5 1956 482 30399PFOSA-168 PFOSA103.D Day 42 4.5 2793 703 3.7 0 0 3.7 0 0 3.7 0 0 3.7 558 237 96 46 3.7 0 0 3.7 0 0 3.7 0 0 3.7 567 241 3.7 0 0 3.7 0 0 3.7 0 0 3.7 550 236 91% 93% 91% MeOH Blank MeOH Blank 99039-14041 99039-14042 99039-14'&03 99039-14044 99039-14045 99039-14046 Method ID: PFOSAIW.D PFOSA105.D PFOSAI06.D PFOSA107.D PFOSA108.D PFOSA109.D PFOSA1lO.D PFOSA1ll.D 0309-15C.M (A) The relative standarddevialfon(RSD) IS not define (B) Exculded; samples 80399PFOSA-094 and -09n5c 4.5 < 12.5 4.5 c 12.5 3.7 < 13.0 3.7 < 13.0 4.5 187 53 4.5 406 101 107% 101% 3.7 25 19 3.7 109 54 3.7 234 104 4.5 998 247 4.5 2105 533 4.5 3653 998 99% 107% 100% 3.7 3.7 2068 3.7 583 1185 262 549 1049 101% InternalStandard quant: ?=0.999 Curve Averaged, Quadrate. Orlgin ignored Cat. ranmgein. and max = 49.9 998 lntemai Standard quant: ?=0.999 Curve Averaged, QuadraticO, rigin ignored Cranl.mgein. and max = 51.0938 Original mnc.= 499.4 Splke conc.= 249.7 Spike conc.= 259.40 then the mean concentration IS zero. nalyzed.due to humanor mechanicalerror; no spike added to sample 80399PFOSA-096. BSA Letlime 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.6 3.8 3.8 3.8 3.8 3.6 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 Area 0 932 934 927 936 951 0 0 946 929 935 951 938 936 935 94 1 937 923 956 953 932 953 953 953 0 0 932 959 927 93 1 940 921 916 930 922 916 905 922 0 0 3.8 3.8 3.8 3.8 3.8 Conc. mean S.D. %SO. 882 913 880 890 903 225 930 19 2.1% Page 63 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Pooled FOSA Data and Slope Regression 0.10 0.05 0 8 0.00 2 -0.05 b 8 0 n 0 ., n r\ 0 8 0 - -0.10 y = -4.425E-06~ 1.997E-02 R2= 2.751E-06 0 -0.15 Dashed Lines: 2 0 Uncertainty Limits (Slope and Intercept) -0.20 I 20 0 10 30 40 50 time (days) SUMMARY OUTPUT RegressionSlalisbcs R Multlple O.Wl658616 2.7R51S0q1Eua-0r6e AdjustRed Squa 4.025638204 Standard Error 0.038763091 Observations 41 Ye 20 slope uncertainty 19309 ANOVA Regression Residual Total 0.058600673 dl ss 1.611211E-07 0.005.080610503059215177 40 MS 1.61211E-07 F SignificanceF O.WO10729 0.991788409 Coefficlenls Standard Ermr Intercept -0.0199726603.010823282 -4.4205.X30201V-E00a4-.r02i06a17.b0293l9e541870878409 1 Slat P-value -1.845304.20575259-02.08481864795 Lower 95% 6.000868587 Upper 95% Lower 95.0% 0-.0.0014911896447795 0.00-008.0509078368587 Upper 95.0% 0.00191947 0.000859736 Page 64 of 126 I I -I BACKTOMAIN 3M Environmental LaboratoryReport No.ELI 132 ELI1 3 2 0 . ~41/2~/2001 5:46PM and Rate TIl2 Calculations Shaded results included in the report. Incubation time (days) IParent FOSA4.994E+02 4.200E+01 Parent MasPsa(grerntlrnole) 4.990E+02 