Document Ra3Z1LY98JQNKQNmzX279vK0z

BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Study Title Hydrolysis Reactions of Perfluorooctanoic Acid (PFOA) Data Requirement: Based on OPPTS: 835.2110 Author Thomas L. Hatfield, Ph.D. Study Completion Date March 30, 2001 Performing Laboratory 3M Environmental Laboratory Building 2-3E-09, 935 Bush Avenue St. Paul, MN 55106 Project Identification 3M Laboratory Report No: E00-1851 Total Number of Pages 99 Page 1 of 99 BACK TO MAIN 3M Environmental Laboratory Keport No. E00-1851 This page has been reserved for specific country requirements. Page 2 of 99 BACK TO MAIN 3M Environmental Laooratory Keport no. tu u - io tn Statement of Non-Compliance Study Title: Hydrolysis Reactions of Perfluorooctanoic Acid (PFOA) Study Identification Number: E00-1851 This study does not fully comply with the requirements of the US EPA Good Laboratory Practices (GLP) Standards at 40 CFR Part 792 (TSCA). However, many GLP standards were used in the development of the analytical method (Appendix A), and many of the quality assurance procedures followed in this study were based on the practices described in the GLP documentation. Page 3 of 99 BACK TO MAIN 3M Environmental Lauuraiury rteport ino. c u u - io i Quality Assurance Statement Study Title: Hydrolysis Reactions of Perfluorooctanoic Acid (PFOA) Study Identification Number: E00-1851 The following table provides details of the audits performed by the 3M Environmental Laboratory Quality Assurance Unit (QAU). Inspection Dates 3/2/01 3/26-30/01 Phase Data and Draft Report Date Re ported to Management Study Director 3/2/01 3/2/01 Data and Draft Report 3/30/01 3/30/01 .n J) QAU Representative fo o /o t ' Dat Page 4 of 99 BACK TO MAIN 3M Environmental Laooratory Keport n o . tu u - w o i Table of Contents Statement of Non-Compliance..............................................................................................3 Quality Assurance Statement................................................................................................4 List of Tables...........................................................................................................................6 List of Figures..........................................................................................................................6 Study Personnel and Contributors.........................................................................................6 Location of Archives............................................................................................................... 7 Summary.................................................................................................................................8 Introduction.............................................................................................................................9 Summary of Kinetics Model................................................................................................. 10 Materials and Methods......................................................................................................... 11 Chemical Characterizations............................................................................................ 11 Sample Preparation........................................................................................................ 11 Sample Analysis.............................................................................................................. 12 Deviations.........................................................................................................................12 Results and Discussion....................................................................................................... 13 Data Quality Objectives (DQO's)....................................................................................13 Anomalous Analytical Results.........................................................................................13 Statistical Methods and Calculations..............................................................................14 Data Summary and Discussion.......................................................................................14 Conclusions...........................................................................................................................18 References............................................................................................................................19 Signatures.............................................................................................................................20 Appendix A: Analytical Method............................................................................................21 Appendix B: Kinetics Model.................................................................................................38 Appendix C: Selected Analytical and Kinetics Results......................................................48 Appendix D: Selected Chromatograms.............................................................................. 71 Page 5 of 99 BACK TO MAIN 3M Environmental uaDoraiory rcepon ino. euu- io i List of Tables Table 1. Summary of Results Based on PFOA Concentrations........................................ 8 Table 2. Summary of Results Based on the Mean and Precision of PFOA Measurements........................................................................................................ 8 Table 3. Characterizations of Test and Reference Substances...................................... 11 Table 4. Observed (50 C) Degradation Rates of PFOA in Aqueous Buffered Solutions and at Various pH Levels......................................................................................15 Table 5. Degradation Rate and Half Life of PFOA in Aqueous Buffered Solutions Using Data Pooled Over pH Levels 5.0, 7.0, and 9.0................................................... 15 Table 6. Degradation Rate and Half Life of PFOA in Aqueous Buffered Solutions Based on the Concentration Mean and Standard Deviation.......................................... 17 List of Figures Figure 1. Structure of the Ammonium Salt of PFOA...........................................................9 Figure 2. Observed PFOA Degradation for Various pH levels.........................................14 Figure 3. Pooled (pH = 5.0, 7.0, and 9.0) PFOA Data and Slope Regression................ 16 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 Laboratory and Professional Services Contributing Personnel Debra Wright Jan Schultz Joseph J. S. Tokos, Ph.D. (Pace Analytical Services, Inc., 1700 Elm St., Minneapolis, MN 55144) Jill Maloney Karen Johnson (Braun Intertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 55439) Grant M. Plummer, Ph.D. (Rho Squared, P.O. Box 61536, Durham, NC 27715) Page 6 of 99 BACK TO MAIN 3M Environmental Laooratory Keport no. tu u - ie tn 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 at least 10 years following the effective date of any related final ruling. Information may be obtained through written inquiry addressed as follows: 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Page 7 of 99 BACK TO MAIN 3M Environmental Laboratory Keport No. E00-1851 Summary We report here the results of our study of the hydrolysis of perfluorooctanoic acid (hereafter, PFOA). Our methods are described below and in Appendix A to this work; our results are based on the observed concentrations of PFOA in buffered aqueous solutions as a function of time. 3M's Environmental Laboratory staff developed the study procedures; they are based on EPA's OPPTS Guideline Document 835.21101but do not fulfill all the requirements of the guideline. Our methods are described below and in Appendix A to this work; our results are based on the observed concentrations of PFOA in buffered aqueous solutions as a function of time. The chosen analytical technique was high performance liquid chromatography with mass spectrometry detection (HPLC/MS). Table 1 summarizes the results of the study. During this study, we prepared and examined samples at six different pH levels from 1.5 to 11.0 over a period of 109 days, and our results indicate no dependence of the degradation rate of PFOA on the sample pH level. Our results based on the PFOA concentrations, pooled over three pH of the six levels (5.0, 7.0, and 9.0), are presented in Tables 1 and 2. Table 1. Summary of Results Based on PFOA Concentrations Observed Rate Constant at 50 C (d a y 1) 8.1 x 10 s Calculated Rate Constant at 25 C (d a y 1) 8.1 x 10b Calculated Half Life at 25 C (years) 235 Calculated (2cr) Minimum Half Life at 25 C (years) 92 Th e m ean value and precision of PFO A concentration measurem ents provide a second estimate of the PFOA half-life, presented in Table 2. Table 2. Summary of Results Based on the Mean and Precision of PFOA Measurements Maximum Possible Rate at 50 C (d a y 1) 2.0 x 10"4 Maximum Calculated Rate at 25 C (d a y 1) 2.0 x10 s Calculated Half Life at 25 C (years) >97 Page 8 of 99 BACK TO MAIN 3M Environmental Laboratory Keport No. tuu-1851 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 hydrolysis of PFOA (or, more generally, its degradation in the presence of H2O) is addressed in this report. The structure of the ammonium salt of the PFOA is illustrated in Figure 1. This is the actual test material used in the study. Figure 1. Structure of the Ammonium Salt of PFOA PFOA FFFFF F F ------------------------------------------------------------- FFFFF F H H -N -H i H Page 9 of 99 BACK TO MAIN IIIIIKMI 3M Environmental Laboratory Report No. E00-1851 Summary of Kinetics Model A full mathematical description of the kinetics model employed in this study is presented in Appendix B. The study data allow two independent estimates of the hydrolytic half-life of PFOA. The first estimate (see Table 1) is based on the observed degradation of the "parent" compound PFOA in dilute, appropriately buffered aqueous solutions. Equation 1 describes the estimated half-life ( ^ ) in terms of the estimated total parent hydrolysis rate k p (see Appendix B, Equation B10): 2) We determined the quantity k pfrom the experimental data as described in Appendix B. To determine the relevant concentration ratios at each pH level (see Equations B8 and B9), we used either the data corresponding to "Day 0" (t = 0) or the earliest available data achieving the data quality objectives of the analytical method. A second half-life estimate (see Equation B37) is available from the mean p and standard deviation c of the observed PFOA concentrations, assuming that they were essentially constant over the experimental portion of the study. This estimate is (T pp '\2 >~ (1t i/p2L\ _ (k 2) ) _ p A 2t a 2 ) ' Eq' 2 where A t represents the sample incubation period. All the samples used in this study were maintained at a reaction temperature of 50 ( 3) C. The quoted results, valid for the reaction temperature 25 C, were estim ated from our experim ental results according to methods described in Appendix B (Eqs. B38 and B39). Page 10 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. EOO-1851 Materials and Methods Details of the characteristics of the test materials, sample preparation techniques, and analytical methods are presented in Appendix A (ETS-8-212.0, "Preparation of Perfluorooctanoic Acid (PFOA) Hydrolysis Samples in Buffered Solutions and Analysis by High Performance Liquid Chromatography with Mass Spectrometry Detection.") A summary of these items is 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 June 15 and November 12, 2000. Chem ical C haracterizations Table 3 describes the sources and properties of the materials used in this work. These materials were used to prepare both the samples and the quantitative standards used to quantify them. For this reason, and because the related calculations involve only ratios of the compound concentrations (see Appendix B, Equations B8 and B36), the resulting rate and half-life estimates are largely independent of the material purity levels. Table 3. Characterizations of Test and Reference Substances Source Chemical Lot Number8 Physical Description Molecular Weight (gm mole'1) PFOA (Ammonium Salt) 3M ICP/PCP Division TCR-00930-30, Lot 332 White powder 431 PFBS (Ammonium salt) 3M Specialty Chemicals TCR-99030-28, Lot 101 White powder 317 Aperfluorobutanesulfonate Sam ple Preparation We prepared four 5.0-mL aqueous buffer samples (a sample, a duplicate, a triplicate, and a "matrix spike") at each of six pH levels (1.5, 3, 5, 7, 9 and 11) for analysis at eight time intervals (0, 7,14, 28, 42, 64, 84 and 109 days). Buffered solutions containing 5154 ng/mL of the analyte PFOA formed the basis of all these samples. The chosen buffer solutions are described fully in Appendix A. All the samples were prepared simultaneously, and all but the "Day 0" samples were placed in an incubator/orbital shaker maintained at 50 ( 3) C. One of the "Day 0" samples and a blank were spiked with the PFOA solution, diluted 7:1 with methanol containing the internal standard perfluorobutanesulfonate (PFBS) and frozen. The resulting PFBS concentration in all these samples was 158 ng/ml; the resulting PFOA concentration in the spiked samples was 143 ng/ml above the original sample concentration. After the appropriate incubation times, subsets of the sample vials were removed from the incubator and then spiked (as required), diluted, and frozen as Page 11 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. EOO-1851 described immediately above. Except during the relatively short periods of time required to prepare them, the samples were shielded from light. Nine calibration standards containing PFOA (25 to 999 ng/ml) and PFBS served as the quantitative basis of the study. All these standards were prepared in 1.5 mL of the appropriate pH buffer solution and 8.5 mL of methanol. Sam ple Analysis The equipment we used for the HPLC/MS 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 G1316A column heater maintained the column temperature at 40C, a quaternary pump supplied a column flow rate of 0.3 mL/min, and an ALS Model G1313A auto-sampler provided 10 pL sample injections. The detector was a Hewlett Packard MSD mass spectrometer, operated in negative-mode electrospray ionization mode; the anions of PFBS and PFOA were detected at the mass-to-charge (m/z) ratios 299 and 413, respectively. We processed the resulting data using the computer program Target NT Genie Integrator. Further analytical details, including the gradient elution program, instrument and detector parameters, and performance specifications, are presented in Appendix A. D ev iatio n s No deviations from the procedures defined in the analytical method (Appendix A) were noted during the study. All calibration and sample results that failed to meet the data quality objectives of the method (and were excluded from further analysis) are noted in the following sections. Page 12 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Results and Discussion D ata Q uality O bjectives (DOC^s) We briefly describe the data quality objectives applied in this study below. Appendix A describes them in greater detail. 