Analyte (LOQ) PFOS5.200E+01 (nrnlLrnOAl)Qn(naglyltrLe(ngOlA)rnQMlarAlnayosnteslael)yte 5.379E+02 Analyte (LOD) PFOS (nglrnLl)O(AgDnrnallrMyntaoeAslens)alyte 5.379E+02 Author: GMP PaPrOen(nt glrnl) 1.300E+01 Date: 4/02/01 PO (nrnlrnl) I.OOIE+OO Analyte LOD (nrnlrnl) 2.417E-02 Dat'aooled @50CSlopes (day-I) Slopes @25C (day-I) Regression Slope-820.68M6inEim-0u5m(day-I) -8.686E-04 Regression-4S.lo4p2e5EV-a0lu7e(day-I) -4.425E-06 Regression Slop8e.25097MEa-x0im5um (day-I) 8.597E-04 (EBq4's1a)8n8d,B9, - MaxH.-Life @25C (yeaCr)alcH.-Lif@e 25(Cyear) (N/A slope positive) 4291 Min. Half-Life @25C Page 65 of 126 BACK TO MAIN 3M Environmental LaboratoryReport No. ELI132 Appendix D: Selected Chromatograms A representative set of chromatograms from the present sitsuidnycluded in this Appendix. Page 66 of 126 BACK TO MAIN 3M Environmental Laboratory ReportNo. ELI 132 Batch Run # 3 of 57 Data File C:\HPCHEM\l\DATA\Ol24OO\PFOSA003.D Sample Name: MeOH Blank lI 100oj !', Page 67of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 B a t c h Run # 5 of 5 1 Data File C:\HPCHEM\1\DATA\Ol24OO\PFOSAOO5.D SampNlaem9e9:039-135-02 Page 68 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 12 of 57 Data File C:\HPCHEM\l\DATA\Ol24OO\PFOSA012.D Sample Name: 081399-BLK-1.5 1000 -! i\ min .. min ?- min . - ., min min min min min Page 69 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 13 of 57 Data File C:\HPCHEM\l\DATA\Ol24OO\PFOSAOl3.D -~ ' 60000 1 ~ 40000j 20000 -1 Sample Name: 081399-LCS-1.5 FOSA Hydrolysis pH 1.5 Lab Control 4 100000 -' 50000 i 1 I 10000~ i Data4 91/22:13/90:036 PM AES/ALS Page 2 of 4 Page 70 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Page 71 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. E L I 132 Page 72 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 : 1wooo 1I A Page 73 of 126 BACK TO MAIN WM Environmental LaborRaepetrtNoo.ErL11y32 BSacEh Efun L8 4i8 oaf 32 onemorzaoorerosness.o ---uaprE EATEN ~ sanpie~ Hane: 80399PFOS1A4-8 =a 2 Sn FOSA Hydrolysis ph 1.5 I{ lO orsECr hTT The ro l reBeia---- 5% ~ A mre m------5 =] i {gleee i Lsoao hs oo j worse TEoraksrosro Ares SS r b mn Imrmrda roncesa B rao msA = [oe Aa bl e redoe ne asderommen n J eer SO - L LEBN ee I =| A |3aotefr_--e I e3e ei e e _ e3 - TE = m --worsmbacbemmoc ssorseresenr wasno! i r i ea ee r Aso--e s Snr r mp 3L .- n ~ nm - Saad 3/21/00 12:45:03 FH ABE/ALS sage 2 of 4 Page 7801 128 BACK TO MAIN SM Enionmenta Laboratory Report No, EL1192 SBaEchNmEun 88 5S0hoef a57s\onmavonzaoorerosaoso. -= ETP] OSES : - -- mL rrosire i 115 frm,ealness/ mr ~ LT am morale ------ 5 = breamheat 2 r ER e nrrerA o ee ro ral re mmr feet: foe- ME ee I i 5eSlE erraraachers ossNemeE- I ay| = \, J mm Fn [L wsee ry odr es o heers TT oT Te ma | 4iL PISA NT Cef/ n -i TM 1be rme ecm kmE resy r----T -------- g A a wl ro ibr WeT lmswrap dee roemsg smsorre 3--3 CL . P 1 wy / sCas tiateSe Te Tn Dacad 3/21/00 12:45:23 BH ASS/NLS Fuge 2 ot 6 Pagoef12s6 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 52 of 57 Data File C:\HPCHEM\l\DATA\Ol240O\PFOSAO52.D Sample Name: 99039-135-02 - , MS0~1~4~;EIC~9~W99~(012400\PF0SA052;D)~APr-ES;Ne~SlM ____ -. - ............. - ..... FOSA Hydrolysis pH 1.5 Std 2 - 2nd inj Page 76 of 126 BACK TO MAIN 3M EnvironmentalLaboratory Report No. ELI132 Batch Run # 2 of 55 Data File C:\HPCHEM\~\DATA\O~~~OO\PFOSAO~~.D Sample Name: MeOH Blank 800 -i Data4 9/26/00 1:04:37 PM AES/ALS min min min min min P i' min min rnin min min min Page 2 of 6 Page 77 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 i ' 400 1 nsn Page 78 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 Batch Run # 11 of 55 Data File C:\HPCHEM\l\DATA\Ol240O\PFOSAO67.D ; 1000: 4 ' 750 Sample Name: 081399-BLK-3.0 .- min min min min ~ .. min min min .I rnin min mln min Page 79 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 ' 340 1 91/:D20a66t/:a00408 PM AES/ALS rnin 6 min rnin min rnin rnin 2 Page min of 6 Page 80 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 17 of 55 Data File C:\HPCHEM\l\DATA\Ol240O\PFOSAO73.D SamplNeame: 80399PFOSA-007 min , 100000 4 50000 { , lO0Oi j 750 4 Page 81 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. E L I 132 Batch Run # 18 of 5 5 Data File C:\HPCHEM\1\DATA\Ol24OO\PFOSAO74.D .-_ - 60000 40000 -: 20000 - Sample Name: 80399PFOSA-008 ~ .~- FOSA Hydrolysis pH 3 Day 0 - Sample Spike Page 82of 126 BACK TO MAIN 3M Environmental Laboratory Report No. EL1 132 Data4 9 / 2 6 / 0 0 1:10:54 PM AES/ALS min Page 2 of 4 Page 83 of 126 ~ ~~~ BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 I 2000 ,0001 A Page 84 of 126 ~~ BACK TO MAIN 3M Environmental LaboratoryReport No. ELI 132 Batch Run # 49 of 55 Data File C:\HPCHEM\1\DATA\Ol24OO\PFOSAlO5.D -~ 500 MSD1-499;lC=~98.6~499(.7012400\PFOSAl05.D~ APCES;Neg;SIM 400 Sample Name: MeOH Blank - ----- --. . FOSA Hydrolysis pH 3 ... MeOH Blank 1000 -; i ! .. . - . . 6 min .- ..6. min I 3504 + 600 91/:D21a61t/:a02400 I i . . 6 . min, .. .6.. min PM AES/ALS ,. I ... Page 2 of 6 Page 85 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 Batch Run # 51 of 55 Data File C:\HPCHEM\1\DATA\Ol24OO\PFOSAlO7.D Sample Name: 99039-136-02 MSD~499;EIC~49899~7~(01240O\PFOSA107:D)~API;ES;Ne~Sl~~ . i 1 10000 v) 5000 . . .- . . . . FOSA Hydrolysis pH 3 Std 2 - 2nd inj rnin I 100000 j i 500004 min min ! 