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 by pH level. Calibrations. The minimum acceptable coefficient of determination (r2) for linear fits to calibration data is 0.990. The acceptance criterion for individual calibration points is that their values fall within 25% of the linear fit value; data outside this range are excluded and the linear fit is recalculated. Data for the high or low calibration standards may be rejected, though this results in a smaller effective calibration range. The average results of calibrations performed before and after the analytical procedures are used to calculate the analyte concentrations. Continuing Calibration Verification (CCV). Selected calibration samples are examined at the beginning of, during, and at the end of each analytical procedure. The results may not deviate by more than 25% of the known values. Sample Spikes. The acceptable percent spike recovery range is 70% to 130%; recoveries outside this range % place the analysis out of control, and require intervention by the Team Leader or designee. Analyte specificity is demonstrated by acceptable analyte spike recoveries. Identically Prepared Samples. Triplicate sample results with relative standard deviations (RSDs) greater than 25% place the analysis out of control, and require intervention by the Team Leader or designee. Solvent Blanks. Concentration results for solvent blanksmust exceed neither 5% of the highest calibration standard nor 25% 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. Anom alous A nalytical Results With the following exceptions, our analytical results met or exceeded the data quality objectives of Appendix A. Spike Recoveries. Results for five of the eight sample triplicates for pH = 3.0 failed to meet this data quality objective. Least squares determinations of a slope and offset from the three remaining data points at this pH would be highly undetermined, so we have excluded all the pH = 3.0 data from further consideration. Similarly, results for seven of the eight sample triplicates for pH = 11.0 failed to meet this data quality objective. No least squares determinations of a slope are possible in this case, so we have excluded all the pH = 11.0 data from further consideration. Finally, the "Day 14" samples at pH = 1.5 (061500-PFOA-075 through 061500PFOA-078) failed to meet this spike recovery data quality objective, and we have excluded these data from the following rate and half-life estimates. Page 13 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 S tatistical M ethods 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 of the acquired data. Our linear regressions included the determination of constant terms, that is, we did not force the regression fits to pass through the origin. As described in Appendix B (Equations B38 and B39), rates measured at 50C were extrapolated to 25C by dividing by a factor of 10; this approximation is valid for reactions with Arrhenius heats of activation near 18 Kcal/mole.2 D ata Sum m ary and Discussion The LOQ is defined as the concentration of the lowest (accepted) standard in the calibration set for which the known concentration exceeds 400% of the indicated solvent blank level (see Appendix A). During this study, the LOQ for PFOA was 25 ng/mL. Results for the internal standard (PFBS) were very consistent throughout the study. The percent relative standard deviations of the measured values, calculated for each of the four pH levels discussed here (1.5, 5.0, 7.0, and 9.0), ranged from 1 to 2%. Figure 2 illustrates the concentration ratios for the four pH levels versus time. Table 4 presents the results of the 50C rate determinations based on these data. Figure 2. Observed PFOA Degradation for Various pH levels. Time (days) Page 14 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Table 4. Observed (50 C) Degradation Rates of PFOA in Aqueous Buffered Solutions and at Various pH Levels. PH Observed Slope (d a y 1) Percent (2o) Slope Uncertainty (day1) 1.5 1.7 x 10`4 5.0 -1.5 x 10'4 7.0 1.8 x 10'5 9.0 -1.1 x 10'4 597 76 664 244 The slopes in Table 4 are small in magnitude, of varying sign, and only poorly determined; their percent relative 2o (95% confidence) uncertainties range from 76% to 664%. The data do not indicate degradation of PFOA at any of the four pH levels. In the absence of a clear trend relating the degradation rate to sample pH, it is appropriate to "pool" the data from all pH levels and to determine the degradation rate using the entire data set. The mean concentrations (ng/ml) at the pH levels 1.5, 5.0, 7.0, and 9.0 are 464, 653, 649, and 657. The pH = 1.5 data are clearly not equivalent to the data at the other three pH levels; this is an effect of ion pairing at the lowest pH level. Under these circumstances, the only reliable data for a pooled estimate are the data at pH levels 5.0, 7.0, and 9.0. Figure 3 illustrates the results of this pooled analysis according to Equation 1, and Table 5 summarizes the results of the analysis. Table 5. Degradation Rate and Half Life of PFOA in Aqueous Buffered Solutions Using Data Pooled Over pH Levels 5.0,7.0, and 9.0 Observed Rate Constant at 50 C (d a y 1) 8.1 x 10 s Percent (2a) Rate Constant Uncertainty at 50 C (d a y 1) 150 Calculated Rate Constant at 25 C (d a y 1) 8.1 x 10 Calculated Half Life at 25C (years) 235 Calculated (2a) Half Life Minimum at 25 C (years) 92 Page 15 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Figure 3. Pooled (pH = 5.0, 7.0, and 9.0) PFOAData and Slope Regression. The mean and standard deviation of the PFOA data provide an alternative estimate of its half-life. Details of the related calculations are presented below in Appendix B. The maximum degradation rate is given in Equation 3 (see Equation B36): k pP < (\ kPp/)max 2cp Pp A t and the minimum half-life is given in Equation 4 (see Equation B37): T 1/2P > (\t *?p )/r bi(2) _ p-p A tln (2 ) (\ k PP/)max 2 a PP Eq. 3 Eq.4 Page 16 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 In both Equations 3 and 4, the mean PFOS concentration ( jlip ) and standard deviation ( a p) can be either molar or mass quantities. Table 6 presents the results of the calculation. Table 6. Degradation Rate and Half Life of PFOAin Aqueous Buffered Solutions Based on the Concentration Mean and Standard Deviation At (days) 109 (ng/ml) 653 oP (ng/ml) 7.0 Maximum Observed Rate at 50 C (day'1) 2.0x10"* Maximum Calculated Rate at 25 C (day'1) 2.0 x 10' Calculated Half Life at 25 C (years) >97 Page 17 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Conclusions We have performed a study of the aqueous hydrolysis of perfluorooctanoic acid (PFOA) at 50C and extrapolated the results to 25C. We included six different pH levels in the study, though data from two of these pH levels (3.0 and 11) failed to meet the data quality objective for matrix spike recovery. We also rejected the data obtained for pH = 1.5 because ion pairing led to artificially low concentrations for all the incubation periods. Our results for the remaining pH levels (5.0, 7.0, and 9.0) indicate no clear dependence of the degradation rate of PFOA on pH. From the data pooled over these three pH levels, we estimate that the hydrolytic half life of PFOA at 25C is greater than 92 years, with the most likely value of 235 years. From the mean value and precision of PFOA concentrations, we estimate the hydrolytic half-life of PFOA to be greater than 97 years. Page 18 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 References "Fate, Transport and Transformation Test Guidelines: 835.2110: Hydrolysis as a Function of pH," U.S. EPA Office of Prevention, Pesticides and Toxic Substances, publication number 712-C-98-057, January 1998. Experimental Physical Chemistry", F. Daniels, et al., McGraw Hill Book Co. (New York), p. 131,1962. Page 19 of 99 Signatures Thomas L. Hatfield BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 rejects Team Leader William K. Reagen, Ph.D., Laboratory Management Date Page 20 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Appendix A: Analytical Method Method Number: ETS-8-212.0, "Preparation of Perfluorooctanoic Acid (PFOA) Hydrolysis Samples in Buffered Solutions and Analysis by High Performance Liquid Chromatography with Mass Spectrometry Detection." This Appendix presents the analytical method employed in this study. Page 21 of 99 I I' BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 3 M E n v ir o n m e n t a l L a b o r a to r y M ethod P r e p a r a t io n o f P e r f l u o r o o c t a n o ic A c id (PFO A) H y d r o l y s is Sa m p l e s i n B u f f e r e d So l u t io n s a n d A n a l y s is b y H ig h Pe r f o r m a n c e L iq u id C h r o m a t o g r a p h y w it h M ass Sp e c t r o m e t r y D t e c t io n Method Number: ETS-8-212.0 Adoption Date: Effective Revision Date: Approved By: Laboratory Management O 3 /2 7 /0 , Date Team Leader D a te ^ ETS-8-212.0 PFOA Hydrolysis andAnalysis by HPLC/MS Page 1 of 16 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 1.0 Scope and Application________________________________ ______________ 1.1 This method describes how to test for possible hydrolysis reactions o f perfluorooctanoic acid (PFOA) in buffered solutions of pHs 1.5, 3.0, 5.0, 7.0,9.0, and 11.0. The method is based on EPA OPPTS:835.2110 (Reference 18.1). Hydrolysis products are analyzed by high performance liquid chromatography (HPLC) with mass spectrometry (MS) detection and quantitation. PFOA anion is quantified using the anion o f perfluorobutanesulfonate (PFBS) as an internal standard. Representative chemical structures are shown in Attachment A. 1.2 Compatible analytes. PFOA and PFBS samples may be prepared and analyzed by this method. 1.3 Acceptable matrices. Aqueous buffered solutions ranging from pH 1.5 to 11.0 are acceptable. 1.4 M ethod Performance. This method is defined as performance-based (see Section 14). 2.0 Summary of Method 2.1 This method is based on OPPTS:835.2110 and has been modified to give additional information. Specifically, multiple time points over far longer periods o f time are used to provide additional information regarding the hydrolytic behavior. Additional pH's are tested to provide insight into acid/base catalysis. Because o f the longer time points used, (e.g. 109 days vs. 7) and the multiple time points (7 or 8 vs. 2) the temperature requirement of 0.1C has been relaxed (it is impossible to hold this tight of temperature and open the incubator to take out samples.) Oxygen is to be excluded (according to the OPPTS methodology) to minimize bacterial growth. However, the 50C temperature used in the present study is forbidding to most mesophillic organisms and the pH dependence for bacterial growth is different than that observed for most chemical reactions that occur in water. Aliquots of PFOA solution are added to sample vials that contain 5 mL of buffered solution of pH 1.5,3.0, 5.0,7.0,9.0, or 11.0. Appropriate quality control samples are prepared. Sample vials are tightly capped and placed into an orbital incubator/shaker at 50 3 C and 100 50 RPM, except for Day 0 samples, which are immediately refrigerated at 4 3 C or frozen at -20 10 C. Sample vials are removed from the incubator/shaker at designated intervals and refrigerated or frozen. When analyzed, all samples are allowed to come to room temperature, diluted with approximately 30 mL of methanol containing an internal standard, spiked (for those samples receiving spikes) and mechanically shaken for approximately 15 minutes. Samples are aliquoted into separate autovials. Calibration and quality control samples are prepared. PFOA is separated on a reverse-phase Dionex IonPacNG-l HPLC column, using an H20/MeOH solvent gradient containing ammonium acetate. Analytes are detected and quantified by electrospray ionization mass spectrometry in the negative-ion mode. ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/MS Page 2 of 16 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3.10 3.11 3.12 3.13 3.14 Definitions M ethod blank. The method blank determines if there is contamination of the matrix. It is prepared identically to other samples, but it does not contain analyte (see Section 12.1.1). It is used alone and in conjunction with a method spike to detect accidental contamination (see Section 14.3). Method spike. A method spike is a spiked method blank (see Section 12.1.1) used to establish that the sample preparation method and analytical method would quantitatively detect target analyte in the method blank, (see Section 14.6). Solvent (methanol) blank. To isolate instrument contamination, pure methanol is analyzed. If the instrument is contaminated, analyte will be detected in the solvent blank, (see section 14.4). Sample triplicates. Samples are prepared in triplicate for each time point and pH, and are analyzed identically (see Section 12.1.1). The averaged result represents the PFOA concentration for that time point and pH. Sample spike. A sample spike confirms that the method recovers analyte effectively from the sample matrix (see Section 14.6). A known amount of analyte is added to a sample after it is incubated (see Sections 12.1.1). Internal standard (IS). An internal standard is used to evaluate and control the precision (Section 3.7) and bias (Section 3.8) of the analytical process. An analytically similar compound is added to all samples and standards, creating a known, fixed concentration in all samples and standards through the entire measurement process. Precision. Precision is the degree of agreement between individual sample results. It is usually expressed as a standard deviation. Bias. Measurements are biased if they are consistently high or low (a systematic error), as compared to a known value. Calibration standard. A calibration standard is a solution containing a known concentration of analyte. A series of calibration standards is used to calibrate analytical instrument response, producing a calibration curve to determine analyte concentrations in samples. Continuing calibration verification (CCV) or Check standard. After the analytical instrument has been calibrated, a single calibration standard is analyzed at selected time intervals throughout the analytical run. The values are compared to the calibration curve to ensure that the calibration curve is valid for all samples over time, that the instrument has not drifted out of calibration. Dilution. A miscible solvent is added to all samples to prepare them for instrumental analysis. Laboratory Water. Water with a measured resistivity of 18.0 MQ-cm (or greater). Limit of quantitation (LOQ). The limit of quantitation (LOQ) is equal to the concentration of the lowest standard in the calibration curve that gives a response of more than four times the response of the solvent blanks and/or MeOH blanks. Use the solvent blanks and/or MeOH blanks that give the highest analyte counts. Residuals. In this method, a residual is the absolute value of the difference between the known, prepared concentration of a calibration standard and its concentration predicted by the calibration curve, divided by the known, prepared concentration, all multiplied by ETS-8-212.CI PFOA Hydrolysis and Analysis by HPLC/MS Page 3 of 16 Page 24 of 99 I! BACK TO MAIN 3M Environmental Laboratory Report No. EOO-1851 100. Residuals for linear calibration curves can be determined using Excel. For non linear calibration curves, the following equation should be used to determine a residual. Residual = [Analyte]*own \AfiaIyte\prvdicled bythe calibration aove x l0 0 % [Analyte]kmwn 4.0 Warnings and Cautions 4.1 Health and safety warnings 4.1.1 Wear the proper lab attire for all parts of this procedure. Wear appropriate gloves and proper eyewear at all times. 4.1.2 For sample preparation and whenever possible, use solvents in the hood. 4.1.3 For potential hazards of each chemical used, refer to material safety data sheets, packing materials, and 3M Environmental Laboratories Chemical Hazard Review. 4.2 Cautions 4.2.1 Rinse all glassware for standards preparation with MeOH and acetone and dry, to reduce the possibility of contamination. 4.2.2 Prepare enough fresh HPLC mobile phase to analyze all samples. Do not allow the HPLC pump to run dry. 4.2.3 Ensure that there is ample memory on the computer hard drive to save all run data. 4.2.4 Ensure that there is enough nitrogen in the supply tank to analyze all samples. 5.0 Interferences 5.1 Contaminants in solvents, reagents, glassware, and other sample preparation or analysis hardware may produce interferences. Routinely analyze method blanks to detect contamination from these sources (see Section 10.4). 5.2 Contaminants from columns, HPLC tubing, and detector components may cause interference at low detection levels. Routinely analyze solvent blanks (methanol) to detect contamination from these sources (see Section 10.5). 6.0 Equipment 6.1 Analytical balance sensitive to 0.0001 g 6.2 Shaker/incubator capable of maintaining a temperature of 50 3 C 6.3 Hewlett-Packard (HP) 1100 HPLC System, or equivalent 6.3.1 Quaternary pump, Model G1311A, or equivalent 6.3.2 Solvent degasser, Model G1322A or equivalent 6.3.3 Autosampler, ALS Model G1313A, variable injection volume capable, or equivalent 6.3.4 Column heater, Model G1316A or equivalent . 6.4 Dionex IonPacNG-l column, 35 mm x 4.0 mm, 10-am diameter packing, or equivalent ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/MS Page 4 of 16 Page 25 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 6.5 Mass spectrometer. Hewlett-Packard LC/MSD, or equivalent, capable o f operating in the selected-ion-monitoring mode 6.6 Digital clock. The same clock should be used during any one step o f sample preparation, to ensure that procedures are performed correctly and documented accurately. 6.7 Coming Model 308 pH/Temperature Meter with 3-in-l gel-filled combination electrode (pH/reference/temperature), or equivalent. The pH meter must be calibrated with suitable buffer standards (e.g. pH 4.0,7.0 and 9.0 - Mallinckrodt or equivalent) as recommended by the manufacturer for this broad of a pH range. 6.8 Refrigerator, capable of maintaining 4 3 C, or a freezer capable o f maintaining -20 10 C 6.9 Data system. A PC computer capable of simultaneously controlling the HPLC system and recording and processing signals from the detector 6.10 Data analysis software. Hewlett-Packard-ChemStation, Version A 6.03 or higher, or Target Software. 7.0 Supplies and Materials 7.1 Vials, 40-mL VOA (I-CHEM or equivalent) 7.2 Crimp-cap autovials, 1.5-mL 7.3 Labels 7.4 Graduated pipets, glass, disposable, 1-mL to 10-mL 7.5 Pasteur pipets, glass, disposable 7.6 Hamilton Gastight syringes (precision 1% of total volume), 10-pL to 1000-pL 7.7 Volumetric flasks, 10-, 25-, 100-, 1000-, and 4000-mL 7.8 Beakers, glass, various sizes 7.9 Automatic pipettor, capable of dispensing 10 to 5000 pL 7.10 Miscellaneous equipment as needed 8.0 Reagents and Solutions 8.1 Reagents 8.1.1 Methanol (MeOH). HPLC/SPEC/GC grade from EM Science, or equivalent 8.1.2 Laboratory Water (LW) 8.1.3 Hydrochloric acid (HCI), reagent grade 8.1.4 Sodium hydroxide (NaOH), reagent grade 8.1.5 Sodium borate decahydrate (borax), reagent grade 8.1.6 Sodium bicarbonate (N aH C 03), reagent grade 8.1.7 Potassium dihydrogen phosphate (KH2P 0 4), reagent grade 8.1.8 Potassium acid phthalate (KHP), reagent grade 8.1.9 Ammonium acetate (CH3C 0 2-NH4), reagent grade 8.1.10 Potassium salt of Perfluorooctanoic acid (PFOA) 8.1.11 Potassium salt of Perfluorobutanesulfonate (PFBS) 8.2 Stock Solutions ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/MS Page 5 of 16 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 8.2.1 Ammonium acetate stock solution. Dissolve approximately 3.9 g CH3C 0 2*NH4 in MeOH to a total volume of 100 mL to give approximately 500 mM CH3C 0 2-NH4. 