1 20000 10000~ min min ,. min .-.- I rnin rnin min ... min .. -.~ mln Page 86 of 126 BACK TO MAIN 3M Environmental LaboratoryReport No. ELI132 Batch Run # 3 of 56 Data File C:\HPCHEM\1\DATA\Ol25OO\PFOSAOO3.D Sample Name: MeOHBlank 4 I ~ 800 : 340 -! Data4 92/:2265/:0005 PM AES/ALS .- .,. I min .. min min min Page 2 of 6 Page 87 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 Page 88 of 126 BACK TO MAIN c- I i 1 10001 i : 2000; c.-_. - - L.--- 1 2 9/D2a6t/a040 2:26:27 PM APEaSg/eALS / 3 \. 4 ___~ _ _ _ ~ 5 . .- ......... ............. 6 ~ - min 2 of 4 Page 89 of 126 BACK TO MAIN 3M Environmental Laboratory Report No.ELI 132 Batch Run # 13 of 56 Data File C:\HPCHEM\1\DATA\Ol25OO\PFOSAOl3.D I ' 60000: 40000 < : 20000 Sample Name: 081399-LCS-5.0 - ... FOSA Hydrolysis pH 5 Lab Conhol Page 90 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 1 I 10000 { Data4 9/26/00 2:27:21 PM AES/ALS Page 2 of 4 Page 91 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 1 100000 50000 i Page 92 of 126 - BACK TO MAIN 3M Environmental Laboratory Report No. EL.1132 ' I 1 J 600 Page 93 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. E L I132 Page 94 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. EL.1132 Batch Run # 50 of 56 Data File C:\HPCHEM\1\DATA\Ol25OO\PFOSAO5O.D Sample Name: MeOH Blank ? , '. 1000 -3 Page 95 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 52 of 56 Data File C:\HPCHEM\l\DATA\Ol250O\PFOSAO52.D I ~ 10000~ 1 5000 8 /k,, I.' Sample Name: 99039-137-02 FOSA Hydrolysis pH 5 Std 2- 2nd inj Page 96 of 126 ~~ BACK TO MAIN 3M Environmental Laboratory Report No. EL1132 Batch Run # 2 of 55 Data File C:\HPCHEM\l\DATA\Ol250O\PFC)~AO~f3.D Sample N a m e : MeOH Blank ~ 4001 600 j 500 i Page 97 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 4 of 5 5 Data File C:\HPCHEM\1\DATA\Ol25OO\PFOSAO6O.D ,4\v) i t5 I 50000: Sample Name: 99039-138-02 FOSA Hydrolysis pH 7 Std 2 -1st inj Page 98 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Page 99 of 126 ~- ~~ BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 ~ 100000 1 50000 1 i I ._ i I Page 100 of 126 BACK TO MAIN 3M Environmental LaboratoryReport No. ELI 132 I 200000 -j 100000j A;s 9/D2a7t/a040 11:13:02 AM APEaSg/eALS rnin 2 of 4 Page 101of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 i 3200000 1000Oo p4 \ .a, Page 102 of 126 ! 100000 -; , 50000, BACK TO MAIN 3M Environmental Laboratory Report No. E L I132 dm. 1% ....3 1 .. -MSD1-427; ElC'426.7:427.7 10000 :i 0 J-.--- - ~__.___-____1 _ - .-. ....... 2 4 5 min ( O l 2 5 O O \ P F O S ~ l O 2 ; D ) ~ A P l ~ E S ~ N e ~ S...l ~ ~ ~ ~ ~ ~ ~ ~~ 2 zv) 8, a ,_~_. ~ 3 4 - . ........ . ... . . ... . 5 6 ...... ~~ .. min 91/D12a:7t1/a704:011 AM AES/ALS Page 2 of 4 Page 103 of 126 ~~~ __ BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 4 7 of 55 Data File C:\HPCHEM\l\DATA\Ol25OO\pFOSA103.D Sample Name: 80399PFOSA-160 1' 8 !-MSD1499;ElC~49~614~~0~2500\PFOS~iO3~~-AP~ES~SlM~~-~~- -~ ' 60000i ' 40000 .u, , 20000; 14 3, . FOSA Hydrolysis p H 7 Day 42 - Sample Spike 100000 , soooo~ 1 lo5o0o0o0o0 .1. 8 '2 a Page 104 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 49 of 55 Data F i l e C:\HPCHEM\1\DATA\Ol25OO\PFOSAlO5.D Sample Name: MeOH Blank Page 105 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 1 20000j I ; 10000~ , 10000 { 0 A .....- . -_ 1 2 9/D2a7t/a040 11:17:57 AM AES/ALS m 0. ..... ..... .- . . ... .. . 3 --4 ....__ 5 . . . . . - 6 .... min Page 2 of 4 Page 106 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. EL112 BBaatetn enusn &# { 3 of R 56 a oe menon r2001i prosan oos 0 Sample Name: Weck Blank I=" sora ere Sg l Toso 1 ee pena ri serch Tro ER SG Fr eeec Ae h 3 e 5m me ee | = I e Tm R I Se momo ------ Bl mS Se Ih rem g Tg . s ri re eer e Te ol ad Norms [I = vr ---------------- -- , PELi-_ re--------a --TTRi I FrBBLew AcA Tl r re a= o Amabepe Nmu nETT ~- worsens redraw 5 TT r von e echo nre waroesaTET om | \ ey Se Datad 5/21/00 3:46:28 mw AS/ALS Page 3 of Page 107 of 126 BACK TO MAIN 3M EnvironmentalLaboratory Report No. ELI132 -; 15000 10000 5000 -: 0 \--..-- i 2 3 3 : 49 6/ 2: 47D7/ 0a0t a 4 PM AES/ALS _ _ _ _ ~ __ ..-. 4 5 -.- .- 6 -. min P a g e 2 of 4 Page 108of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 4 1500 1000 4 + 4000 2000 : -: - _ _ _ 93/:D24a77t/:a05400 - -iII >,:''\\ __ 1 2 PM AES/ALS /. 3 4 ~ 5 ... - . _ _ _ ~ _. .._............. -. 6... . min 2 Page of 6 Page 109 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 j 100000 S, , g , 50000 -j 0: , , , , .,, , , I ,__-_I---- .. ... -__ . . . ---. 1 2 3 4 5 6 - - rnin MSDl427;ElC=426.7727:7~(01260U\PFOSAO~l3ID~API~ES~~IM~~~~~~~ 15000 10000 4 5000 4 0: , , , ' , . . 1 2 av) E\%, 3 4 _ _ .____ __ 5 6 ..... min Data4 9/27/00 3:48:01 PM AES/ALS Page 2 of 4 Page 110 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 18 of 5 6 DatFaile C:\HPCHEM\1\DATA\Ol26OO\PFOSAOl8.D _- -MS[Tl~499~EIC~498T619~7(012600\PFOSAOTB1D)APFES~~lM 10000 j SamplNeame8:0399PFOSA-019 ._ __. FOSA Hydrolysis pH9 Day 0 - Sample Trip 2 j 50000{ min .min min min Page 111 of 126 ~~ ~ ~~~~~ BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 19 of 56 DatFaile C:\HPCHEM\1\DATA\Ol26OO\PFOSAOl9.D _ _ -.-- M s D r 4 9 9 ; E I C ~ 4 9 ~ 6 ~ 9 ~ U ~ 2 6 O O ~ P F U S A ON~elgE. SDIM~ P ~ S . I:e':., ! 