8.2.2 PFOA stock solution. Dissolve approximately 0.1000 g o f PFOA in MeOH to a total volume of 10 mL to give approximately 10,000 pg/mL PFOA. 8.2.3 PFBS stock solution. Dissolve approximately 0.0500 g of PFBS in MeOH to a total volume of 25 mL to give approximately 2,000 pg/mL PFBS. 8.2.4 Hydrochloric acid (HC1) stock solution. Add approximately 8.6 mL of concentrated HC1 to approximately 600 mL LW, dilute to a total volume o f 1 L to give approximately 0.1 M HC1. 8.2.5 Sodium hydroxide (NaOH) stock solution. Dissolve approximately 4.0 g o f solid NaOH in LW to a total volume of 1 L to give approximately 0.1 M NaOH. 8.2.6 Potassium dihydrogen phosphate stock solution. Dissolve approximately 13.6 g of KH2P 0 4in LW to a total volume of 1 L to give approximately 0.1 M (KH2P 0 4). 8.2.7 Borax stock solution. Dissolve approximately 9.54 g of NajB40 7-10H2O in LW to a total volume of 1 L to give approximately 0.025 M N a ^ O ,. 8.2.8 Sodium bicarbonate stock solution. Dissolve approximately 4.2 g of N aH C03 in LW to a total volume of 1 L to give approximately 0.05 M NaHC03. 8.3 PFOA test analyte solution. Dilute 2 mL of PFOA stock solution (Section 8.2.2) with MeOH to a total volume of 10 mL to give approximately 2,000 pg/mL PFOA. 8.4 PFOA spike solution. Dilute 0.5 mL o f PFOA stock solution (Section 8.2.2) with MeOH to a total volume of 10 mL to give approximately 500 pg/mL PFOA. 8.5 PFBS diluting solution. Dilute 400 pL of PFBS stock solution (Section 8.2.3) with MeOH to a total volume of 4 L to give approximately 200 ng/mL PFBS. 8.6 Chrom atographic solvents ' 8.6.1 Chrom atographic solvent A. Dilute 10 mL of ammonium acetate stock solution (Section 8.2.1) LW to a total volume of 1 L to give approximately 5 mM CH3C 0 2-NH4. 8.6.2 Chrom atographic solvent B. Dilute 10 mL of ammonium acetate stock solution (Section 8.2.1) with MeOH to a total volume o f 1 L to give approximately 5 mM CH3C 02-NH4. 8.7 Calibration buffers for pH meter. Use commercially available pH meter calibration buffers of pH 4.0,7.0, and 10.0 (Mallinckrodt or equivalent) as recommended by the manufacturer for this broad of a pH range. 8.8 Hydrolysis buffers. Buffer solutions should be made following EPA and CRC Handbook of Chemistry and Physics guidelines (References 18.1 and 18.2) 8.8.1 Hydrolysis buffer pH 1.5 a) Add 207 mL 0.1 N HC1,250 mL 0.1 M KC1 to a 1 L volumetric flask. b) Adjust pH to 1.5 with HC1 stock solution c) Dilute to mark with LW 8.8.2 Hydrolysis buffer pH 3.0 a) Dissolve approximately 10.2 g of potassium acid phthalate (KHP) with approximately 600 mL of LW water in a 1 L volumetric flask. b) Add approximately 223 mL of HC1 stock solution (Section 8.2.4). ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/MS Page 6 of 16 Page 27 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 8.83 8.8.4 8.8.5 8.8.6 c) Adjust the pH to 3.0 with either HC1 stock solution (Section 8.2.4) or NaOH stock solution (Section 8.2.5). d) Bring to a final volume of 1 L with LW. Hydrolysis buffer pH 5.0 a) Dissolve approximately 10.2 g of potassium acid phthalate (KHP) with approximately 600 mL of LW in a 1 L volumetric flask. b) Add approximately 226 mL of NaOH stock solution (Section 8.2.5). c) Adjust the pH to 5.0 with either HC1 stock solution (Section 8.2.4) or NaOH stock solution (Section 8.2.5). d) Bring to a final volume of 1 L with LW. Hydrolysis buffer pH 7.0 a) Add approximately 500 mL of potassium dihydrogen phosphate stock solution (Section 8.2.6) to a 1 L volumetric flask. b) Add approximately 291 mL of NaOH stock solution (Section 8.2.5). c) Adjust the pH to 7.0 with either HC1 stock solution (Section 8.2.4) or NaOH stock solution (Section 8.2.5). d) Bring to a final volume of 1 L with LW. Hydrolysis buffer pH 9.0 a) Add approximately 500 mL of borax stock solution (Section 8.2.7) to a 1 L volumetric flask. b) Add approximately 46 mL of HC1 stock solution (Section 8.2.4). c) Add LW to a total volume o f approximately 950 mL. d) Adjust the pH to 9.0 with either HC1 stock solution (Section 8.2.4) or NaOH stock solution (Section 8.2.5). e) Bring to a final volume of 1 L with LW. Hydrolysis buffer pH 11.0 a) Add approximately 500 mL of sodium bicarbonate stock solution (Section 8.2.8) to a 1 L volumetric flask. b) Add approximately 227 mL of NaOH stock solution (Section 8.2.5). c) Add LW to a total volume of approximately 950 mL. d) Adjust the pH to 11.0 with NaOH stock solution (Section 8.2.5). e) Bring to a final volume of 1 L with LW. 9.0 Sample Handling 9.1 Record the times that samples were initially prepared, removed from the incubator, placed in the freezer (when applicable), removed from the freezer (when applicable) and subsequently diluted, using the fluorochemical degradation (hydrolysis) analysis sample preparation sheet (Attachment B). All samples for the same pH group should be analyzed together. Refrigerate or freeze them if necessary, and dilute them immediately preceding the analysis. 10.0 Quality Control 10.1 See Section 12 for directions on preparing quality control samples. ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/MS Page 7 of 16 Page 28 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 10.2 10.3 10.4 10.5 10.6 10.7 10.8 11.0 11.1 11.2 Calibration standards. Analyze a complete series of calibration standards before and after each analytical run for use as calibration curve. At the discretion of the analyst, this complete series may be run more often in the analytical run. Continuing calibration verification (CCV). A CCV sample should be analyzed after no more than 20 sample injections. A single calibration standard or a complete series of such standards (for use as a calibration curve) will satisfy this requirement. M ethod blank. Analyze a minimum of one method blank per time point per pH (e.g., Day 42, pH 7.0). Solvent blank. Analyze one solvent blank before and after every calibration curve as well as before and after every CCV. Sample triplicates. Prepare and analyze all hydrolysis samples in triplicate to determine analysis precision. Sample spikes. Prepare a sample spike for each pH and time point used in the study. Final (diluted) spike concentrations should approximate a mid-range calibration standard. The sample spike sample should be analyzed immediately following the sample triplicates to which it corresponds. Internal standards. Aliquots of PFBS stock solution (Section 8.2.3) are added to calibration standards to give a final internal standard concentration o f approximately 158 ng/mL PFBS. Samples should also contain approximately the same concentration of PFBS. Calibration and Standardization_____________ ___________________________ Standard preparation. Prepare at least five calibration standards of approximately 25 to 1000 ng/mL PFOA, containing approximately 158 ng/mL PFBS internal standard. Standard curve. Relate the ratio of the analyte peak area of the calibration standards to the internal standard peak area, using linear regression software. If calibration ratios are inconsistent, external standard calibration may be used. Consult the Team Leader or designated supervisor for recommendations before using external calibration. 12.0 Procedures ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/MS Page 8 of 16 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 12.1 Sample preparation and hydrolysis 12.1.1 The following table summarizes sample preparation. Analyte Buffer Calibration standards Continued Calibration verification (CCV) Method blank0 Solvent blank Sample Duplicate Triplicate Sam ple spike6 Method spike0 X X --X X X X - X X X X X X X X Diluting solution containing internal standard X X X " X X X X X a Also called Blank 6 Also called Spike, Matrix spike, and Replicate spike c Also called Blank spike Spike - -- --- -X X Methanol Incubate only /shake - -- -- - -- X X-- X -X -X -- X -- X 12.1.2 Determine the number of time points and corresponding samples to be analyzed. Each time point should have six vials per pH: sample, duplicate, triplicate, sample spike, method spike, and method blank. 12.1.3 Obtain the appropriate number of 40-mL VOA vials with caps, and the partitioned cardboard box they were shipped in. It will be helpful to use a separate box to hold the vials for each time point. 12.1.4 Prepare sample preparation worksheets (Attachment B), and label the vials with the sample number, pH, time point, and initials of the analyst. Record the pH and buffer ID o f each hydrolysis buffer solution. 12.1.5 Add 5 mL of the appropriate buffer solution to all of the labeled vials. Always recap each vial immediately to minimize solvent evaporation. 12.1.6 Using a 10-pL Gastight syringe, add 15 pL of PFOA test analyte solution (Section 8.3) to the following sample types for each time point and pH: sample, duplicate, triplicate, and sample spike (see Section 12.1.1). ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/MS Page 9 of 16 Page 30 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 12.1.7 Make sure all vials are well-sealed, and place them into a partitioned cardboard case (with cover) to exclude light. It will be helpful to use a separate box to hold the vials for each time point. 12.1.8 Refrigerate Day 0 samples at 4 3 C, or freeze them at -20 10 C. 12.1.9 Place the remaining samples into a pre-warmed incubator/shaker for the appropriate time. Record the time, temperature, and shaking rate (RPM). Continue to manually monitor the incubator temperature daily during the entire incubation. Record the temperature on the sample preparation sheet (Attachment B). 12.1.10 Remove each case from the incubator at the designated time. Refrigerate them at 4 3 C, or freeze them at -20 10 C, until all samples from all time points can be analyzed together. 12.1.11 Before analysis, allow the incubated vials to come to room temperature. 12.1.12 Add 30 mL of PFBS diluting solution (Section 8.5) to all vials. 12.1.13 Using a 10-pL Gastight syringe, add 10 pL of PFOA spike solution (Section 8.4) to the method spike and sample spike vials (see Section 12.1.1). Recap the vials tightly, and invert them several times to mix. 12.1.14 Aliquot approximately 1 mL of each sample into the appropriately labeled autovial. Cap the vials. 12.1.15 Transfer the vials to the HPLC autosampler. 12.2 HPLC set-up 12.2.1 Review instrument method 1101 PFOA.M. Note that thefollowing instrumentation set-up procedures apply to Hewlett-Packard/'Agilent HP1100 equipment only. 12.2.2 For each analysis, ensure the appropriate HPLC column is in the instrument (Dionex IonPacNG-l, 35 mm x 4.0 mm, 10-pm diameter packing, or equivalent). 12.2.3 Ensure the correct type and amount of eluent is loaded in the instrument. Be sure there is enough loaded to complete the analytical sequence. 12.2.4 Place the samples in the autosampler tray and construct a sequence table with calibration standards, calibration check standards, and solvent blanks. 12.2.5 Verify that all samples and standards are positioned correctly. Enter sequence information: sample or standard ID, method name, and one injection per sample. 12.2.6 Save sequence as analysis date (e.g., on September 14,2000 save sequence as 091400.s). Save data to a subdirectory labeled with analysis date (e.g., 091400). 12.2.7 Set the post-sequence command macro to shut the system down ("standby" on HP systems). 12.2.8 Use the following solvents (see Section 8.6), gradient, and instrument settings (or equivalent - note that the following instrumentation set-up procedures apply to Hewlett-Packard/Agilent HP 1100 MSD equipment only). 12.2.8.1 Chromatographic solvent A (Section 8.6.1). 12.2.8.2 Chromatographic solvent B (Section 8.6.2). 12.2.8.3 Solvent Gradient ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/MS Page 10 of 16 Page 31 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Time (min) 0.0 1.0 8.0 15.0 Percent A 95 95 0 0 Percent B 5 5 100 100 Flow Rate (mL/min) 0.3 0.3 0.3 0.3 12.2.8.4 Instrument settings Injection volume (fiL) Back pressure Column (bar) compartment temperature (C) 10.0 6-12 40 Stop time (min) 12.50 Post time (min) 5.00 12.3 Mass spectrometer set-up 123.1 Use the following tables (or equivalent) to-set up the mass spectrometer. (Note that the following instrumentation set-up procedures apply to HewlettPackard/Agilent HP 1100 MSD equipment only.) Acquisitio Ionizatio n Mode nMode Selected Ion (SIM) API-ES Peak width (min) 0.25 Polarity Negative Drying Gas Flow (L/min) 8 Nebulize r Pressure (P*ig) 30 Drying Gas Temp (C) 350 Captila Voltage (V) 3500 Analyte PFBS PFOA HPLC Column Retention Time (min) 8.1 9.4 Selected Ion (amu) 299 (M-H*)* 413 (M-H*)* Gain (EMV) 4.0 4.0 Fragmentor (V) Var. Var. Dwell Time (msec) 739 739 * M-H+is the molecular ion with a loss of proton. For example, the molecular weight of PFBS is 300, when it loses a proton, it assumes a negative charge and has a mass o f 299. 12.4 Autosampler set-up 12.4.1 Use the following parameters (or equivalent) to set up the autosampler. Autosampler ALS Model G1313A Autosampler Program None Injection volume (pL) 10.0 ETS-8-212.0 PFOA Hydrolysis andAnalysis by HPLC/MS Page 11 of 16 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 12.5 Sample analysis 12.5.1 After setting-up the HPLC, the mass spectrometer, and the autosampler, analyze a CCV after every 20 sample injections, and the calibration standards at the end of the sequence. To check for analyte carry-over, run solvent blanks after the highest calibration standard as well as before and after the CCV (see Section 10.0) . 12.5.2 Identify the electronic acquisition files with an appropriate prefix. Do not exceed five characters if the sequence contains more than 99 lines. 13.0 Data Analysis and Calculations___________________________________________ 13.1 Peak evaluation. Analyte and internal standard peaks must be symmetrical - if peak tailing is observed, consult team leader or designee for direction. They must be identified by measuring their retention times and by the compound-specific ions. When generating a calibration curve, analyte peak heights must be greater than four times the baseline noise and/or solvent blank for that region of the chromatogram. Peak areas are integrated manually or automatically from baseline to baseline through the peak. If present, analyte isomers appearing as either a shoulder or a discrete second peak in the chromatogram should be integrated with the analyte peak, unless otherwise indicated. Quantitation data are calculated using PFBS as the internal standard. However, external standard calibration may be acceptable. Consult the Team Leader or designated supervisor before using external calibration methodology. 13.2 Calculations involving analyte purity. In calculations where analyte purity ratios cancel each other (e.g., calculation of the hydrolysis rate constant, k based on loss of parent material), purity does not need to be considered. 13.3 Percent recovery. Calculate the percent of PFOA recovered from each of the sample spikes using the following equation. y JUgQyy [PjPOA] detected in sample spike - [PFOA] detectedm [PFOA] in sample spike, added via spike * 100% 13.4 Sample triplicates. Use the following equation to calculate the relative standard deviation (RSD) for the triplicate samples. ^ = Standard Deviation xW 0% Mean Concentration The RSD is also known as the coefficient of variation, a measure of the precision. 13.5 Calculation of k. Calculate the PFOA concentrations in each of the pH matrices using the calibration and internal (or external) standard curves. Assuming first-order kinetics a rate constant (k) can be determined by plotting ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/MS Page 12 of 16 Page 33 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 \p f o a \, \ Ln [.PFQ/l]) versus i e 8a^ ve elapsed time (-t), where the subscripts t and 0 refer to analyte concentrations at time t and at t = 0, respectively. The slope of the resulting line is k. i 14.0 Method Performance 14.1 Calibration curves. An acceptable coefficient of determination (R2) for linear curves is 0.990 or greater. Accuracy should be verified, particularly at upper and lower calibration limits by calculating the residuals -residuals generated in curve-fitting must be between 0 and 25%. Alternative methods o f curve-fitting (e.g., quadratic) require a coefficient o f determination (r2) of 0.990 or greater. Record the reason(s) for using quadratic curve fitting in the raw data. If the quality control parameters are not met, consult team leader or designee for direction. 