4 40000 i v) 20000 2 SamplNeame: 80399PFOSA-020 - -. . FOSA Hydrolysis pH 9 Day 0 - Sample Spike I ? , 50000$ 1 100000 50000 Page 112 of 126 ~ _ _ _ ~ ~ ~~~~~ ~~ BACK TO MAIN 3M Environmental Laboratory Report No.EL1132 /? i I ~ 10000~ Data4 9/27/00 3:52:59 PM AES/ALS Page 2 of 4 Page 113 of 126 ~~ ~ BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 48 of 56 Data F i l e C:\HPCHEM\l\DATA\Ol260O\PFOSAO48.D Sample Name: 80399PFOSA-164 I M S r r r 4 9 9 ; E l ~ E ~ ~ ~ ~ ~ ~ ~ P F O S ~ O ~ E ~ ~ P F E ~ -~_M_- -. .- 1 400004 I 2ooooj av) ,,,:./ . FOSA Hydrolysis p H 9 Day 42 - Sample Spike ~ 500001 low00 50000 ~ D a t a 4 9/27/00 3:53:08 PM AES/ALS Page 2 of 4 Page 114 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 50 of 56 Data File C:\HPCHEM\1\DATA\Ol26OO\PFOSAO5O.D Sample Name: MeOH Blank 1 ,, 1000 -j r\ Page 115 of 126 BACK TO MAIN 3M Environmental Laboratory Report No.ELI132 Batch Run # 52 of 56 Data File C:\HPCHEM\1\DATA\Ol26OO\PFOSAO52.D Sample Name: 99039-139-02 MSor49s;El~~9~~49~~26O~FOSAU5~~~~~slM 10000 ; 5000 : /: . 8v) FOSA Hydrolysis pH 9 - '( Std 2 2nd inj 0: IC -., -._ --I I 1 2 3 4 5 6 ~ M S ~ f 2 9 a ; E r C ~ 2 9 ~ ~ ; 2 6 0 0 ~ P F O 5 ~ 0 5 Z ; D T A P F E S ~ N ~ S l M ~- ~ ~ ~ ~ ~ - ~ - - - i 50000: ' 4 20000 10000 -i Data4 9/27/00 3:53:50 PM AES/ALS Page 2 of 4 Page 116 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 2 of 55 Data F i l e C:\HPCHEM\l\DATA\Ol260O\PFOSAO58.D 5w -! Sample Name: MeOH Blank FOSA Hydrolysis pH 11 MeOH Blank 500 .i . 400 : 300 +-...._ . ._ . ___ __- __ ~ , - ., ._.__. - - _. -. _ - _.-- . 1 2 3 4. ...MSD1-427;EIC=426:77427;7 (012600\PFOSA058.D) --API-ES, Neg;SIM -1 600 -i 500 __ -.__ 400: . . . . . _.__.c_-l__-_ .- _ -... _ ___1 2_ - .. .--~ - 3 4 Data4 9 / 2 8 / 0 0 9:58:36 AM AES/ALS . ~. .. .... 5 --..- _ - __5_ _ _ ..... - . .. 6 min ._. ~ .... ........ 6. min Page 2 of 6 Page 117 of 126 50000 ; BACK TO MAIN 3M Environmental Laboratory Report No. EL1132 rnin ? I 2OWO { ~ loooor 10000 -: .......... 0 -:____:_. 99/D:2a58t8/a:04505 3 r _ _ ~ 1 - . . _ - Le- _ _ _ ............ _ ~ -, ~ ~ 1 2 _ ~ 3 _ 4 ~ __5 .... 6 rnin AM AES/ALS Page 2 of 4 Page 118 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 Batch Run # 11 of 55 Data File C:\HPCHEM\1\DATA\Ol26OO\PFOSAO67.D Sample Name0:81399-BLK-11.0 1 600 500 -! ' 1oooj ~ 800 I 6001 /-'j ! 'I 9/D2a8t/a040 9:59:57 AM AES/ALS Page 2 of 6 Page 119 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 B a t c h Run # 12 of 5 5 D a t a File C:\HPCHEM\1\DATA\Ol26OO\PFOSAO68.D 60000 L 40000 ; 20000 : ' 2 500001 S a mNpal me e : 081393-LCS-11.0 FOSA Hydrolysis pH 11 Lab Control ~~ . rnin min - .