14.2 Continuing calibration verification (CCV). Analyte concentration must not differ by more than 25% of its expected value, relative to the initial calibration curve. Accept only those samples analyzed before the last accepted calibration verification. Reanalyze remaining samples with a new calibration curve. 14.3 M ethod blank. If the contamination levels are greater than 5% for any particular target, consult the Team Leader or designated supervisor for recommendations. For example, if PFOA were targeted at 500 ppb, contamination should be less than 25 ppb. In those instances where the 5% level would be below the lowest point o f the calibration curve, a 25% value is used rather than the 5% (as 5% cannot be quantified and the 25% level brings this in line with the LOQ definition, see section 14.8). 14.4 Solvent blanks. Solvent blanks should show no more than a 5% carry-over from a high standard or CCV. If they do, two solvent blanks should be analyzed to rule out instrument contamination. If solvent blanks are still showing more than 5% carry-over, or are adversely affecting the LOQ (see Section 14.8), the run should be stopped. This indicates that the instrument is contaminated and should be thoroughly cleaned. Pay particular attention to the electrospray source. The column and tubing may need to be replaced. When the solvent blanks are improved, reanalyze the sequence beginning at the last; acceptable CCV or calibration curve, starting with a new calibration curve. 14.5 Sample triplicates. If RSD precision values are 25% or greater, consult the Team Leader or designated supervisor for recommendations. 14.6 Sample spikes. If sample spike recoveries are less than 70% or greater than 130%, consult the Team Leader or designated supervisor for recommendations. 14.7 Residuals. The acceptance criterion for the residuals is less than or equal to 25%. If the residuals are higher than this, consult team leader or designee for direction. No calibration curve will be accepted with residuals outside this range. 14.8 Lim it of Quantitation. The limit of quantitation (LOQ) is equal to the lowest standard in the calibration curve that gives a response of more than four times that o f the test anailyte in the solvent blanks. 14.9 M ethod Spike. If method spike recoveries are less than 70% or greater than 130%, consult the Team Leader or designated supervisor for recommendations. ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/MS Page 13 of 16 Page 34 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 15.0 Pollution Prevention and Waste Management_____________________________ 15.1 Dispose of sample waste by placing it in high or low BTU containers as appropriate. Use broken glass containers to dispose of glass pipettes. 15.2 Collect HPLC solvent waste in the satellite accumulation can. When the satellite can is full, empty it into the flammable storage drum in the hazardous waste collection area on the second floor. 16.0 Records ____________________ 16.1 Print out hard copies of all graphics and data analysis summaries for archiving. 16.2 Sign and date all graphics, and label with the instrument ID. 16.3 Immediately fill out the hydrolysis sample preparation worksheet completely, including all initials and dates. 16.4 Print chromatograms and internal standard reports for all analyses. 16.5 Print calibration tables and curve information, and store them in the raw data file. 16.6 Store hydrolysis sample preparation worksheets in the raw data file. 16.7 Enter all standard preparation information in the standards preparation logbook. Make a photocopy of the logbook page and include the copy in the raw data file. 16.8 Archive electronic data to appropriate media when necessary. 17.0 At tachments____________________________________________________________ 17.1 Attachment A. Representative Chemical Structures 17.2 Attachment B. Hydrolysis Sample Log sheet 18.0 References ____________________ 18.1 Fate, Transport and Transformation Test Guidelines OPPTS 835.2110: Hydrolysis as a Function o fpH; EPA 712-C-98-057; U.S. Environmental Protection Agency, Office o f Prevention, Pesticides and Toxic Substances, U.S. Government Printing Office: Washington, DC, 1998. 18.2 CRC Handbook o f Chemistry and Physics, 1st Student Edition; Weast, R. C., Ed., CRC Press: Cleveland, OH, 1988; p. D-87. 19.0 Affected Documents_____________________________________________________ None. 20.0 Revisions___________________________________________________ Revision Number Reason for Revision ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/MS Page 14 of 16 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 I : ........................ . ................. Attachment A. Representative Chemical Structures R+= NH4+in this study, but may also be Li*, N a \ K+, H+. 1. PFOA (Perfluorooctanoic Acid) MW (anion) = 413 R+= N IV 2. PFBS (Perfluorobutanesulfonate) MW (anion) = 299 R+= K+ ETS-8-212.0 PFOA Hydrolysis andAnalysis by HPLC/MS Page 15 o f 16 BACK TO MAIN 3M Environmental Laboratory Report No. EOO-1851 Attachment B. Sample Preparation Sheet TEST ANAYLTE:____________ U h Request Numb a n ____________ Nominal IrttMval:_________ Nominal T m p o n rtur a ; _________ *c Sample No. Data'. Tima: Wttala: lo t Tamp pH rl 14 r2 1.5 r3 1.5 ms 15 Wk 14 rl 3 ra 3 r3 3 ms 3 Uk 3 rl 3 r2 5 r3 5 ms 5 bK 5 r1 7 i2 7 r3 7 ms 7 b* 7 rt 9 (2 1 a9 ms 9 bik 9 rl 11 r2 11 r3 11 ma 11 bik 11 B uffer Fluorochemical Degradation (Hydrolysis) Ansitysls Incubator ID :_______________________________ S tart Date:_______________ Tim a:________ Stop Date:_______________ Tima: Incubation Interval;______ d a y s _______ b o v rs______ min Test A nalyte Spike S olution D ilu tio n iW ve n t Freezer ID: Stan D ata:________________ Stop Data:________________ Tim a: Tim a: In te rn a l Standard C om m an Solution ID Amount tmL) Solution - - - .. - Component Amount (PL) - Solution ID _ - _-- -- _- - -- -- _- ~ - - -- _ - Co-ne. (pg/m L) - Component Amount <l*> _ --- -- - Solution ID - - _ - - --_ - - _ ~ - Co-ne, <M5*nL) Component Am ount Im L) S d u tto * ID Cone. (pgfm L) Component Am ount (pL) Cone. (pg/m L) Commenta: ETS-8-212.0 PFOA Hydrolysis and Analysis byHPLC/MS Page 16 of 16 Page 37 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Appendix B: Kinetics Model This Appendix includes a mathematical description of the kinetics model em ployed in the study. Page 38 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Kinetics Model B1. Reaction Components and Rates The arguments below are based on the following idealized set of reactions representing the hydrolysis of a parent compound P and its hydrolysis products A m, 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 Pm(forthe parent) and k Am(forthe parent's hydrolysis products). P + H 20 n m A m+ Y ml (m = 1 to N) (B1) A m + H 20 Y, (m = 1 to N) (B2) where the general symbols Yml and Y m2 represent all the other hydrolysis products. B2. Parent Compound Concentrations Equation B1 indicates that the pseudo-first order differential change in the parent concentration P is given by which is equivalent to the separable differential equation Equation B4 may be directly integrated to obtain the general solution (B3) (B4) With the initial condition P(t = 0 ) s P 0, the specific solution to Equation B4 is P = P0 exp using the additional definition of the total parent hydrolysis rate (B6) Page 39 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 N (B7) m=l Equation B6 can be re-written in a form that allows a least-squares estimate of the total parent hydrolysis rate: (B8) Using the initial (t = 0) measured value of the parent concentration P0and later values P measured at later times t , one can calculate and plot the (linear) quantity [ - h (P/P0)J versus time and obtain a least -squares estimate of the slope of the line. The resulting slope is the least-squares estimate k p of the total parent hydrolysis rate. Equation B6 indicates that over a period of time T 1^ (the parent hydrolysis half-life) the parent concentration P is reduced through hydrolysis by a factor of two, where t i/2_ H 2 ) pu (B9) A least squares estimate of the parent hydrolysis half-life is therefore available from b<2) T Kr p (B1C B3. Product Compound Concentrations The pseudo-first order differential changes in the product concentrations An (using Equations B2 and B6) are d A m = ( n mk PmP - k AmA m) d t = ( n mk PmP0 e-k- 1- k AmA m)d t (B11) and the (first order, non-separable) differential equation governing the product concentrations is dA dt The "standard form" of Equation B12 is (B12) Page 40 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 A m+ S ( t ) A m = Q (t) where the "function" S (t) is actually a constant: S (0 = k Am and Q(t) = nmk PmP0 e 'kpt . The general solution A mto Equation B12 is contained in (B13) (B14) (B15) A m eJS(t)dt = J Q (t)e iS(t)dl dt + C (B16) where and g is ( t ) d t _ e fS (t')d t' .. g k A n . J d t gkAnjt (B17) jQ (t)e ^ s(t')dt'd t + C = nmk PmP0J ek- ` e-kptdt + C (B18) There are two cases of Equation B18 to consider. In the circumstance that k Am = k p , which occurs only when the hydrolysis rate of the mth product is identical to the total parent hydrolysis rate, the general solution to Equation B18 is (for k Am= k P) e P = n n,kpmP0 t + C (B19) and, using the initial condition A m(t = 0) = A ^ , the specific solution to Equation18 is (fo rk Am= k p) Am= (nmkPmP0 t + Am0) e kp* (B20) We note that when k ^ = k p = 0 (that is, when both the parent and potential product are hydrolytically stable), Equation B7 requires (also) that k Pm= 0 , so Equation B20 becomes Page 41 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 A,, = A,, (B21) indicating, as required, that the product concentration does not change with time. The circumstance k Am = k p 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 rate k pand the product hydrolysis rate k ^ approach each other. In the more probable case, for which k Am ^ k p (i.e. that the hydrolysis rate of the mth product is different from the total parent hydrolysis rate), the general solution to Equation B18 is +c/V g ^ A m * -- ^ m ^ P m ^ O g (kAm k p ) t m If _ 1c K Am K P (B22) and the specific solution to Equation B18 with the initial condition A m(t = 0) = A m0 is A_ = A m0 + n mk PmP 0 kp k Am n mk PmP 0 e -kP . (B23) Of greatest interest here is the case in which the product compounds are known to be hydrolytically stable, that is, when k ^ = 0 for all m. In this case, Equation B23 becomes (for hydrolytically stable products) Kp (B24) B4. Relationships Between the Parent and Compound Concentrations Equations B7 and B24 can be combined to obtain (for hydrolytically stable products) N k P v ( A m - A mo) m=l V1 e / m=l r0 (B25) Page 42 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 so that or (for hydrolytically stable products) c- k p t ) _ ^ (Am - A m0) r po (for hydrolytically stable products) (B26) k pt = - I n 1 ^ (A m ~ A ,no) . m=l P0 (B27) If the changes in the product concentrations are all small compared to the original parent concentration, that is, if y A m - A m0 1, r 1 po we may use the expression (valid for -1 < X < 1 ) (B28) ln(l + X ) = X - - X 2 + - X 3 - - X 4 + . 234 and Equation B23 becomes (for hydrolytically stable products and ,A m ^ m O <<P0) If N a - AA mO ^ M =,, p. (B29) (B30) Page 43 of 99 or (for hydrolytically stable products and kptS BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 (B31) B5. Parent Half-Life Estimates Based on Limits of Quantification of the Products In every experimental determination of k p, there is some set of values A " q (the "limits of quantitation") below which the product concentrations A mcannot be reliably measured. If during an experiment carried out over the period of timeA t all the product concentrations A mremain below their limits of quantitation, then the maximum possible value of the rate k p is obtained by assuming (for all the products) that 1) A m0 = 0 and 2) at time t = A t , the product concentrations have increased to the values A m= A ^OQ. With these assumptions, the experimental data indicate that the reaction rate k pis less than some maximum value (kp^ as follows: (for hydrolytically stable products at concentrations below the limits of quantitation) k P < (kP)m = 0 m=l ` (B32) N Under the same circumstances and assumptions, the experimental data indicate that the parent half-life T 1^ (see Equation B9) is greater than the value (t ^ ) . as follows: (for hydrolytically stable products at concentrations below the limits of quantitation) M T'p L = ?\ j!PT/maLx = A , p "1,,(2) Ah0Q (B33) The reader should note that Equations B32 and B33 are valid only when both 1) the products are hydrolytically stable and 2) the concentrations of all the potential products are measured. Otherwise, the quantity ( k p ) ^ in Equation B32 may not actually represent the maximum possible value of the rate constant k p, and the related result in Equation B33 for (t ^ ) is also questionable. . Page 44 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 B6. Parent Half-Life Estimates Based on Limits of Quantification and Experimental Precision of Product Concentrations in certain experiments, some hydrolysis products are present at quantifiable but essentially constant concentrations over the time ( A t ) of the experiment. In this case, it is the experimental precision of the measured product concentrations, rather than the limits of quantitation, which contribute to the estimate of the maximum value of the parent hydrolysis rate k p. If the set of concentrations measured for the mth product have the mean value p mand standard deviation o m, the data do not exclude the possibility that the product concentration increased from the initial value o m- p mto the value a m+ p mat time t = A t . Taking this possibility to be the actual case for the measured products, the maximum value of the quantity (A m- A m0) is 2c m. This reasoning suggests that the following estimate of the maximum parent hydrolysis rate is appropriate: (for hydrolytically stable products at either 1) constant measured concentrations with standard deviation om or 2) concentrations below the limits of quantitation) Below LOQ Cons tan t (B34) Under these circumstances and assumptions, the experimental data indicate that the parent half-life T 1^P is greater than the value (' T ^P /)min as follows: (for hydrolytically stable products at either 1) constant measured concentrations with standard deviation am or 2) concentrations below the limits of quantitation) XT 'i 2 fI " i L = 7 'T PT/mLax = A ' P . ^ 2) A" + Below LOQ Cons tan t - 1-1 (B35) The reader should note that Equations B34 and B35 are valid only when both 1) the products are hydrolytically stable and 2) the concentrations of all the potential products are measured. B7. 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 rate k p. If the set of concentrations measured for the parent have the mean value p pand standard deviation o p, the data do not exclude the possibility Page 45 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 that the product concentration increased from the initial value p p - crP to the value HP+ o P 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 value p pand standard deviation O p) k' s(k' )~ = ; ^ ? <B36> Under these circumstances and assumptions, the experimental data indicate that the parent half-life T 1^" is greater than the value (xt ^P ')m in as follows: (for essentially constant parent concentrations with mean value p pand standard deviation o P) ' 1/2 P > M' P2')m in = -(.irM\2) VK P /m ax p P A t ln(2) 2o d (B37) B8. Temperature Dependence of the Reaction Rate and Half-Life In order to increase the speed of the reactions of interest, we conducted this experimental study using samples maintained at the temperature 50C = 323 K. Of greater interest are the corresponding results for the environmentally important temperature 25C = 298 K. When the Arrhenius activation energy for a reaction is A H a, Equation B38 81 provides the following relationship between the hydrolysis rates (k, and k2) for that reaction at two different absolute temperatures (T, and T 2): where R = 1.99 x 10'3 Kcal mole'1 K'1is the ideal gas constant. Using the value82 A H a=18 Kcal/mole, the rate ratio k , / k 2 at the corresponding temperatures T, =298 K and T 2=323 K is ki = exp-[^------1-8----- r 1 k 2 [1.99x10 323 = exp(-2.35) = 0.095 . (B39) Page 46 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Equation B39 indicates that the hydrolysis reactions of interest proceed approximately ten times more slowly at 25C than at the chosen experimental temperature of 50C. Accordingly, the rate reactions reported here for the temperature 25C are ten times lower than those measured at 50C, and the hydrolysis half-life estimates reported here for 25C samples are ten times longer than those calculated from the 50C experimental data. References to Appendix B: B1 I. N Levine, "Physical Chemistry," McGraw-Hill (New York), pp. 498-501 (1978). 