~. rnin .rnin .~ , min ! .. mi? _ _- 1 2 3 4 ~SD1~526;EIC~525;7826;r(Oi(2600\PFOSA06~D)~API:ES;N(rg;SIM-~~' 4 4 100000 3 50000 8 10000 : 9 0 D a t a 4 9/28/00 10:00:08 AM AES/ALS rnin I I .I rnin' .5............. --6 .... rnin min rnm Page 2 of 4 Page 120 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 I 1 i l o ~ o o l r Data4 9 / 2 8 / 0 0 10:00:55 AM AES/ALS Page 2 of 4 Page 121 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI132 Batch Run # 18 of 55 Data File C:\HPCHEM\l\DATA\Ol260O\PFOSAO74.D Sample Name: 80399PFOSA-024 MSD1-499~EIC~~98;6199~(0~26OO\PFOSAO7~D~~~ES~Neg~SlM~~~ ! I i FOSA Hydrolysis pH 11 8 - I 40000 j ; 20000 /h. Day 0 Sample Spike io. I 200000~ 1 100000 4 9/D2a8t/a040 10:01:03 AM2 APEaSg/eALS of 4 Page 122 of 126 BACK TO MAIN 3M Environmental Laboratory Report No. ELI 132 Batch Run # 4 6 of 55 Data File C:\HPCHEM\1\DATA\Ol26OO\PFOSAlO2.D SamplNeame: 80399PFOSA-167 I M S D ~ l ~ ~ 9 ; E l ~ 4 9 8 ~ 6 ~ ~ 9 9 ~ ( 0 ~ 6 0 0 ~ F O ~ ~ i O 2 ~ A P F E S ~ e ~ .l M ... - ... ~ 10000, FOSA Hydrolysis pH 11 Day 42 - Sample Trip 50000 4 ; Q B -___ 1 2 3 4 5 -M S D 1 - 4 2 7 ; E I ~ ~ 2 6 ~ 7 ~ 2 ~ U l 2 6 0 0 ~ P F O S R I O Z D ~ F E S ~ ~ S l M 1 v) 10000 r /$i 0 .-L - i I + \.. - 2 3 4 ___ 5 . 9/D2a8t/a040 10:05:07 AM AES/ALS -.- -. . 6 .rnin ............ -~ 6 min . ~ ~~ Page 2 of 4 Page 123 of 126 BACK TO MAIN Batch Run # 47 of 5 5 DatFaile C:\HPCHEM\l\DATA\Ol2600\PFOSA103.D SamplNeame8:0399PFOSA-168 --MS~~49s;Er~9~6~499~~Ul2600~PFOSA1D31D~APFES~N~Sl~ - - .; 9 40000 v) FOSA Hydrolysis pH 11 i - 20000; j a& '> i' Day 42 Sample Spike ___ o : , , , . ..-....-.. - .. i 2 3 4 5 6 mn I1 5000041 ; 10000 0: 9/D2a8t/a040 I 9 0 1 2""' 10:05:15 AM APEaSg/eALS In 3 4 ___ ___ _ _ _ _ ~ _ _ >. ~ _ . 5 6 -..l i n ~ 2 of 4 Page 124 of 126 BACK TO MAIN aM Environmental Laboratory Roport No. EL1132 sBaetelaeun #&4e5 oif t55 onmmorzsooprosaios.o Savple Nave: eo Blanc S I; E ; Fosuois itn Lm fo MeOH Blank P s l > or rac ree m AserTe T m E r e s P R e mmn mve e Mr Sm To AS r TEe Te wl A woraroclersaes eros sr 3 4mm i| =nJ = rerse r T A e TT 2 telox SN pe T re[ER |= Nps iF B reS s Abee r merIecEe SS A Bl| " hat S-- | = OTE BIC S16 ITOFOSATOSDY PRESNRSW rs . rr Es i: B re. cl h_ rre e om rm oe aoerros [--S --sh aoreareecnloeeranrre oemseadsmoenT orl = al A emer Data 3/20/00 10:05:34 Mn ABE/ALS vage 2 of 6 Page 125.01 126 BACK TO MAIN 3M Environmental Laboratory Report No.ELI 132 Batch Run # 51 of 55 Data File C:\HPCHEM\1\DATA\Ol26OO\PFOSAlO7.D I 10000~ 5000 .: Sample Name: 99039-140-02 --.~ FOSA Hydrolysis Std 2 - 2nd inj pH 11 Page 126 of 126