82 F. Daniels, et al., "Experimental Physical Chemistry", McGraw Hill (New York), p.131 (1962). Page 47 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Appendix C: Selected Analytical and Kinetics Results This Appendix includes selected sample data and their related kinetics results. Page 48 of 99 3M Environmental Laboratory Report No. E00-1851 PFOA Buffer Hydrolysis Study at 50 C. All concentrations in ng/ml. PH Time (Days) Cone. 1.5 14 378 1.5 0 496 1.5 7 445 1.5 28 432 1.5 42 464 1.5 64 470 1.5 84 457 1.5 109 480 lnflPM Plo) (A) 0.000 -0.107 -0.137 -0.066 -0.054 -0.081 -0.032 PFOA @ 50 C pH 1.5 ra te constant grap h 0.050,00 -0.05- y = 1.69E-04X - 7.63E-02 R2 = 2.20E-02 -0.10- -0.15- 50 100 Time (days) pH Time (Days) Cone. ln([P]t/[P]o) 5.0 0 657 0.000 5.0 7 656 -0.002 5.0 14 656 -0.002 5.0 28 655 -0.003 5.0 42 656 -0.002 5.0 64 643 -0.021 5.0 84 654 -0.005 5.0 109 645 -0.018 0.05- PFOA @ 50 C pH 5.0 rate constant grap h . 0.00' g-0.05- *5-0.10- y = -1.54E-04x+ 1.68E-04 R2= 5.36E-01 -0.15- Time (days) SUMMARY OUTPUT Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.14822 0.02197 -0.17364 0.04960 7 Regression Residual Total Intercept X Variable 1 % 2o Slope Uncertainty 597% -0.07628 0.00017 SUMMARY OUTPUT Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.73221 0.53613 0.45882 0.00605 8 0.00028 0.01230 0.01257 0.03048 0.00050 Regression Residual Total Intercept X Variable 1 % 2o Slope Uncertainty 76% df 1 6 7* SS 0.00025 0.00022 0.00047 Coefficients 0.00017 -0.00015 Standard Error 0.00333 0.00006 (A) Data in italics have been excluded from the fits on the basis of the data quality objectives (see text). BACK TO MAIN Page 49 of 99 3M Environmental Laboratory Report No. EOO-1851 PFOA Buffer Hydrolysis Study at 50 C. AJI concentrations in ng/ml. pH Time (Days) Cone. 07.0 653 7.0 7 649 7.0 14 642 7.0 28 645 7.0 42 650 7.0 64 650 7.0 84 652 7.0 109 647 Intt0P.0M00Plo) -0.007 -0.017 -0.012 -0.005 -0.005 -0.001 -0.009 PFOA @ SOC pH Tim e (D ays) Cone. ln ttP M P lo ) 9.0 0 653 0 .000 9.0 7 661 0.012 9.0 14 666 0.020 9.0 28 654 0.001 9.0 42 660 0.010 9.0 64 667 0.020 9.0 84 640 -0.020 9.0 109 657 0.005 PFOA @ 50 C pH 9.0 rate constant graph U.Ub . 0.00' * a. g-0.05' --0.10 1 y = -1.06E-04X + 1.08E-02 R2 = 1.01E-01 -0.15' 50 100 Time (days) SUMMARY OUTPUT Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.12196 0.01487 -0.14931 0.00611 8 Regression Residual Total Intercept X Variable 1 % 2o Slope Uncertainty 664% -0.00780 0.00002 SUMMARY OUTPUT R e g re s s io n S ta tis tic s Multiple R R Square Adjusted R Square Standard Error Observations 0.31722 0.10063 -0.04927 0.01338 8 0.00000 0.00022 0.00023 0.00336 0.00006 Regression Residual Total Intercept X Variable 1 % 2o Slope Uncertainty 244% df 1 6 7 SS 0.00012 0.00107 0.00119 Coefficients 0.01081 -0.00011 Standard Error 0.00735 0.00013 BACK TO MAIN Page 50 of 99 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH 1.5 Page 1 of 3 Retention times (RT) in minutes All concentrations in ng/ml ______ PFOA____________________________________________________ 1f\ MeOH 00023-94-00pH1.5 00028-94-01 pH1.5 S S taR t3? S" HILL0012.D HILL0013.D HILL0014.D RT 9.4 9.4 9.4 Area 0 0 87108 r -rc 0 0 25 '/Standard or . % Spike RSD Recovery 101% 00028-94-02pH1.5 HILL0015.D 9.4 269160 74 98% 00028-94-03pH1.5 HILL0016.D 9.4 567497 155 103% 00028-94-04pH1.5 00028-94-05pH1.5 00028-94-06pH1.5 00028-94-07pH1.5 00028-94-08pH1.5 00028-94-09pH1.5 MeOH HILL0017.D HILL0018.D HILL0019.D HILL0020.D HILL0021.D HILL0022.D HILL0023.D 9.4 1088824 9.4 1544196 9.4 2074680 9.4 2396263 9.4 2742512 9.4 3048151 9.4 0 305 446 627 749 886 1040 0 102% 99% 105% 100% 99% 104% 00028-94-05pH1.5 MeOH 061500-PFOA-001 HILL0024.D HILL0025.D HILL0026.D 9.4 1536260 9.4 0 9.4 0 445 0 0 99% 061500-PFOA-002 061500-PFOA-003 HILL0027.D HILL0028.D 9.4 620229 9.4 1618896 171 469 119% 061500-PFOA-004 061500-PFOA-005 061500-PFOA-006 061500-PFOA-037 061500-PFOA-038 061500-PFOA-039 HILL0029.D HILL0030.D HILL0031.D HILL0032.D HILL0033.D HILL0034.D 9.4 1736393 9.4 1724702 9.4 2128004 9.4 0 9.4 615225 9.4 1550782 511 508 655 0 169 449 5% 111% 118% 061500-PFOA-040 HILL0035.D 9.4 1538986 445 061500-PFOA-041 HILL0036.D 9.4 1535116 443 061500-PFOA-042 HILL0037.D 9.4 1989327 588 1% 99% 061500-PFOA-073 HILL0038.D 9.4 0 0 061500-PFOA-074 HILL0039.D 9.4 615864 167 117% 061500-PFOA-075 HILL0040.D 9.4 1346582 380 061500-PFOA-076 HILL0041.D 9.4 1424910 402 061500-PFOA-077 HILL0042.D 9.4 1254577 350 061500- PFOA-078 HILL0043.D 9.4 2049553 609 7% 162% MeOH HILL0044.D 9.4 0 0 00028-94-OOpH1.5 HILL0045.D 9.4 0 0 00028-94-01 pH 1.5 00028-94-02pH 1.5 00028-94-03pH 1.5 00028-94-04pH 1.5 00028-94-05pH 1.5 00028-94-06pH 1.5 00028-94-07pH1.5 00028-94-08pH 1.5 00028-94-09pH 1.5 MeOH 00028-94-05pH1.5 MeOH HILL0046.D HILL0047.D HILL0048.D HILL0049.D HILL0050.D HILL0051.D HILL0052.D HILL0053.D HILL0054.D HILL0055.D HILL0056.D HILL0057.D . 9.4 88571 9.4 268237 9.4 555918 9.4 1074890 9.4 1528049 9.4 2065254 9.4 2395045 9.4 2735814 9.4 3013737 9.4 0 9.4 1518810 9.4 0 25 72 150 296 433 618 734 862 997 0 431 0 101% 96% 100% 99% 96% 103% 98% 96% 100% 96% Method ID: Internal Standard Quant r2= Curve averaged: Linear Include origin Calibration range: (A) Data excluded on the basis of data quality objectives: see text. PFBS Time Point Day 0 Day 0 Day 0 Day 0 Day 0 Day 7 Day 7 Day 7 Day 7 Day 7 (A) (A) (A) (A) (A) RT 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 Mean S.D. %RSD Area 0 908059 909951 903676 905788 906337 907182 904809 902107 904455 892593 0 904425 0 902654 900524 908989 904339 903184 894784 909299 904599 906295 906151 908224 917055 920280 913287 914168 919381 918619 915934 0 929035 924527 925699 918088 921247 921183 911706 916752 921529 910181 0 920701 0 910945 8520 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 Page 51 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. EOO-1851 PFOA Hydrolysis Study 50C pH 1.5 Page 2 of 3 Retention times (RT) in minutes in MeOH 00028-94-OOpH1.5 00028-94-01 pH1.5 00028-94-02pH1.5 00028-94-03pH1.5 00028-94-04pH1.5 00028-94-05pH1.5 00028-94-06pH 1.5 00028-94-07pH 1.5 00028-94-08pH 1.5 00028-94-09pH 1.5 MeOH 00028-94-05pH1.5 MeOH 061500-PFOA-109 061500-PFOA-110 061500-PFOA-111 061500-PFOA-112 061500-PFOA-113 061500-PFOA-114 061500-PFOA-145 061500-PFOA-146 061500-PFOA-147 061500-PFOA-148 061500-PFOA-149 061500-PFOA-150 061500-PFOA-181 061500-PFOA-182 061500-PFOA-183 061500-PFO A-184 061500-PFOA-185 061500-PFOA-186 MeOH 00028-94-OOpH1.5 00028-94-01 pH1.5 00028-94-02pH1.5 00028-94-03pH 1.5 00028-94-04pH 1.5 00028-94-05pH 1.5 00028-94-06pH 1.5 00028-94-07pH1.5 00028-94-08pH1.5 00028-94-09pH1.5 MeOH 00028-94-05pH 1.5 MeOH Method ID: ft* HILL0004.D HILL0005.D HILL0006.D HILL0007.D HILL0008.D HILL0009.D HILL0010.D HILL0011.D HILL0012.D HILL0013.D HILL0014.D HILL0015.D HILL0016.D HILL0017.D HILL0018.D HILL0019.D HILL0020.D HILL0021.D HILL0022.D H1LL0023.D HILL0024.D HILL0025.D HILL0026.D HILL0027.D HILL0028.D HILL0029.D HILL0030.D HILL0031.D HILL0032.D HILL0033.D HILL0034.D HILL0035.D HILL0036.D HILL0037.D HILL0038.D HILL0039.D HILL0040.D HILL0041.D HILL0042.D HILL0043.D HILL0044.D HILL0045.D HILL0046.D HILL0047.D HILL0048.D HILL0049.D : RT Area 9.4 0 0 9.4 0 0 9.4 86727 25 9.4 263618 72 9.4 566304 155 9.4 1086829 303 9.4 1527963 439 9.4 2057013 620 9.4 2397916 741 9.4 2723201 877 9.4 3008216 1015 9.4 0 0 9.4 1530134 442 9.4 0 0 9.4 0 0 9.4 611006 167 9.4 1566907 455 9.4 1449273 418 9.4 1470566 424 9.4 1896744 566 9.4 0 0 9.4 612576 168 9.4 1539839 453 9.4 1645514 488 9.4 1539497 452 9.4 2004080 612 9.4 0 0 9.4 614207 170 9.4 1586941 470 9.4 1588535 471 9.4 1593078 468 9.4 2031466 615 9.4 0 0 9.4 0 0 9.4 85229 25 9.4 263990 73 9.4 547960 152 9.4 1055076 299 9.4 1507704 441 9.4 2029865 619 9.4 2358294 744 9.4 2709145 877 9.4 2974918 1016 9.4 0 0 9.4 1490907 438 9.4 0 0 Internal Standard Quant r2= Curve averaged: Linean Include origin Calibration range: /Standard or PSD 99% 96% 104% 101% 97% 104% 99% 98% 102% 5% 4% 0% 98% 97% 101% 100% 98% 103% 99% 98% 102% % Spike Recovery 98% 117% 94% 117% 103% 119% 102% 97% Time Point Day 28 Day 28 Day 28 Day 28 Day 28 Day 42 Day 42 Day 42 Day 42 Day 42 Day 64 Day 64 Day 64 Day 64 Day 64 RT 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 8.1 Mean S.D. %RSD Area 0 934078 925925 921833 920312 929345 927676 919442 922937 916170 905079 0 922724 0 909201 923114 920705 918974 919948 917238 909762 922354 907792 908048 909243 906119 914222 913174 904415 904333 912714 914516 0 920372 920248 917644 908656 913334 909832 909575 904499 910954 894725 0 905282 0 914913 8270 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 Page 52 o f 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH 1.5 Page 3 of 3 Retention times (RT) in minutes Ail concentrations in ng/ml___________________ PFOA_________________________________________ __________ ______________ PFBS in MeOH : - ; :i HILL0036.D RT 9.4 Area 0 "/Standard or % Spike PCp Recovery Time Point RT 0 8.1 00028-94-00pH1.5 HILL0037.D 9.4 0 0 8.1 00028-94-01pH 1.5 HILL0038.D 9.4 85229 25 101% 8.1 00028-94-02pH 1-5 HILL0039.D 9.4 263990 74 98% 8.1 00028-94-03pH 1.5 HILL0040.D 9.4 547960 154 103% 8.1 00028-94-04pH 1.5 HILL0041.D 9.4 1055076 303 101% 8.1 00028-94-05pH1.5 H1LL0042.D 9.4 1507704 447 99% 8.1 00028-94-06pH1.5 HILL0043.D 9.4 2029865 627 105% 8.1 00028-94-07pH1.5 HILL0044.D 9.4 2358294 755 101% 8.1 00028-94-08pH 1.5 HILL0045.D 9.4 2709145 890 99% 8.1 00028-94-09pH1.5 HILL0046.D 9.4 2974918 1031 103% 8.1 MeOH HILL0047.D 9.4 0 0 8.1 00028-94-05pH1.5 HILL0048.D 9.4 1490907 444 99% 8.1 MeOH HILL0049.D 9.4 0 0 8.1 061500-PFOA-217 HILL0050.D 9.4 0 0 8.1 061500-PFOA-218 HILL0051.D 9.4 604624 172 120% Day 84 8.1 061500-PFOA-219 HILL0052.D 9.4 1517361 456 Day 84 8.1 061500-PFOA-22Q HILL0053.D 9.4 1510944 451 Day 84 8.1 061500-PFOA-221 HILL0054.D 9.4 1539754 465 Day 84 8.1 061500-PFO A-222 HILL0055.D 9.4 1960046 611 2% 108% Day 84 8.1 061500-PF OA-253 H1LL0056.D 9.4 0 0 8.1 061500-PFOA-254 061500-PFOA-255 HILL0057.D HILL0058.D 9.4 560356 9.4 1595422 162 492 113% Day 109 Day 109 8.1 8.1 0 6 1500-PFOA-256 HILL0059.D 9.4 1537794 474 Day 109 8.1 061500-PFOA-257 HILL0060.D 9.4 1535979 474 Day 109 8.1 061500-PFOA-258 HILL0061.D 9.4 1990160 641 2% 112% Day 109 8.1 MeOH HILL0062.D 9.4 0 0 8.1 00028-94-00pH 1.5 HILL0063.D 9.4 0 0 8.1 00028-94-01pH1.5 HLL0064.D 9.4 79881 25 99% 8.1 00028-94-02pH 1,5 HILL0Q65.D 9.4 247801 72 96% 8.1 00028-94-03pH 1.5 HILL0066.D 9.4 514837 151 100% 8.1 00028-94-04pH 1.5 HILL0067.D 9.4 1001851 299 100% 8.1 00028-94-05pH1.5 HILL0068.D 9.4 1402353 433 96% 8.1 00028-94-06pH1.5 HILL0069.D 9.4 1903303 613 102% 8.1 00028-94-07pH1.5 HILL0070.D 9.4 2201968 731 98% 8.1 00028-94-08pH 1.5 HILL0071.D 9.4 2518146 863 96% 8.1 00028-94-09pH 1.5 HILL0072.D 9.4 2781745 1001 100% 8.1 MeOH HLL0073.D 9.4 0 0 8.1 00028-94-05pH1.5 HILL0074.D 9.4 1402132 433 96% 8.1 MeOH HILL0075.D 9.4 0 0 8.1 Method ID: Internal Standard Quant r2= Mean Curve averaged: Linear Include origin S.D. Calibration range: %RSD Area 0 920372 920248 917644 908656 913334 909832 909575 904499 910954 894725 0 905282 0 914526 901245 899701 905411 897771 897808 893109 884363 883585 881033 878889 875500 0 886792 882599 884472 873915 876948 871142 868907 867391 867226 855161 0 870879 0 892162 17947 2% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 BACK TO MAIN Page 53 of 99 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH 3.0 Page 1 of 3 Retention times (RT) in minutes All concentrations in ng/ml___________________ PFOA_____________________________________________________________________PFBS in - `/Standard r % Spike RT Area Cone. 1 -fm Recovery Tme Point RT MeOH HILL0012.D 9.4 0 0 8.1 00028-95-00 pH3 HILL0013.D 9.4 0 0 8.1 00028-95-01 pH3 HILL0014.D 9.5 82288 27 107% 8.2 00028-95-02 pH3 HILL0015.D 9.5 269055 73 98% 8.2 00028-95-03 pH3 HILL0016.D 9.5 579192 150 100% 8.2 00028-95-04 pH3 HILL0017.D 9.5 1147139 302 101% 8.2 00028-95-05 pH3 HILL0018.D 9.5 1655072 443 98% 8.2 00028-95-06 pH3 HILL0019.D 9.5 2202783 611 102% 8.2 00028-95-07 pH3 HILL0020.D 9.5 2587642 745 99% 8.2 00028-95-08 pH3 HILL0021.D 9.5 3017472 901 100% 8.2 00028-95-09 pH3 HILL0022.D 9.5 3283065 1007 101% 8.2 MeOH HILL0023.D 9.4 0 0 8.2 00028-95-05 pH3 HILL0024.D 9.5 1650531 443 98% 8.1 MeOH HILL0025.D 9.4 0 0 8.2 061500-PFOA-007 HILL0026.D 9.4 0 0 8.1 061500-PFOA-008 061500-PFOA-009 061500-PFOA-010 061500-PFOA-011 061500-PFOA-012 061500-PFOA-043 HILL0027.D HILL0028.D HILL0029.D HILL0030.D HILL0031.D HILL0032.D 9.5 614033 9.5 2150355 9.5 1886072 9.5 2258658 9.5 2755176 9.4 0 161 601 519 634 802 0 10% 113% (A) 8.2 (A) 8.2 (A) 8.2 (A) 8.2 152% (A) 8.2 8.2 061500-PFOA-044 061500-PFOA-045 061500-PFOA-046 061500-PFOA-047 061500-PFOA-048 061500-PFOA-079 HILL0033.D HILL0034.D HILL0035.D HILL0036.D HILL0037.D HILL0038.D 9.5 611332 9.5 1905798 9.5 2206679 9.5 2221831 9.5 2752943 9.4 0 163 527 620 628 798 0 10% 114% (A) 8.2 (A) 8.2 (A) 8.2 (A) 8.2 144% (A) 8.2 8.2 061500-PFOA-080 061500-PFOA-081 061500-PFOA-082 061500-PFOA-083 061500-PFOA-084 MeOH HILL0039.D HLL0040.D HILL0041.D HILL0042.D HILL0043.D HILL0044.D 9.5 604571 9.5 1898593 9.5 2232596 9.5 2237534 9.5 2702174 9.4 0 161 526 630 630 796 0 10% 113% (A) 8.2 (A) 8.2 (A) 8.2 (A) 8.2 140% (A) 8.2 8.2 00028-95-00 pH3 HILL0045.D 9.4 0 0 8.1 00028-95-01 pH3 HILL0046.D 9.5 81670 27 108% 8.2 00028-95-02 pH3 HILL0047.D 9.5 266593 72 96% 8.2 00028-95-03 pH3 HILL0048.D 9.5 . 566629 150 100% 8.2 00028-95-04 pH3 HILL0049.D 9.5 1138030 301 100% 8.2 00028-95-05 pH3 HILL0050.D 9.5 1633153 444 99% 8.2 00028-95-06 pH3 HILL0051.D 9.5 2188592 611 102% 8.2 00028-95-07 pH3 HILL0052.D 9.5 2570321 742 99% 8.2 00028-95-08 pH3 HILL0053.D 9.5 3007296 890 99% 8.2 00028-95-09 pH3 HILL0054.D 9.5 3275642 997 100% 8.2 MeOH 00028-95-05 pH3 MeOH HILL0055.D HILL0056.D HILL0057.D 9.4 0 9.5 1631027 9.4 0 0 445 0 99% 8.2 8.1 8.2 Method ID: Internal Standard Quant r2= Mean Curve averaged: Linear. Indude origin S.D. Calibration range: %RSD (A) Data exduded on the basis of data quality objectives; see text. Area 0 927094 921572 910546 921285 911307 915905 910530 900619 896540 892929 0 912435 0 905282 908646 901399 901753 903197 901146 899419 896272 899635 899752 895897 904182 892381 895655 896661 897898 899923 888923 0 918573 903510 915431 903493. 907618 901434 904628 897410 901962 897625 0 898547 0 903975 8669 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 Page 54 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study SOC pH 3.0 Page 2 of 3 Retention times (RT) in minutes AH concentrations in ng/ml____________________PFOA_____________________________________________________________________PFBS "/Standard or %Spika in pyfe tnti ____ RT Area Cone. RSD Recovery Time Point RT MeOH HILL0044.D 9.4 0 0 8.1 00028-95-00 pH3 HILL0045.D 9.4 0 0 8.2 00028-95-01 pH3 HILL0046.D 9.5 81670 27 109% 8.2 00028-95-02 pH3 HILL0047.D 9.5 266593 72 96% 8.2 00028-95-03 pH3 HILL0048.D 9.5 566629 149 100% 8.2 00028-95-04 pH3 HILL0049.D 9.5 1138030 300 100% 8.2 00028-95-05 pH3 HILL0050.D 9.5 1633153 443 98% 8.2 00028-95-06 pH3 HILL0051.D 9.5 2188592 610 102% 8.2 00028-95-07 pH3 HILL0052.D 9.5 2570321 741 99% 8.2 00028-95-08 pH3 HILL0053.D 9.5 3007296 889 99% 8.2 00028-95-09 pH3 HILL0054.D 9.5 3275642 997 100% 8,2 MeOH HILL0055.D 9.4 0 0 8.1 00028-95-05 pH3 HILL0056.D 9.5 1631027 444 99% 8.2 MeOH HILL0057.D 9.4 0 0 8.1 061500-PFOA-115 HILL0058.D 9.4 0 0 8.2 061500-PFOA-116 HILL0059.D 9.5 613665 164 115% Day 28 8.2 061500-PFOA-117 HILL0060.D 9.5 2267521 642 Day 28 8.2 061500-PFOA-118 HILL0061.D 9.5 2205319 625 Day 28 8.2 061500-PFOA-119 HILL0062.D 9.5 2248453 635 Day 28 8.2 061500-PFOA-120 HILL0063.D 9.5 2696754 787 1% 107% Day 28 8.2 061500-PFOA-151 HILL0064.D 9.4 0 0 8.2 061500-PFOA-152 HILL0065.D 9.5 306384 84 59% Day 42 8.2 061500-PFOA-153 HILL0066.D 9.5 2229287 642 Day 42 8.2 0615 0 0 -P F O A -1 5 4 H1LL0067.D 9.5 2291761 654 Day 42 8.2 061500-PFO A-155 061500-PFOA-156 HILL0068.D HILL0069.D 9.5 2222262 9.5 2728089 632 801 2% 118% Day 42 Day 42 8.2 8.2 061500-PFOA-187 HILL0070.D 9.4 0 0 8.2 061500-PFO A-188 061500-PFOA-189 061500-PFOA-190 061500-PFOA-191 061500-PFOA-192 MeOH H ILL0071.D HILL0072.D HILL0073.D HILL0074.D HILL0075.D HILL0076.D 9.5 5 9 7 7 6 8 9.5 2230834 9.5 2220767 9.5 2175592 9.5 2218869 9.4 0 158 636 624 617 634 0 2% 111% 6% (A) 8.2 (A) 8.2 (A) 8.2 (A) 8.2 (A) 8.2 8.1 00028-95-00 pH3 HILL0077.D 9.4 0 0 8.2 00028-95-01 pH3 HILL0078.D 9.5 81990 27 109% 8.2 00028-95-02 pH3 HILL0079.D 9.5 263046 72 96% 8.2 00028-95-03 pH3 HILL0080.D 9.5 561799 149 100% 8.2 00028-95-04 pH3 HILL0081.D 9.5 1126245 303 101% 8.2 00028-95-05 pH3 HILL0082.D 9.5 1628681 450 100% 8.2 00028-95-06 pH3 HILL0083.D 9.5 2163770 605 101% 8.2 00028-95-07 pH3 HILL0084.D 9.5 2571272 749 100% 8.2 00028-95-08 pH3 HILL0085.D 9.5 3008963 899 100% 8.2 00028-95-09 pH3 HILL0086.D 9.5 3281436 1009 101% 8.2 MeOH HILL0087.D 9.4 0 0 8.1 00028-95-05 pH3 HILL0088.D 9.5 1627096 448 99% 8.2 MeOH HILL0089.D 9.4 0 0 8.1 Method ID: Internal Standard Quant r2= Mean Curve averaged: Linear Include origin S.D. Calibration range: %RSD (A) Data excluded on the basis of data quality objectives; see text. Area 0 918573 '903510 915431 903493 907618 901434 904628 897410 901962 897625 0 898547 0 889427 888249 894950 891533 896567 894156 892946 889139 880874 890001 889193 891422 892118 899210 888466 899035 889806 886188 0 908306 900139 902844 896488 890938 885914 900861 888898 894472 890276 0 889550 0 896055 8041 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 Page 55 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH 3.0 Page 3 of 3 Retention times (RT) in minutes All concentrations in ng/ml PFOA____________________________________________________ _______ PFBS a * ----- 1t \ T................... -- - i w . P T Area %Standard or pert % Spike Recovery Time Point RT MeOH HILL0036.D 9.5 0 0 8.1 00028-95-00 pH3 00028-95-01 pH3 HILL0037.D HILL0038.D 9.5 0 9.5 81990 0 27 108% 8.2 8.2 00028-95-02 pH3 H1LL0039.D 9.5 263046 72 96% 8.2 00028-95-03 pH3 HILL0040.D 9.5 561799 149 99% 8.2 00028-95-04 pH3 HILL0041.D 9.5 1126245 302 101% 8.2 00028-95-05 pH3 HILL0042.D 9.5 1628681 448 100% 8.2 00028-95-06 pH3 HILL0043.D 9.5 2163770 601 100% 8.2 00028-95-07 pH3 HILL0044.D 9.5 2571272 744 99% 8.2 00028-95-08 pH3 HILL0045.D 9.5 3008963 892 99% 8.2 00028-95-09 pH3 HILL0046.D 9.5 3281436 1000 100% 8.2 MeOH HILL0047.D 9.4 0 0 8.1 00028-95-05 pH3 HILL0048.D 9.5 1627096 445 99% 8.2 MeOH HILL0049.D 9.4 0 0 8.1 061500-PFOA-223 HILL0050.D 9.4 0 0 8.2 061500-PFOA-224 HILL0051.D 9.5 612098 163 114% (A) 8.2 061500-PFOA-225 HILL0052.D 9.5 2228621 626 (A) 8.2 061500-PFOA-226 HILL0053.D 9.5 2239448 636 (A) 8.2 061500-PFOA-227 HILL0054.D 9.5 2240728 622 (A) 8.2 061500-PFOA-228 HILL0055.D 9.5 2760460 815 1% 131% (A) 8.2 061500-PFOA-259 HILL0056.D 9.4 0 0 8.2 061500-PFOA-260 HILL0057.D 9.5 616878 163 114% Day 109 8.2 061500-PFOA-261 HILL0058.D 9.5 2250975 633 Day 109 8.2 061500-PFOA-262 HILL0059.D 9.5 2240681 627 Day 109 8.2 061500-PFOA-263 HILL0060.D 9.5 2271686 645 Day 109 8.2 061500-PFOA-264 HILL0061.D 9.5 2756615 808 1% 121% Day 109 8.2 MeOH HILL0062.D 9.4 0 0 8.1 00028-95-00 pH3 HILL0063.D 9.4 0 0 8.2 00028-95-01 pH3 00028-95-02 pH3 00028-95-03 pH3 00028-95-04 pH3 HILL0064.D HILL0065.D HILL0066.D HILL0067.D 9.5 82634 9.5 263401 9.5 566621 9.5 1133921 27 72 150 302 109% 96% 100% 101% 8.2 8.2 8.2 8.2 00028-95-05 pH3 00028-95-06 pH3 HILL0068.D HILL0069.D 9.5 1637254 9.5 2208136 445 619 99% 103% 8.2 8.2 00028-95-07 pH3 00028-95-08 pH3 HILL0070.D HILL0071.D 9.5 2589080 9.5 3039283 740 895 99% 100% 8.2 8.2 00028-95-09 pH3 MeOH 00028-95-05 pH3 HILL0072.D HILL0073.D HILL0074.D 9.5 3335024 9.4 0 9.4 1640712 1010 0 446 101% 99% 8.2 8.1 8.2 MeOH HILL0075.D 9.4 0 0 8.1 Method ID: Internal Standard Quant r2~ Mean Curve averaged: Linear Include origin S.D. Calibration range: %RSD (A) Data excluded on the basis of data quality objectives; see text. Area 0 908306 900139 902844 896488 890938 885914 900861 888898 894472 890276 0 889550 0 888561 891000 895116 887463 904510 883345 899277 894729 895567 898600 889165 888556 0 903980 893569 902304 893639 896773 896616 896206 899125 901039 897706 0 895452 0 895323 5879 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 BACK TO MAIN Page 56 of 99 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH 5.0 Page 1 of 3 Retention times (RT) in minutes Alt concentrations in ng/mi______________ ::': "is: ! * r " MeOH 00028-96-00 pH5 00028-96-01 pH5 00028-96-02 pH5 00028-96-03 pH5 00028-96-04 pH5 00028-96-05 pH5 00028-96-06 pH5 00028-96-07 pH5 00028-96-08 pH5 00028-96-09 pH5 MeOH 00028-96-05 pH5 MeOH 061500-PFOA-013 061500-PFOA-014 061500-PFOA-015 061500-PFOA-016 061500-PFOA-017 061500-PFOA-018 061500-PFOA-049 061500-PFOA-050 061500-PFOA-051 061500-PFOA-052 061500-PFOA-053 061500-PFOA-054 061500-PFOA-085 061500-PFOA-086 061500-PFOA-087 061500-PF OA-088 061500-PFOA-089 061500-PFOA-090 MeOH 00028-96-00 pH5 00028-96-01 pH5 00028-96-02 pH5 00028-96-03 pH5 00028-96-04 pH5 00028-96-05 pH5 00028-96-06 pH5 00028-96-07 pH5 00028-96-08 pH5 00028-96-09 pH5 MeOH 00028-96-05 pH5 MeOH Method ID: " '' IW C T . :i HILL0013.D HILL0014.D HILL0015.D HILL0016.D HILL0017.D HILL0018.D HILL0019.D HILL0020.D HILL0021.D HILL0022.D HILL0023.D HILL0024.D HILL0025.D HILL0026.D HILL0027.D HILL0028.D HILL0029.D H1LL0030.D HILL0031.D HILL0032.D HILL0033.D HILL0034.D HILL0035.D HILL0036.D HILL0037.D HILL0038.D HILL0039.D HILL0040.D HILL0041.D HILL0042.D HILL0043.D HILL0044.D HILL0045.D HILL0046.D HILL0047.D HILL0048.D HILL0049.D HILL0050.D HILL0051.D HILL0052.D HILL0053.D HILL0054.D HILL0055.D HILL0056.D HLL0057.D HILL0058.D PFOA _________________________________________________________________ PFBS `Standard or % Spike RT Area Cone. oerj Recovery Time Point RT 9.4 0 0 8.1 9.4 0 0 8.1 9.5 82475 22 89% 8.2 9.5 255658 70 93% 8.2 9.5 562034 9.5 1058309 9.5 1526761 9.5 2024353 157 305 455 620 104% 102% 101% 104% 8.2 8.2 8.2 8.2 9.5 2321582 9.5 2786856 9.5 3056755 718 903 1021 96% 100% 102% 8.2 8.2 8.2 9.4 0 9.5 1515645 9.4 0 9.4 0 0 449 0 0 100% 8.2 8.1 8.2 8.1 9.5 574463 9.5 2136301 161 655 113% Day 0 Day 0 8.2 8.2 9.5 2146831 9.5 2133454 9.5 2608029 9.4 0 9.5 606301 9.5 2158146 9.5 2167566 9.5 2181107 9.5 2647149 9.4 0 9.5 607581 9.5 2184729 9.5 2158052 9.5 2152055 659 657 822 0 169 654 657 657 828 0 168 654 657 657 0% 0% 115% 118% 120% 117% Day 0 Day 0 Day 0 Day 7 Day 7 Day 7 Day 7 Day 7 Day 14 Day 14 Day 14 Day 14 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 9.5 2605276 819 0% 114% Day 14 8.2 9.4 0 9.4 0 9.5 84676 0 0 22 89% 8.2 8.1 8.2 9.5 260410 9.5 571088 9.5 1096775 9.5 1553008 9.5 2059026 9.5 2349365 9.5 2880656 9.5 3135872 9.4 0 9.5 1562785 9.4 0 69 155 306 449 610 709 901 1001 0 453 0 92% 103% 102% 100% 102% 95% 100% 100% 101% 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.1 8.2 Internal Standard Quant r2= Curve averaged: Linear Include origin Calibration range: Mean S.D. %RSD Area 0 921369 915365 924155 923989 917918 912758 916325 924366 915970 909916 0 917581 0 920231 919417 921753 921718 918250 926469 922553 927505 932092 932872 938261 934544 940621 933688 944180 928637 925961 928366 0 940846 941774 951765 950664 949249 939795 945478 945728 948113 948233 0 947886 0 930659 12253 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 . 158 158 158 158 158 158 158 0 158 0 Page 57 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH 5.0 Page 2 of 3 Retention times (RT) in minutes All concentrations in ng/ml______ PFOA____________________________________________________________________ PFBS 1r\ ______git,:..- 1------------ RT "/Standard or ocr\ % Spike Rscsvery Time Point RT MeOH HILL0045.D 9.5 0 0 8.1 00028-96-00 pH5 HILL0046.D 9.5 0 0 8.2 00028-96-01 pH5 HILL0047.D 9.5 84676 23 91% 8.2 00028-96-02 pH5 HILL0048.D 9.5 260410 70 94% 8.2 00028-96-03 pH5 00028-96-04 pH5 HILL0049.D HILL0050.D 9.5 571088 9.5 1096775 156 302 104% 101% 8.2 8.2 00028-96-05 pH5 HILL0051.D 9.5 1553008 446 99% 8.2 00028-96-06 pH5 HILL0052.D 9.5 2059026 612 102% 8.2 00028-96-07 pH5 HILL0053.D 9.5 2349365 713 95% 8.2 00028-96-08 pH5 00028-96-09 pH5 MeOH 00028-96-05 pH5 MeOH 061500-PFOA-121 061500-PFOA-122 061500-PFOA-123 061500-PFOA-124 061500-PFOA-125 061500-PFOA-126 HILL0054.D HILL0055.D HILL0056.D HILL0057.D HILL0058.D HILL0059.D HILL0060.D HILL0061.D HILL0062.D HILL0063.D HLL0064.D 9.5 2880656 9.5 3135872 9.5 0 9.5 1562785 9.5 0 9.5 0 9.5 605920 9.5 2183595 9.5 2158582 9.5 2189482 9.5 2631516 898 990 0 452 0 0 166 656 652 656 823 100% 99% 0% 100% 116% 118% Day 28 Day 28 Day 28 Day 28 Day 28 8.2 8.2 8.1 8.2 8.1 8.2 8.2 8.2 8.2 8.2 8.2 061500-PFOA-157 061500-PFOA-158 061500-PFOA-159 HILL0065.D HILL0066.D HILL0067.D 9.5 0 9.5 614384 9.5 2177138 0 168 652 118% Day 42 Day 42 8.2 8.2 8.2 061500-PFOA-160 HILL0068.D 9.5 2203841 664 Day 42 8.2 061500-PFOA-161 HILL0069.D 9.5 0 0 8.2 061500-PFOA-162 HILL0070.D 9.5 605707 166 116% Day 64 8.2 061500-PF OA-193 HILL0071.D 9.5 2166222 651 Day 42 8.2 061500-PFOA-194 HILL0072.D 9.5 2631811 816 1% 112% Day 42 8.2 061500-PFOA-195 HILL0073.D 9.5 2170827 651 Day 64 8.2 061500-PFOA-196 HILL0074.D 9.5 2143552 643 Day 64 8.2 061500-PFOA-197 HILL0075.D 9.5 2135796 635 Day 64 8.2 061500-PFOA-198 HILL0076.D 9.5 2616028 810 1% 116% Day 64 8.2 MeOH 00028-96-00 pH5 00028-96-01 pH5 00028-96-02 pH5 HILL0077.D HILL0078.D HILL0079.D HILL0080.D 9.5 0 9.5 0 9.5 86643 9.5 262432 0 0 23 70 91% 93% 8.1 8.2 8.2 8.2 00028-96-03 pH5 HILL0081.D 9.5 570398 155 104% . 8.2 00028-96-04 pH5 00028-96-05 pH5 00028-96-06 pH5 HILL0082.D HILL0083.D HILL0084.D 9.5 1088630 9.5 1546530 9.5 2054021 308 453 617 103% 101% 103% 8.2 8.2 8.2 00028-96-07 pH5 00028-96-08 pH5 00028-96-09 pH5 HILL0085.D HILL0086.D HILL0087.D 9.5 2310100 9.5 2796128 9.5 3056737 718 917 1021 96% 102% 102% 8.2 8.2 8.2 MeOH 00028-96-05 pH5 MeOH HILL0088.D HILL0089.D HILL0090.D 9.5 0 9.5 1542658 9.5 0 0 442 0 8.1 98% 8.2 8.1 Method ID: Internal Standard Quant r2= Mean Curve averaged: Linear Indude origin S.D. Calibration range: %RSD Area 0 940846 941776 951765 950664 949249 939795 945478 945728 948113 948233 0 947886 0 951447 946797 950023 944305 952558 945243 945258 946659 952533 948708 947409 946637 949001 952353 950698 949324 955977 952636 0 955228 958845 949601 947310 958868 948139 948905 935500 935500 946508 0 953869 0 948384 5146 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 Page 58 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH 5.0 Page 3 of 3 Retention times (RT) in minutes All concentrations in ng/ml______ e.m .1. i n MeOH 00028-96-00 pH5 00028-96-01 pH5 00028-96-02 pH5 00028-96-03 pH5 00028-96-04 pH5 00028-96-05 pH5 00028-96-06 pH5 00028-96-07 pH5 00028-96-08 pH5 00028-96-09 pH5 MeOH 00028-96-05 pH5 MeOH 061500-PFOA-229 061500-PFOA-230 061500-PFOA-231 061500-PFOA-232 061500-PFOA-233 061500-PFOA-234 061500-PFOA-265 061500-PFOA-266 061500-PFOA-267 061500-PFOA-268 061500-PFOA-269 061500-PFOA-270 MeOH 00028-96-00 pH5 00028-96-01 pH5 00028-96-02 pH5 00028-96-03 pH5 00028-96-04 pH5 00028-96-05 pH5 00028-96-06 pH5 00028-96-07 pH5 00028-96-08 pH5 00028-96-09 pH5 MeOH 00028-96-05 pH5 MeOH Method ID: ______:T HILL0077.D HILL0078.D HILL0079.D HILL0080.D HILL0081.D HILL0082.D HILL0083.D HILL0084.D HILL0085.D HILL0086.D HILL0087.D H1LL0088.D HILL0089.D HILL0090.D HILL0091.D HILL0092.D HILL0093.D HILL0094.D HILL0095.D HILL0096.D HILL0097.D HILL0098.D HILL0099.D HtLL0100.D HILL0101.D HILL0102.D HILL0103.D HILL0104.D HILL0105.D HILL0106.D HILL0107.D HILL0108.D HILL0109.D HILL0110.D HILL0111.D HILL0112.D HILL0113.D HILL0114.D HILL0115.D HILL0116.D PFOA__________________ _________________________________________________ PFBS "/Standard or . % Spike RT Area Cone, RSD Recovery ~HmePo*nf RT 9.5 0 0 8.1 9.5 0 0 8.2 9.5 86643 22 89% 8.2 9.5 262432 70 93% 8.2 9.5 570398 155 103% 8.2 9.5 1088630 301 100% 8.2 9.5 1546530 446 99% 8.2 9.5 2054021 613 102% 8.2 9.5 2310100 715 95% 8.2 9.5 2796128 902 100% 8.2 9.5 3056737 996 100% 8.2 9.4 0 0 8.1 9.5 1542658 442 98% 8.2 9.4 0 0 8.1 9.4 0 0 8 .2 9.5 608076 163 114% Day 84 8 .2 9.5 2176525 659 Day 84 8 .2 9.5 2174338 650 Day 84 8.2 9.5 2188043 652 Day 84 8 .2 9.5 2641765 818 1% 115% Day 84 - 8.2 9.4 0 0 8 .2 9.5 614037 165 115% Day 109 8 .2 9.5 2165828 646 Day 109 8 .2 9.5 2158127 645 Day 109 8 .2 9.5 2158778 646 Day 109 8 .2 9.5 2614502 815 0% 119% Day 109 8 .2 9.4 0 0 8.1 9.4 0 0 8.2 9.5 85429 22 87% 8.2 9.5 272871 72 95% 8.2 9.5 591035 158 106% 8.2 9.5 1112890 309 103% 8.2 9.5 1573750 450 100% 8.2 9.5 2082125 617 103% 8.2 9.5 2358719 719 96% 8.2 9.5 2859084 914 102% 8.2 9.5 3126850 1013 101% 8.2 9.4 0 0 8.1 9.5 1586479 453 101% 8.2 9.4 0 0 8.1 Internal Standard Quant r2= Mean Curve averaged: Linear Indude origin S.D. Calibration range: %RSD Area 0 955228 958844 949601 947310 958868 948139 948905 935500 935500 946508 0 953869 0 949997 961668 944432 955071 957682 956518 957086 960587 956380 953814 953458 949340 0 949450 960609 960835 960977 958033 956723 956217 950202 947024 955639 0 959032 0 953207 6605 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 BACK TO MAIN Page 59 of 99 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH 7.0 Page 1 of 3 Retention times (RT) in minutes %spii"AH concentrations in ng/ml ______ ___ ________ PFOA____________________________________________________________________ PFBS "/Standard or in O ste & U g M ' RT Area" RSD Recovery RT MeOH HILL0013.D 9.5 0 0 8.2 00028-97-00 pH7 HILL0014.D 9.5 0 0 8.2 00028-97-01 pH7 HILL0015.D 9.5 89549 27 110% 8.2 00028-97-02 pH7 HILL0016.D 9.5 273000 74 98% 8.2 00028-97-03 pH7 HILL0017.D 9.5 564682 149 99% 8.2 00028-97-04 pH7 HILL0018.D 9.5 1118278 300 100% 8.2 00028-97-05 pH7 HILL0019.D 9.5 1584297 436 97% 8.2 00028-97-06 pH7 H1LL0020.D 9.5 2153006 616 103% 8.2 00028-97-07 pH7 HILL0021.D 9.5 2550401 749 100% 8.2 00028-97-08 pH7 HILL0022.D 9.5 2901395 880 98% 8.2 00028-97-09 pH7 HILL0023.D 9.5 3194702 1004 100% 8.2 MeOH HILL0024.D 9.5 0 0 8.2 00028-97-05 pH7 HILL0025.D 9.5 1599875 440 98% 8.2 MeOH HILL0026.D 9.5 0 0 8.2 061500-PFOA-019 HILL0027.D 9.5 0 0 8.2 061500-PFOA-020 HILL0028.D 9.5 623804 165 116% Day 0 8.2 061500-PFOA-021 HILL0029.D 9.5 2274515 662 Day 0 8.2 061500-PFOA-022 HILL0030.D 9.5 2249080 645 Day 0 8.2 061500-PFOA-023 HILL0031.D 9.5 2269461 652 Day 0 8.2 061500-PFOA-024 HILL0032.D 9.5 2742883 818 1% 116% Day 0 8.2 061500-PFOA-055 HILL0033.D 9.5 0 0 8.2 061500-PFOA-056 HILL0034.D 9.5 619990 166 116% Day 7 8.2 061500-PFOA-057 HILL0035.D 9.5 2255587 648 Day 7 8.2 061500-PFOA-058 HILL0036.D 9.5 2246779 648 Day 7 8.2 061500-PFOA-059 HILL0037.D 9.5 2234292 650 Day 7 8.2 061500-PFOA-060 HILL0038.D 9.5 2714705 816 0% 117% Day 7 8.2 061500-PFOA-091 HILL0039.D 9.5 0 0 8.2 061500-PFOA-092 HILL0040.D 9.5 621311 166 116% Day 14 8.2 061500-PFOA-093 HILL0041.D 9.5 2242645 653 Day 14 8.2 061500-PFOA-094 HILL0042.D 9.5 2192603 633 Day 14 8.2 061500-PFOA-095 HILL0043.D 9.5 2182058 641 Day 14 8.2 061500-PFOA-096 HILL0044.D 9.5 2717288 822 2% 125% Day 14 8.2 MeOH HILL0045.D 9.5 0 0 8.2 00028-97-00 pH7 HILL0046.D 9.5 0 0 8.2 00028-97-01 pH7 H1LL0047.D 9.5 87291 27 108% 8.2 00028-97-02 pH7 HILL0048.D 9.5 271707 74 98% 8.2 00028-97-03 pH7 HILL0049.D 9.5 556644 150 100% 8.2 00028-97-04 pH7 HILL0050.D 9.5 1104538 301 100% 8.2 00028-97-05 pH7 HILL0051.D 9.5 1574928 443 99% 8.2 00028-97-06 pH7 HILL0052.D 9.5 2120131 617 103% 8.2 00028-97-07 pH7 HILL0053.D 9.5 2501752 746 100% 8.2 00028-97-08 pH7 HILL0054.D 9.5 2834850 890 99% 8.2 00028-97-09 pH7 HILL0055.D 9.5 3142471 1010 101% 8.2 MeOH HILL0056.D 9.5 0 0 8.2 00028-97-05 pH7 HILL0057.D 9.5 1571464 437 97% 8.2 MeOH HILL0058.D 9.5 0 0 8.2 Method ID: Internal Standard Quant r2= Mean Curve averaged: Linear Include origin S.D. Calibration range: %RSD (A) Data excluded on the basis of data quality objectives; see text. Area 0 1000845 979100 974706 973127 969992 970056 968853 973022 972623 968378 0 971523 0 968331 968193 962126 972489 972809 973930 972244 959302 971393 968350 960307 966356 952539 960551 960092 964008 949386 961815 0 995123 970814 966617 953431 955535 949127 952380 957556 941774 948270 0 958489 0 965889 11537 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 Page 60 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. EOO-1851 BACK TO MAIN oco: O PFOA Hydrolysis Study 50C pH 7.0 Page 2 of 3 Retention times (RT) in minutes AH concentrations in ng/ml Ssmpls !.D. MeOH 00028-97-00 pH7 00028-97-01 pH7 00028-97-02 pH7 00028-97-03 pH7 00028-97-04 pH7 00028-97-05 pH7 00028-97-06 pH7 00028-97-07 pH7 00028-97-08 pH7 00028-97-09 pH7 MeOH 00028-97-05 pH7 MeOH 061500-PFOA-127 061500-PFOA-128 061500-PFOA-129 061500-PFOA-130 061500-PFOA-131 061500-PFOA-132 061500-PFOA-163 061500-PFOA-164 061500-PFOA-165 061500-PFOA-166 061500-PFOA-167 061500-PFOA-168 061500-PFOA-199 061500-PFOA-200 061500-PFOA-201 061500-PFOA-202 061500-PFOA-203 061500-PFOA-204 MeOH 00028-97-00 pH7 00028-97-01 pH7 00028-97-02 pH7 00028-97-03 pH7 00028-97-04 pH7 00028-97-05 pH7 00028-97-06 pH7 00028-97-07 pH7 00028-97-08 pH7 00028-97-09 pH7 MeOH 00028-97-05 pH7 MeOH Method ID: HILL0045.D HILL0046.D HILL0047.D HILL0048.D HILL0049.D HILL0050.D HILL0051.D HILL0052.D HILL0053.D HILL0054.D HILL0055.D HILL0056.D HILL0057.D HILL0058.D H1LL0059.D HILL0060.D HILL0061.D HILL0062.D HILL0063.D HILL0064.D HILL0065.D HILL0066.D HILL0067.D HILL0068.D HLL0069.D HILL0070.D HILL0071.D HILL0072.D HILL0073.D HILL0074.D HILL0075.D HILL0076.D HILL0077.D HILL0078.D HILL0079.D HILL0080.D HILL0081.D HILL0082.D HILL0083.D HILL0084.D HILL0085.D HILL0086.D HILL0087.D HILL0088.D HILL0089.D HLL0090.D PFOA ; : t RT Area 9.5 0 0 9.5 0 0 9.5 87291 28 9.5 271707 74 9.5 556644 150 9.5 1104538 300 9.5 1574928 443 9.5 2120131 618 9.5 2501752 748 9.5 2834850 895 9.5 3142471 1018 9.5 0 0 9.5 1571464 437 9.5 0 0 9.5 0 0 9.5 605620 163 9.5 2204642 649 9.5 2192955 642 9.5 2206098 645 9.5 2699217 828 9.5 0 0 9.5 602566 163 9.5 2185187 654 9.5 2190101 650 9.5 2194629 647 9.5 2644173 814 9.5 0 0 9.5 605657 164 9.5 2167144 652 9.5 2213132 655 9.5 2214971 643 9.5 2656837 820 9.5 0 0 9.4 0 0 9.5 85517 27 9.5 266273 74 9.5 546536 149 . 9.5 1086341 299 9.5 1541845 436 9.5 2069653 613 9.5 2447183 751 9.5 2779965 880 9.5 3006154 991 9.5 0 0 9.5 1524429 436 9.5 0 0 Internal Standard Quant r2= Curve averaged: Linear Indude origin Calibration range: `Standard or RSD 110% 99% 100% 100% 98% 103% 100% 100% 102% 1% 1% 1% 110% 98% 100% 100% 97% 102% 100% 98% 99% % Spike Recovery 97% 114% 128% 114% 115% 114% 119% 97% PFBS Time Point Day 28 Day 28 Day 28 Day 28 Day 28 Day 42 Day 42 Day 42 Day 42 Day 42 Day 64 Day 64 Day 64 Day 64 Day 64 RT 8.1 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.1 8.2 8.1 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.3 8.2 8.1 8.2 8.2 8.2 8.2 8.3 8.2 8.3 8.3 8.2 8.3 8.1 8.3 8.1 Mean S.D. %RSD Area 0 995126 970814 966617 953431 955535 949127 952380 957556 941774 948270 0 958489 0 946761 952433 949777 953745 955727 952217 949483 946443 935651 942456 947731 945474 947388 947990 929447 946316 961798 944627 0 976974 956841 950814 938192 943983 943263 935696 933778 935659 925184 0 930947 0 949398 13021 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 Page 61 of 99 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH Page 3 of 3 Retention times (RT) in minutes All concentrations in ng/ml _________ _______ PFOA ____________________________________________________________ PFBS "/Standard o r % Spike Sample t.O. RT ; Arsa Cons. RSO Recovery Time Point RT MeOH HILL0077.D 9.5 0 0 8.2 00028-97-00 pH7 HILL0078.D 9.5 0 0 8.2 00028-97-01 pH7 HILL0079.D 9.5 85517 27 110% 8.2 00028-97-02 pH7 HILL0080.D 9.5 266273 74 99% 8.2 00028-97-03 pH7 HILL0081.D 9.5 546536 150 100% 8.2 00028-97-04 pH7 HILL0082.D 9.5 1086341 300 100% 8.3 00028-97-05 pH7 HILL0083.D 9.5 1541845 437 97% 8.2 00028-97-06 pH7 HILL0084.D 9.5 2069653 616 103% 8.3 00028-97-07 pH7 HILL0085.D 9.5 2447183 754 101% 8.3 00028-97-08 pH7 HILL0086.D 9.5 2779965 884 98% 8.2 00028-97-09 pH7 HILL0087.D 9.5 3006154 996 100% 8.3 MeOH HILL0088.D 9.5 0 0 8.3 00028-97-05 pH7 HILL0089.D 9.5 1524429 438 97% 8.3 MeOH HILL0090.D 9.5 0 0 8.3 061500-PFOA-235 HILL0091.D 9.5 0 0 8.3 061500-PFOA-236 HILL0092.D 9.5 595311 166 116% Day 84 8.2 061500-PFOA-237 HILL0093.D 9.5 2174118 648 Day 84 8.3 061500-PFOA-238 HILL0094.D 9.5 2168837 652 Day 84 8.3 061500-PFOA-239 HILL0095.D 9.5 2176750 657 Day 84 8.2 061500-PFOA-240 HILL0096.D 9.5 2587928 821 1% 118% Day 84 8.2 061500-PFOA-271 HILL0097.D 9.5 0 0 8.3 061500-PFOA-272 HILL0098.D 9.5 602602 167 117% Day 109 8.3 061500-PFOA-273 HILL0099.D 9.5 2146703 651 Day 109 8.3 061500-PF OA-2 74 HILL0100.D 9.5 2137239 645 Day 109 8.3 061500-PFOA-275 HILL0101.D 9.5 2138359 645 Day 109 8.3 061500-PFOA-276 HILL0102.D 9.5 2596175 818 1% 120% Day 109 8.2 MeOH HILL0103.D 9.5 0 0 8.2 00028-97-00 pH7 H(LL0104.D 9.5 0 0 8.3 00028-97-01 pH7 HILL01Q5.D 9.5 84002 28 110% 8.2 00028-97-02 pH7 HILL0106.D 9.5 259555 73 98% 8.3 00028-97-03 pH7 HILL0107.D 9.5 541262 149 99% 8.2 00028-97-04 pH7 HILL0108.D 9.5 1067145 300 100% 8.2 00028-97-05 pH7 HILL0109.D 9.5 1526624 439 98% 8.3 00028-97-06 pH7 HILL0110.D 9.5 2052935 613 102% 8.2 00028-97-07 pH7 HILL0111.D 9.5 2429369 749 100% 8.2 00028-97-08 pH7 HILL0112.D 9.5 2778668 890 99% 8.3 00028-97-09 pH7 . HILL0113.D 9.5 3050552 1012 101% 8.2 MeOH HILL0114.D 9.5 0 0 8.2 00028-97-05 pH7 HILL0115.D 9.5 1519453 443 98% 8.2 MeOH HILL0116.D 9.5 0 0 8.2 Method ID: Internal Standard Quant r2= Mean Curve averaged: Linear: Indude origin S.D. Calibration range: %RSD Area 0 976974 956842 950814 938192 943983 943263 935696 933778 935659 925184 0 930947 0 922799 924193 941364 933629 931718 923066 927163 924895 925297 928837 929665 928467 0 959979 933019 933058 933578 925993 930801 931533 932217 930620 927764 0 919683 0 934431 11856 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 BACK TO MAIN Page 62 of 99 3M Environmental Laboratory Report No. EOO-1851 PFOA Hydrolysis Study 50C pH 9.0 Page 1 of 3 Retention times (RT) in minutes All concentrations in ng/ml______________ _____ n MeOH 00028-98-00 pH9 00028-98-01 pH9 00028-98-02 pH9 00028-98-03 pH9 00028-98-04 pH9 00028-98-05 pH9 00028-98-06 pH9 00028-98-07 pH9 00028-98-08 pH9 00028-98-09 pH9 MeOH 00028-98-05 pH9 MeOH 061500-PFOA-025 061500-PFOA-026 061500-PFOA-027 061500-PFOA-028 061500-PFOA-029 061500-PFOA-030 061500-PFOA-061 061500-PF OA-062 061500-PFOA-063 061500-PFOA-064 061500-PFOA-065 061500-PFOA-066 061500-PFOA-097 061500-PFO A-098 061500-PFOA-099 061500-PFOA-100 061500-PFOA-101 061500-PFOA-102 MeOH 00028-98-00 pH9 00028-98-01 pH9 00028-98-02 pH9 .00028-98-03 pH9 00028-98-04 pH9 00028-98-05 pH9 00028-98-06 pH9 00028-98-07 pH9 00028-98-08 pH9 00028-98-09 pH9 MeOH 00028-98-05 pH9 MeOH Method ID: HILL0002.D HILL0003.D HILL0004.D HILL0005.D HILL0006.D HILL0007.D HILL0008.D HILL0009.D HILL0010.D HILL0011.D HILL0012.D HILL0013.D HILL0014.D HILL0015.D HILL0016.D HILL0017.D HILL0018.D HILL0019.D HILL0020.D HLL0021.D HILL0022.D HILL0023.D HILL0024.D HILL0025.D HILL0026.D HILL0027.D HILL0Q28.D HILL0029.D HLL0030.D HILL0031.D HILL0032.D HILL0033.D HILL0034.D HILL0035.D HILL0036.D HILL0037.D HILL0038.D HILL0039.D HILL0040.D HILL0041.D HILL0042.D HILL0043.D HILL0044.D HILL0045.D HILL0046.D HILL0047.D PFOA________ _____________________________ _________ ____________________ PFBS %Standard or % Spike RT Arsa Cons. RSD Recovery Time Point RT 9.5 0 0 8.2 9.5 0 0 8.2 9.5 81677 25 98% 8.2 9.5 263406 73 97% 8.2 9.5 547426 148 99% 8.2 9.5 1080831 298 99% 8.3 9.5 1551837 434 96% 8.2 9.5 2097408 603 101% 8.2 9.5 2492449 740 99% 8.2 9.5 2883027 879 98% 8.2 9.5 3151926 991 99% 8.2 9.5 0 0 8.2 9.5 1545140 435 97% 8.2 9.5 0 0 8.2 9.5 0 0 8.2 9.5 611497 168 117% Day 0 8.2 9.5 2234987 661 Day 0 8.2 9.5 2204470 643 Day 0 8.2 9.5 2240142 656 Day 0 8.2 9.5 2657993 806 1% 107% Day 0 8.2 9.5 0 9.5 623086 0 171 119% Day 7 8.2 8.3 9.5 2248154 663 Day 7 8.2 9.5 2237255 9.5 2250744 662 659 Day 7 Day 7 8.2 8.2 9.5 2715890 807 0% 102% Day 7 8.2 9.5 0 9.5 627431 0 171 120% Day 14 8.2 8.2 9.5 2266363 669 Day 14 8.2 9.5 2264539 668 Day 14 8.2 9.5 2246680 662 Day 14 8.2 9.5 2735222 824 1% 110% Day 14 8.2 9.5 0 0 8.2 9.5 0 0 8.2 9.5 84910 26 103% 8.2 9.5 273512 75 100% 8.2 9.5 569596 155 103% 8.2 9.5 1116548 309 103% 8.2 9.5 1561236 445 99% 8.2 9.5 2104613 614 102% 8.2 9.5 2519089 761 102% 8.2 9.5 2937090 904 101% 8.2 9.5 3225468 1015 102% 8.2 9.5 0 0 8.2 9.5 1562031 442 98% 8.2 9.5 0 0 8.2 Internal Standard Quant r2= Mean Curve averaged: Linear Include origin S.D. Calibration range: %RSD Area 0 919589 922127 913873 919337 912713 919513 919055 911116 909972 901274 0 913746 0 893446 906490 902721 912251 910419 903282 906146 908411 905087 901785 911263 921345 915788 910482 904859 905811 905698 912348 0 911956 906017 920039 916507 912425 903511 907628 899479 906115 904792 0 908839 0 909931 6628 1% Cone 0.0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 Page 63 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH 9.0 Page 2 of 3 Retention times (RT) in minutes All concentrations in ng/ml______________ c 8r*pic i n MeOH 00028-98-00 pH9 00028-98-01 pH9 00028-98-02 pH9 00028-98-03 pH9 00028-98-04 pH9 00028-98-05 pH9 00028-98-06 pH9 00028-98-07 pH9 00028-98-08 pH9 00028-98-09 pH9 MeOH 00028-98-05 pH9 MeOH 061500-PFOA-133 061500-PFOA-134 061500-PFOA-135 061500-PFOA-136 061500-PFOA-137 061500-PFOA-138 061500-PFOA-169 061500-PFOA-170 061500-PFOA-171 061500-PFOA-172 061500-PFOA-173 061500-PFOA-174 061500-PFOA-205 061500-PFOA-206 061500-PFOA-207 061500-PFOA-208 061500-PFOA-209 061500-PFOA-210 MeOH 00028-98-00 pH9 00028-98-01 pH9 00028-98-02 pH9 00028-98-03 pH9 00028-98-04 pH9 00028-98-05 pH9 00028-98-06 pH9 00028-98-07 pH9 00028-98-08 pH9 00028-98-09 pH9 MeOH 00028-97-05 pH9 MeOH Method ID: -- - yw. ctt HILL0034.D HILL0035.D HILL0036.D HILL0037.D HILL0038.D HILL0039.D HILL0040.D HILL0041.D H1LL0042.D HILL0043.D HILL0044.D HILL0045.D HILL0046.D HILL0047.D HILL0048.D HILL0049.D HILL0050.D HJLL0051.D HILL0052.D HILL0053.D HILL0054.D HILL0055.D HILL0056.D HILL0057.D HILL0058.D HILL0059.D HILL0060.D HILL0061.D HILL0062.D HILL0063.D HILL0064.D HILL0065.D HILL0066.D HILL0067.D HILL0068.D HILL0069.D HILL0070.D HILL0071.D HILL0072.D HILL0073.D HILL0074.D HILL0075.D HILL0076.D HILL0077.D HILL0078.D HILL0079.D PFOA _____________________________________________________ "/(Standard or % Spike RT Arses RSD 9.5 0 9.5 0 9.5 84910 0 0 24 98% 9.5 273512 73 97% 9.5 569596 152 101% 9.5 1116548 305 102% 9.5 1561236 9.5 2104613 9.5 2519089 439 607 753 98% 101% 101% 9.5 2937090 895 100% 9.5 3225468 1006 101% 9.5 0 0 9.5 1562031 9.5 0 9.5 0 437 0 0 97% 9.5 603971 162 114% 9.5 2212354 645 9.5 2275081 661 9.5 2257809 656 9.5 2725058 819 1% 115% 9.5 0 0 9.5 618961 9.5 2247447 170 662 119% 9.5 2248403 9.5 2249101 659 659 9.5 2731098 9.5 0 9.5 614187 827 0 166 0% 117% 116% 9.5 2240109 663 9.5 2275575 663 9.5 2293097 674 9.5 2749459 9.5 0 9.4 0 829 0 0 1% 113% 9.5 84937 24 98% 9.5 270230 73 98% 9.5 562673 . 153 102% 9.5 1110329 307 102% 9.5 1547236 9.5 2088611 438 606 97% 101% 9.5 2497789 746 100% 9.5 2900192 892 99% 9.5 3160795 999 100% 9.5 0 0 9.5 1537078 433 96% 9.5 0 0 Internal Standard Quant r2= Curve averaged: Linear Include origin Calibration range: PFBS Time Poiiif Day 28 Day 28 Day 28 Day 28 Day 28 Day 42 Day 42 Day 42 Day 42 Day 42 Day 64 Day 64 Day 64 Day 64 Day 64 RT 8.1 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.1 8.2 8.1 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.1 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.1 8.2 8.1 Mean S.D. %RSD Area 0 911956 906017 920039 916507 912425 903511 907628 899479 906115 904792 0 908839 0 899557 909020 903567 909866 909542 905938 900135 893492 897955 901858 902172 900387 895344 902893 893072 908254 901413 904831 0 898777 907357 905164 899013 901618 898747 902197 898658 897407 891718 0 902240 0 903488 6096 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 Page 64 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. EOO-1851 PFOA Hydrolysis Study 50C pH 9.0 Page 3 of 3 Retention times (RT) in minutes MeOH 00028-98-00 pH9 00028-98-01 pH9 00028-98-02 pH9 00028-98-03 pH9 00028-98-04 pH9 00028-98-05 pH9 00028-98-06 pH9 00028-98-07 pH9 00028-98-08 pH9 00028-98-09 pH9 MeOH 00028-97-05 pH9 MeOH 061500-PFOA-241 061500-PFOA-242 061500-PFO A-243 0615 0 0 -P F O A -2 4 4 061500-PFO A-245 061500- PFOA-246 061500-PFOA-277 0 6 1 5 0 0-P F O A -278 061500-PFO A-279 061500-PFO A-280 061500-P F O A -281 061500-PFOA-282 MeOH 00028-98-00 pH9 00028-98-01 pH9 00028-98-02 pH9 00028-98-03 pH9 00028-98-04 pH9 00028-98-05 pH9 00028-98-06 pH9 00028-98-07 pH9 00028-98-08 pH9 00028-98-09 pH9 MeOH 00028-98-05 pH9 MeOH Method ID: ; B is HILL0066.D HILL0067.D HILL0068.D HILL0069.D HILL0070.D HILL0071.D HILL0072.D HILL0073.D HILL0074.D HILL0075.D HILL0076.D HILL0077.D HILL0078.D HILL0079.D HILL0080.D HILL0081.D HLL0082.D H IL L 0 0 8 3 .D HILL0084.D HILL0085.D HILL0086.D HILL0087.D HILL0088.D H ILL0089.D H1LL0090.D HILL0091.D HILL0092.D HILL0093.D HILL0094.D HILL0095.D HILL0096.D HILL0097.D HILL0098.D HILL0099.D HILL0100.D HILL0101.D HILL0102.D. HILL0103.D HILL0104.D HILL0105.D PFOA RT Arsa Cons 9.5 0 0 9.5 0 9.5 84937 0 26 9.5 270230 74 9.5 562673 153 9.5 1110329 305 9.5 1547236 434 9.5 2088611 601 9.5 2497789 740 9.5 2900192 884 9.5 3160795 990 9.5 0 0 9.5 1537078 429 9.5 0 0 9.5 0 0 9.5 614030 166 9.5 2 1 6 8 8 9 5 633 9.5 2233715 9.5 2 2 1 4 3 6 3 644 644 9.5 2685763 812 9.5 0 0 9.5 605776 166 9.5 2 2 3 7 8 8 8 660 9.5 2215935 653 9.5 2221268 657 9.5 2705639 827 9.5 0 9.5 0 0 0 9.5 81580 25 9.5 261882 73 9.5 546205 150 9.5 1083979 302 9.5 1535318 440 9.5 2087627 616 9.5 2478930 764 9.5 2891451 907 9.5 3142079 1009 9.5 0 0 9.5 1538828 439 9.5 0 0 Internal Standard Quant i2 Curve averaged: Linear Include origin Calibration range: "/Standard or RSD 103% 99% 102% 102% 97% 100% 99% 98% 99% 1% 1% 101% 98% 100% 101% 98% 103% 102% 101% 101% % Spike Recovery 95% 116% 120% 116% 119% 98% PFBS Time Point Day 84 Day 84 Day 84 Day 84 Day 84 Day 109 Day 109 Day 109 Day 109 Day 109 RT 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 . 8.2 8.2 8.2 Mean S.D. %RSD Area 0 898777 907357 905164 899013 901618 898747 902197 898658 897407 891718 0 902240 0 890731 903188 894803 906955 898578 891932 895005 893945 889480 889193 885882 885088 0 887837 892635 887309 887505 888627 881276 881348 867135 875807 872831 0 884407 0 892188 9602 1% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 BACK TO MAIN Page 65 of 99 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH 11 Page 1 of 3 Retention times (RT) in minutes A--H---c--o--n--c-e--n-t-r-a--t-i-o-n--s---i-n--n- g--/-m---l------- PFOA f t ....... DT Area MeOH 00028-99-00 pH 11 00028-99-01 pH11 00028-99-02 pH 11 00028-99-03 pH 11 00028-99-04 pH11 00028-99-05 pH11 00028-99-06 pH11 00028-99-07 pH11 00028-99-08 pH11 00028-99-09 pH11 MeOH 00028-99-05 pH11 MeOH 061500-PFOA-031 061500-PFOA-032 HILL0002.D HILL0003.D HILL0004.D HILL0005.D HILL0006.D HILL0007.D HILL0008.D HILL0009.D HILL0010.D HILL0 011 -D HILL0012.D HILL0013.D HILL0014.D HILL0015.D HILL0016.D HILL0017.D 9.5 0 9.5 0 9.5 77656 9.5 249935 9.5 537047 9.5 1042553 9.5 1500587 9.5 1977142 9.5 2325011 9.5 2707083 9.5 2985254 9.5 0 9.5 1506903 9.5 0 9.5 0 9.5 574651 0 0 25 72 152 303 445 610 744 900 1015 0 449 0 0 166 061500-PFOA-033 HILL0018.D 9.5 2088515 654 061500-PFOA-034 061500-PFOA-035 HILL0019.D HILL002.D 9.5 2097206 9.5 2169713 653 683 061500-PFOA-036 HILL0021.D 9.5 2666925 ' 879 061500-PFOA-067 061500-PFOA-068 061500-PFOA-069 061500-PFOA-070 061500-PF OA-071 061500-PFOA-072 HILL0022.D HILL0023.D HILL0024.D HILL0025.D HILL0026.D HILL0027.D 9.5 0 9.5 565130 9.5 2078787 9.5 2115304 9.5 1528187 9.5 2655140 0 163 654 665 461 870 061500-PFOA-103 061500-PFOA-104 061500-PFOA-105 HILL0028.D HILL0029.D HILL0030.D 9.5 0 9.5 584023 9.5 2084579 0 166 650 061500-PFOA-106 HILL0031.D 9.5 2152418 668 061500-PFOA-107 061500-PFOA-108 HILL0032.D HILL0033.D 9.5 2076572 9.5 2704060 646 884 MeOH 00028-99-00 pH 11 HILL0034.D HILL0035.D 9.5 9.5 0 0 0 0 00028-99-01 pH11 00028-99-02 pH11 00028-99-03 pH11 HILL0036.D HILL0037.D HILL0038.D 9.5 78888 9.5 250493 9.5 546767 25 71 153 00028-99-04 pH11 00028-99-05 pH11 00028-99-06 pH11 HILL0039.D HILL0040.D HILL0041.D 9.5 1065800 9.5 1513697 9.5 2026496 304 444 613 00028-99-07 pH11 HILL0042.D 9.5 2360153 732 00028-99-08 pH11 00028-99-09 pH 11 HILL0043.D HILL0044.D 9.5 2751023 9.5 3029716 883 1001 MeOH HILL0045.D 9.5 0 0 00028-99-05 pH11 MeOH HILL0046.D HILL0047.D 9.5 1546259 9.5 0 445 0 Method ID: Internal Standard Quant r2= Curve averaged: Linear Include origin Calibration range: (A) Data excluded on the basis of data quality objectives; see text. "/.Standard or 99% 96% 101% 101% 99% 102% 99% 100% 102% 3% 19% 2% 100% 95% 102% 101% 99% 102% 98% 98% 100% % S p tt Recovery 100% 116% 151% 114% 194% 116% 160% 99% PFBS Time Point (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) RT 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 Mean S.D. %RSD Area 0 836994 842003 838243 842722 832105 837049 832100 826734 824144 827886 0 833679 0 827649 824926 827776 832611 828560 827032 827614 825475 824330 826822 825808 830218 827882 835459 830844 838043 832314 835109 0 847430 846510 848213 850916 847577 847024 849962 850765 850709 849247 0 862345 0 836321 9919 1% Cone. 0.0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 Page 66 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study SOC pH 11 Page 2 of 3 Retention times (RT) in minutes c. j . i n ' :: j RT Area Cone. MeOH HILL0034.D 9.5 0 0 00028-99-00 pH 11 HILL0035.D 9.5 0 0 00028-99-01 pH 11 HILL0036.D 9.5 78888 25 00028-99-02 pH11 HILL0037.D 9.5 250493 71 00028-99-03 pH11 HILL0038.D 9.5 546767 153 00028-99-04 pH 11 HILL0039.D 9.5 1065800 305 00028-99-05 pH 11 HILL0040.D 9.5 1513697 444 00028-99-06 pH 11 HILL0041.D 9.5 2026496 611 00028-99-07 pH 11 HILL0042.D 9.5 2360153 729 00028-99-08 pH 11 HILL0043.D 9.5 2751023 877 00028-99-09 pH 11 HILL0044.D 9.5 3029716 993 MeOH HILL0045.D 9.5 0 0 00028-99-05 pH 11 HILL0046.D 9.5 1546259 445 MeOH HILL0047.D 9.5 0 0 061500-PFOA-139 HILL0048.D 9.5 0 0 061500-PFOA-140 HILL0049.D 9.5 575939 161 061500-PFOA-141 HILL0050.D 9.5 2115608 636 061500-PFOA-142 HILL0051.D 9.5 2188859 664 061500-PF OA-143 HILL0052.D 9.5 2259548 678 061500-PFOA-144 HILL0053.D 9.5 2714384 850 061500-PFOA-175 HILL0054.D 9.5 0 0 061500-PFOA-176 HILL0055.D 9.5 1152389 327 061500-PFOA-177 HILL0056.D 9.5 2065839 616 061500-PFOA-178 HILL0057.D 9.5 2007513 675 061500-PFOA-179 HILL0058.D 9.5 1866921 708 061500-PFOA-180 HILL0059.D 9.5 2269428 897 061500-PFOA-211 HILL0060.D 9.5 0 0 061500-PFOA-212 HILL0061.D 0.0 0 0 061500-PFOA-213 HILL0062.D 9.5 2151980 647 061500-PFOA-214 HILL0063.D 9.5 2245485 683 061500-PFOA-215 HILL0064.D 9.5 2272096 683 061500-PFOA-216 HILL0065.D 9.5 2747811 845 MeOH HILL0066.D 9.5 0 0 00028-99-00 pH11 HILL0067.D 9.4 0 0 00028-99-01 pH11 HILL0068.D 9.5 80241 24 00028-99-02 pH11 HILL0069.D 9.5 262214 71 00028-99-03 pH11 HILL0070.D 9.5 .565808 152 00028-99-04 pH11 HILL0071.D 9.5 1105592 304 00028-99-05 pH11 HILL0072.D 9.5 1598046 448 00028-99-06 pH11 HILL0073.D 9.5 2122804 616 00028-99-07 pH11 HILL0074.D 9.5 2492123 740 00028-99-08 pH11 HILL0075.D 9.5 2912475 900 00028-99-09 pH11 HILL0076.D 9.5 3188696 1032 MeOH HILL0077.D 9.5 0 0 00028-99-05 pH11 HILL0078.D 9.5 1590283 448 MeOH HILL0079.D 9.5 0 0 Internal Standard Quant r2= Curve averaged: Linear. Indude origin Calibration range: (A) Data exduded on the basis of data quality objectives; see text. "/Standard or RSD 100% 95% 102% 102% 99% 102% 97% 98% 99% 3% 7% 3% 97% 95% 101% 101% 100% 103% 99% 100% 103% % Spike Recovery 99% 113% 133% 229% 161% 0% 122% 99% PFBS Time Point (A) (A) (A) (A) (A) (A) (A) (A) (A) (A) Day 64 Day 64 Day 64 Day 64 Day 64 RT 8.1 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.1 8.2 8.1 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 0.0 0.0 8.2 8.2 8.2 8.2 8.1 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.1 8.2 8.1 Mean S.D. %RSD Area 0 847430 846510 848213 850916 847577 847024 849962 850765 850709 849247 0 862345 0 859034 851490 857366 854675 865743 860627 862052 857129 860411 772681 689691 688888 0 0 859405 855708 865487 875709 0 882190 882930 893562 885381 882529 885743 884851 887106 882114 867461 0 882607 0 810082 193054 24% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 158 158 158 158 158 158 158 158 158 158 158 158 0 0 158 158 158 158 0 158 158 158 . 158 158 158 158 158 158 158 0 158 0 Page 67 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 PFOA Hydrolysis Study 50C pH 11 Page 3 of 3 Retention times (RT) in minutes Cn.nu i n D a te ra i* / RT Are3 MeOH HILL0066.D 9.5 0 0 00028-99-00 pH11 HILL0067.D 9.5 0 0 00028-99-01 pH11 HILL0068.D 9.5 80241 26 00028-99-02 pH 11 HILL0069.D 9.5 262214 72 00028-99-03 pH11 HILL0070.D 9.5 565808 152 00028-99-04 pH 11 HILL0071.D 9.5 1105592 302 00028-99-05 pH 11 HILL0072.D 9.5 1598046 444 00028-99-06 pH 11 HILL0073.D 9.5 2122804 609 00028-99-07 pH 11 HILL0074.D 9.5 2492123 731 00028-99-08 pH 11 HILL0075.D 9.5 2912475 888 00028-99-09 pH 11 HILL0076.D 9.5 3188696 1016 MeOH HILL0077.D 9.5 0 0 00028-99-05 pH 11 HILL0078.D 9.5 1590283 444 MeOH HILL0079.D 9.5 0 0 061500-PFOA-247 HILL0080.D 9.5 0 0 061500-PFOA-248 HILL0081.D 9.5 609981 166 061500-PFOA-249 HILL0082.D 9.5 2202106 637 061500-PFOA-250 HILL0083.D 9.5 2350972 694 061500-PFOA-251 HILL0084.D 9.5 2826619 858 061500-PFOA-252 HILL0085.D 9.5 0 0 061500-PFOA-283 HILL0086.D 9.5 0 0 061500-PFOA-284 HILL0087.D 9.5 604634 162 061500-PFOA-285 HILL0088.D 9.5 2263208 652 061500-PFOA-286 HILL0089.D 9.5 2338785 680 061500-PFOA-287 HILL0090.D 9.5 1363306 349 061500-PFOA-288 HILL0091.D 9.5 2649738 781 MeOH HILL0092.D 9.5 0 0 00028-99-00 pH11 HILL0093.D 9.5 0 0 00028-99-01 pH11 HLL0094.D 9.5 81748 25 00028-99-02 pH11 HILL0095.D 9.5 267734 72 00028-99-03 pH11 HILL0096.D 9.5 575392 152 00028-99-04 pH11 HILL0097.D 9.5 1128511 302 00028-99-05 pH11 HILL0098.D 9.5 1640031 447 00028-99-06 pH 11 HILL0099.D 9.5 2183352 617 00028-99-07 pH11 HILL0100.D 9.5 2558520 746 00028-99-08 pH11 HILL0101.D 9.5 2974153 891 00028-99-09 pH11 HILL0102.D 9.5 3267410 1002 MeOH HILL0103.D 9.5 0 0 00028-99-05 pH11 HILL0104.D 9.5 1651887 450 MeOH HILL0105.D 9.5 0 0 Method ID: Internal Standard Quant r2= Curve averaged: Linear Include origin Calibration range: (A) Data excluded on the basis of data quality objectives; see text. "/Standard o r RSD 102% 95% 101% 101% 99% 102% 98% 99% 102% 6% 33% 102% 96% 101% 101% 99% 103% 100% 99% 100% % Spille Recovery 99% 116% 134% 113% 154% 100% PFBS Time Point (A) (A) (A) (A) (A) (A) (A) (A) (A) RT 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 8.2 Mean S.D. %RSD Area 0 882189 882932 893562 885381 882529 885743 884851 887106 882114 867461 0 882607 0 0 871661 882950 874463 880217 0 883613 887173 888570 885977 946290 891813 0 900429 904090 903277 901713 900366 904513 900220 894872 897865 898862 0 904102 0 838809 213297 25% Cone. 0 158 158 158 158 158 158 158 158 158 158 0 158 0 0 158 158 158 158 0 158 158 158 158 158 158 0 158 158 158 158 158 158 158 158 158 158 0 158 0 BACK TO MAIN Page 68 of 99 3M Environmental Laboratory Report No. EOO-1851 Figure 3. Pooled PFOA Data and Slope Regression (pH = 5.0, 7.0, and 9.0 only) 0 20 40 60 80 100 120 time (days) SUMMARY OUTPUT R egression Statistics Multiple R 0.273674341 R Square 0.074897645 Adjusted R Square 0.032847538 Standard Error 0.010843571 Observations 24 ANOVA Regression Residual Total d f SS M S 1 0.000209433 0.000209433 22 0.002586827 0.000117583 23 0.00279626 Intercept X Variable 1 C o e ffic ie n ts Standard E rror 0.001060684 0.003440702 tS tat 0.308275508 -8.08191 E-05 6.05569E-05 -1.334598181 F Significance F 1.781152306 0.195657077 P -v a lu e Lower 95% 0.76077268 -0.006074903 0.195657077 -0.000206407 Upper 95% Low er 95.0% Upper 95.0% 0.008196271 -0.006074903 0.0081963 4.47683E-05 -0.000206407 4.477E-05 Page 69 of 99 BACK TO MAIN EE1851I.XLS 3/30/2001 3:05 PM 3M Environmental Laboratory Report No. E00-1851 Rate and T1/2 Calculations Incubation time (days) Parent PFOA Rates and Half-Lives from p and o (Eq's B37 and B41) Pooled Data Regression Slope 2a Minimum (day-1) Regression Slope Value (day-1) Regression Slope 2cr Maximum (day-1) (Eq's B8, B9, and B41) 1.090E+02 Parent Mass (gm/mole) N/A Max Rate @50C (day-1) 1.957E-04 Slopes @50C (day-1) -2.064E-04 -8.082E-05 4.477E-05 Max. H-Life @25C (year) N/A - Slope positve Author: GMP Date: 3130101 Parent mean p (ng/ml) 6.528E+02 Parent stdev a (nm/ml) 6.963E+00 Max Rate @25C (day-1) 1.957E-05 Min Half-Life @25C (year) 97.0 Slopes @25C (day-1) -2.064E-05 -8.082E-06 4.477E-06 Calc. H-Llfe @25C (year) 235 - - Min. Half-Life @25C (year) 92 : | BACK TO MAIN Page 70 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Appendix D: Selected Chromatograms A representative set of chromatograms from the present study is included in this Appendix. Page 71 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300a\HILL0045.D Report Date: 08-Nov-2000 14:14 Page 1 3M Environmental Lab Data file \\Etshillary\D\Data\H110300\H110300a\HILL0045.D Lab Smp Id Inj Date 04-NOV-2000 00:37 Operator Smp Info DDW MeOH ,. Inst ID: hillary.i ' Mise Info Comment Method \\Etshillary\D\Data\H110300\H110300a\PFOA1103.m Meth Date 08-Nov-2000 14:12 wright Quant Type: ISTD Cal Date 03-NOV-2000 15:20 Cal File: HILL0015.D Als bottle 100 Dil Factor 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 Compounds * 1 PFBS 75 PFOA QUANT SIG MASS 299 413 CONCENTRATIONS ON-COLUMN FINAL RT EXP RT REL RT RESPONSE (ng/mL) (ng/mL) Compound Not Detected. Compound Not Detected. Page 72 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 lata Filai SSEtihi11 ary\D\DataSHil0300\H110300aSHILL0045.D Page 2 Page 73 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300a\HILL0Q46.D Report Date: 08-Nov-2000 14:14 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\H110300\H110300a\HILL0046.D Lab Smp Id: Inj Date : 04-NOV-2000 00:55 Operator : DDW Inst ID: hillary.i Smp Info : 00028-97-00 pH7 Mise Info : Comment : Method : \\Etshillary\D\Data\H110300\H110300a\PFOA1103.m Meth Date : 08-NOV-2000 14:12 wright Quant Type: ISTD Cal Date : 03-NOV-2000 15:20 Cal File: HILL0015.D Als bottle: 1 Dil Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host : WW19507 Compounds * 1 PFBS 75 P F O A QUANT SIG MASS 299 413 CONCENTRATIONS ON-COLUMN FINAL RT EXP RT REL RT RESPONSE (ng/mL) (ng/mL) 8 .226 8.226 (1.000) 995123 Compound Not Detected. 158.000 Page 74 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data Filet WEtshillary\D\DataSH110300\H1103<>Oa\HILL0046*D Pa** 2 * 1 PFBS Page 75 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300a\HILL0047.D Report Date: 08-Nov-2000 14:14 Page 1 3M Environmental Lab Data file \\Etshillary\D\Data\H110300\H110300a\HILL0047.D Lab Smp Id Inj Date 04-NOV-2000 01:14 Operator DDW Inst ID: hillary.i. Snip Info 00028-97-01 pH7 Misc Info Comment Method \\Etshillary\D\Data\Hll0300\H110300a\PFOA1103.m Meth Date 08-Nov-2000 14:14 wright Quant Type: ISTD Cal Date 03-NOV-2000 15:20 Cal File: HILL0015.D . Als bottle 2 Calibration Sample, Level: Dil Factor 1.00000 Integrator HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 11 Compounds * 1 PFBS 75 PFOA QUANT SIG MASS 299 413 RT EXP RT REL RT R E S P O N S E 8.229 9.502 8.229 (1.000) 9.502 (1.155) 970814 87291 AMOUNTS CAL-AMT ON-COL (ng/mL) (ng/mL) 158.000 25.0000 27.02 Page 76 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: SSEtshi11arySDSData\H110300\H110300a\HILL0047.D 73 PFOA Page 77 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300a\HILL0055 .D Report Date: 08-Nov-2000 14:15 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\H110300\H110300a\HILL0055.D Lab Smp Id: Inj Date : 04-NOV-2000 03:42 Operator : DDW Inst ID: hillary.i Smp Info : 00028-97-09 pH7 Mise Info : Comment : Method : \\Etshillary\D\Data\H110300\H110300a\PFOA1103.m Meth Date : 08-Nov-2000 14:15 wright Quant Type: ISTD Cal Date : 04-NOV-2000 03:42 Cal File: HILL0055.D Als bottle: 10 Calibration Sample, Level: Dii Factor: 1 . 0 0 0 0 0 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host : WW19507 19 Compounds * 1 PFBS 75 PFOA QUANT SIG MASS 299 413 AMOUNTS CAL-AMT ON-COL RT EXP RT REL RT RESPONSE (ng/mL) (ng/mL) 8.226 9.498 8.226 (1.000) 9.498 (1.155) 948270 3142471 158.000 999.000 1010 Page 78 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 D ata F U #* SSEtfthi lla ryM )S D a ta S m i0 3 0 0 \H 1 1 0 3 0 0 a \H IU -0 0 5 5 ,D Pag# 2 7 5 PFOA Page 79 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300a\HILL0027.D Report Date: 08-Nov-2000 14:13 Page 1 3M Environmental Lab Data file \\Etshillary\D\Data\H110300\H110300a\HILL0027.D Lab Smp Id Inj Date 03-NOV-2000 19:03 Operator DDW Inst ID: hillary.i Smp Info 06150O-PFOA-019 Mise Info Comment Method \\Etshillary\D\Data\H110300\H110300a\PFOA1103.m Meth Date 08-NOV-2000 14:12 wright Quant Type: ISTD Cal Date 03-NOV-2000 15:20 Cal File: HILL0015.D Als bottle 11 Dii Factor 1 . 0 0 0 0 0 Integrator HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host : WW19507 Compounds * 1 PFBS 75 PFOA QUANT SIQ MASS 299 413 CONCENTRATIONS ON-COLUMN PINAL RT EXP RT REL RT RESPONSE (rtg/mL) (ng/raL) 8.228 8.226 (1.000) 968331 Compound Not Detected. 158.000 Page 80 of 99 BACK TO MAIN IRInIUIIIIBMI 3M Environmental Laboratory Report No. E00-1851 Hta Fil? \SEtahillarySDSBataSHil0300SH110300aSHILL0027.I) Page 81 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300a\HILL0028.D Report Date: 08-Nov-2000 14:13 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\H110300\H110300a\HILL0028.D Lab Smp Id: Inj Dat : 03-NOV-2000 19:22 Operator : DDW Inst ID: hillary.i Smp Info : 0S1500-PFOA-020 Mise Info : Comment : Method : \\Etshillary\D\Data\H1103 00\H1103 00a\PFOA1103.m Meth Date : 08-NOV-2000 14:12 wright Quant Type: ISTD Cal Date : 03-NOV-2000 15:20 Cal File: HILL0015.D Ala bottl: 12 Dii Factor: 1 . 0 0 0 0 0 Integrator : HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host : WW19507 Compounds * 1 PFBS 75 PFOA QUANT SIG MASS 299 413 CONCENTRATIONS ON-COLUMN FINAL RT EXP RT REL RT RESPONSE (ng/mti) (ng/mL) 8.226 9.479 8.226 a.ooo) 9.498 (1.152) 968193 623804 158.000 165.237 165.2 Page 82 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data Filai SSEtshillarySD\Data\H110300SHli0300aSHILL0028.D 78 PFOA Page 83 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300a\HILL0029.D Report Date: 08-Nov-2000 14:13 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\H110300\H110300a\HILL0029.D Lab Smp Id.: Inj Date : 03-NOV-2000 19:40 Operator : DDW Inst ID: hillary.i Smp Info : 061500-PFOA-021 Mise Info : Comment : Method : \\Etshillary\D\Data\H110300\H110300a\PFOA1103.m Meth Date : 08-Nov-2000 14:12 wright Quant Type: ISTD Cal Date : 03-NOV-2000 15:20 Cal File: HILL0015.D Als bottle: 13 Dil Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version : 4.04 Processing Host: WW19507 Compounds * 1 PFBS 75 PFOA QUANT SIG MASS 299 413 CONCENTRATIONS ON-COLUMN FINAL RT EXP RT REL RT RESPONSE (ng/mL) <ng/mU 8.228 9.482 8.225 (1.000) 9.498 (1.152) 962126 2274515 1S8.000 662.113 662.1 Page 84 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data Filas SSEt*hillaraSDSData\H110300SH110300a`sHILL0029.D Page 2 7B PFOft Page 85 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 DReaptoartFilDea:te:\\E0 8t-sNhOilVl- a2 0r0y0\D1\3D:a5t6a\H110300\H110300c\HILL0103.D Page 1 3M Environmental Lab Data file \\Etshillary\D\Data\H1103 00\H1103 00c\HILL0103.D Lab Strip Id Inj Date 04-NOV-2000 18:33 ' Operator DDW Inst ID: hillary.i Smp Info MeOH ' Mise Info Comment Method \\Etshillary\D\Data\H110300\H110300c\PFOA1103.m Meth Date 08-Nov-2000 13:54 wright Quant Type: ISTD Cal Date 04-NOV-2000 11:08 Cal File: HILL0079.D Als bottle 100 Dii Factor: 1.00000 , Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 Compounds * 1 PFBS 75 PFOA QUANT SIG MASS 299 413 CONCENTRATIONS ON-COLUMN PINAL RT EXP RT REL RT RESPONSE (ng/mL) (ng/rnL) Com pound Not Detected. Com pound Not Detected. Page 86 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File* SSEthillaraSDSDataSHlli>30i>SH110300cSHILL0103.D Page 87 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300c\HILL0104.D Report Date: 08-NOV-2000 13:56 Page 1 3M Environmental Lab Data file \\Etshillary\D\Data\H110300\H110300c\HILL0104.D Lab Smp Id Inj Date 04-NOV-2000 18:51 Operator DDW Inst ID: hillary.i Smp Info 00028-97-00 pH7 Misc Info Comment Method \\Etshillary\D\Data\H110300\H110300c\PFOA1103.m . Meth Date 08-NOV-2000 13:54 wright Quant Type: ISTD Cal Date 04-NOV-2000 11:08 Cal File: HILL0079.D Ale bottle: 1 Dil Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 Compounds *. 1 P F B S 7S PFOA QUANT SIO MASS 299 413 CONCENTRATIONS ON-COLUMN FINAL R T E X P RT R 2 L RT R E S P O N S E (ng/mL) (ng/mL) 8 . 2 5 0 8.249 (1.000) 959979 Compound Not Detected. 158.000 Page 88 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Fil; NSEtsh1lrySDSDat\H110300\Hil0300c\HILL0104.D Page 89 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300c\HILL0105.D Report Date: 08-Nov-2000 13:56 Page 1 3M Environmental Lab Data file \\Etshillary\D\Data\H110300\H110300c\HILL0105.D Lab Smp Id Inj Date 04-NOV-2000 19:10 Operator DDW Inst ID: hillary.i Smp Info 00028-97-01 pH7 Mise Info Comment Method \\Etshillary\D\Data\H110300\H110300c\PFOA1103.m Meth Date 08-Nov-2000 13:56 wright Quant Type: ISTD Cal Date 04 NOV-2000 11:08 Cal File: HILL0079.D Als bottle 2 Calibration Sample, Level: Dil Factor 1 . 0 0 0 0 0 Integrator HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 11 Compounda * 1 PFBS 75 PFOA QUANT SIG MASS 299 413 R T E X P R T RELr R T R E S P O N S E 8.248 9.479 8,248 (1.000) 9,479 (1.149) 933019 84002 AMOUNTS CAL-AMT ON-COL (ng/mL) (ng/mL) 158.000 25.0000 27,59 Page 90 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data Fil*t SSEtshi 1larySDSDataSHlO3>OSHllO3OOcSHIU.O105.D H 1 PFBS Page 91 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300c\HILL0113.D Report Date: 08-Nov-2000 13:57 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\H1103 00\H110300c\HILL0113.D Lab Smp Id: Inj Date : 04-NV-2000 21:38 Operator : DDW Inst ID: hillary.i Smp Info : 00028-97-09 pH7 Mise Info : Comment : Method : \\Etshillary\D\Data\H110 00\H110300c\PFOA1103.m Meth Date : 08-Nov-2000 13:57 wright Quant Type: ISTD Cal Date : 04-NOV-2000 21:38 Cal File: HILL0113.D Als bottle: 10 Calibration Sample, Level: Dii Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 19 Compounds 1 PFBS 75 PFOA QUANT SIG MASS 299 413 RT EXP RT REL RT RESPONSE 8.230 9.479 8.230 (1.000) 9.479 (1.152) 927764 3050552 AMOUNTS CAL-AMT ON-COL (ng/mL) (ng/mL) 158.000 999.000 1012 Page 92 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 FiU: SSEtthi1lary\DSD*t*SH110300\H110300cSHILL0113.D Page 93 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H1103 00c\HILL0097.D Report Date: 08-Nov-2000 13:55 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\H110300\H110300c\HILL0097.D Lab Smp Id: Inj Date : 04-NOV-2000 16:41 Operator : DDW Inst ID: hillary.i Smp Info : 061500- PFOA-271 Mise Info : Comment : Method : \\Etshillary\D\Data\H110300\H110300c\PFOA1103.m Meth Date : 08-Nov-2000 13:54 wright Quant Type: ISTD Cal Date : 04-NOV-2000 11:08 Cal File: HILL0079.D Als bottle: 53 Dii Factor: 1 . 0 0 0 0 0 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host : WW19507 Compounds * 1 PPBS 75 PFOA . QUANT SIO . MASS 299 413 CONCENTRATIONS ON-COLUMN FINAL RT EXP RT REL RT RESPONSE (ng/mLJ (ng/wiL) 8-250 8.249 (1.000) 927163 Compound Not Detected. 158.000 Page 94 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data Files SSEtshi 11araSB\BateSH110300SH110300c\HILL0097.B Page 95 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300c\HILL0098.D Report Date: 08-Nov-2000 13:55 Page 1 3M Environmental Lab Data file \\Etshillary\D\Data\H110300\H110300c\HILL0098.D Lab Smp Id Inj Date 04-NOV-2000 17:00 Operator DDW Inst ID: hillary.i Smp Info 061500-PFQA-272 Mise Info Comment Method \\Etshillary\D\Data\H110300\H110300c\PFOA1103.m Meth Date 08-NOV-2000 13:54 wright Quant Type: ISTD Cal Date 04-NOV-2000 11:08 Cal File: HILL0079.D Als bottle 54 Dil Factor 1.00000 Integrator HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 Compounds * 1 PFBS 75 PFOA QUANT SIG MASS 299 413 CONCENTRATIONS ON-COLUMN FINAL RT EXP R T REI R T R E S P O N S E (ng/mL) (ng/mL) 8.249 9.499 8 . 249 (1.000) 9 .'499 (1.151) 924895 602602 158.000 167.470 167.5 Page 96 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data Filai SSEtshi11arySDSDataSH110300SH110300c\HILL0093*D 73 PFOA Page 97 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\H110300\H110300c\HILL0099.D Report Date: 08-Nov-2000 13:56 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\H110300\H110300c\HILL0099.D Lab Smp Id: Inj Date : 04-NOV-2000 17:19 Operator : DDW Inst ID: hillary.i Smp Info : 061500-PFOA-273 Mise Info : Comment : Method : \\Etshillary\D\Data\H110300\H110300c\PFOA1103.m Meth Date : 08-NOV-2000 13:54 wright Quant Type: ISTD Cal Date : 04-NOV-2000 11:08 Cal File: HILL0079.D Als bottle: 55 Dii Factor: 1 . 00000 Integrator : HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host : WW19507 Compounds 1 PFBS 75 PFOA QUANT SIG MASS 299 413 CONCENTRATIONS ON-COLUMN FINAL RT EXP R T R E L R T R E S P O N S E (ng/mL) (ng/mL) 8.250 9.500 8.249 (1.000) 9.499 (1.152) 925297 2146703 158.000 651.301 651.3 Page 98 of 99 Data File; SSEthillarySDSDataSH110 30 0 SHil0300cSHILL0 0 9 9 .D BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 :I Page 99 of 99