Document vBNQ7348zpb5Y9Vye9darqdr8

BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Study Title Hydrolysis Reactions of 2-(A/-ethylperfluoroctanesulfonamido)-Ethyl Alcohol (/V-EtFOSE Alcohol) Data Requirement: Based on OPPTS: 835.2110 Author Thomas L. Hatfield, Ph.D. Study Completion Date March 23, 2001 Performing Laboratory 3M Environmental Laboratory Building 2-3E-09, 935 Bush Avenue St. Paul, MN 55106 Project Identification 3M Laboratory Report No: W1872 Total Number of Pages 83 Page 1 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 This page has been reserved for spcifie country requirements. Page 2 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Statement of Non-Compliance Study Title: Hydrolysis Reactions of 2-(/V-ethylperfluoroctanesulfonamido)-Ethyl Alcohol (A/-EtFOSE Alcohol) Study Identification Number: W1872 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 the quality assurance procedures followed in this study were based on the practices described in the GLP documentation. This is a revised report in that the statistics on the study data and the discussion were changed from the initial study report. Changes to these interpretive sections were made to better represent the experimental results of the study. Sponsor Representative Date Page 3 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Quality Assurance Statement Study Title: Hydrolysis Reactions of 2-(A/-ethylperfluoroctanesulfonamido)-Ethyl Alcohol (N-EtFOSE Alcohol) Study Identification Number: W1872 The following table provides details of the audits performed by the 3M Environmental Laboratory Quality Assurance Unit (QAU). Inspection Dates 9/21,22, 25/2000 10/2/2000 3/14, 15/2001 Phase Data and Draft Report Date Re ported to Management Study Director 10/03/00 10/03/00 Data and Draft Report 10/03/00 10/03/00 Draft Report 3/15/01 3/15/01 Page 4 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 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 S u m m a ry ................................................................................................................................... 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.................................................................................................. 40 Appendix C: Selected Analytical and Kinetics Results.......................................................50 Appendix D: Selected Chromatograms................................................................................61 Page 5 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 List of Tables Table 1. Summary of Results Based on A/-EtFOSE Alcohol Concentrations.................... 8 Table 2. Summary of Results Based on PFOS Limit of Quantification..............................8 Table 3. Characterizations of Test and Reference Substances....................................... 11 Table 4. Observed (50 C) Degradation Rates of A/-EtFOSE Alcohol in Aqueous Buffered Solutions and at Various pH Levels...................................................... 14 Table 5. Degradation Rate and Half Life of N-EtFOSE Alcohol in Aqueous Buffered Solutions Using Data Pooled Over pH Levels..................................................... 15 Table 6. Degradation Rate and Half Life of /V-EtFOSE Alcohol in Aqueous Buffered Based on PFOS Limit of Quantification................................................................17 List of Figures Figure 1. Structures of N-EtFOSE Alcohol and the Potassium Salt of PFOS............... 9 Figure 2. Observed N-EtFOSE Alcohol Degradation for Various pH levels....................15 Figure 3. Pooled A/-EtFOSE Alcohol Data and Slope Regression................................... 16 Study Personnel and Contributors 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 (651) 778-7863 3M Environmental Laboratory and Professional Services Contributing Personnel Kuruppu Dharmasiri, Ph.D Mark T. McCann Anthony E. Scales Joseph J. S. Tokos, Ph.D (Pace Analytical Services, Inc., 1700 Elm St., Minneapolis, MN 55144) Gregory Maisel Jill Maloney (Braun Intertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 55439) Page 6 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 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 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Summary We report here the results of our study of the hydrolysis of 2-(/V-ethylperfluorooctanesulfonamido)-ethyl alcohol (hereafter, N-EtFOSE alcohol). Our methods are described below and in Appendix A to this work; our results are based on the observed concentrations of N-EtFOSE alcohol and its potential hydrolysis product perfluorooctane sulfonate (PFOS) in buffered aqueous solutions as a function of time. The chosen analytical technique was high performance liquid chromatography with mass spectrometry detection (HPLC/MS). Tables 1 and 2 summarize 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 49 days, and our results indicate no dependence of the degradation rate of A/-EtFOSE alcohol on the sample pH level. Our results based on the A/-EtFOSE alcohol concentrations, pooled over the observed pH levels, are presented in Table 1. Table 1. Summary of Results Based on Af-EtFOSE Alcohol Concentrations Observed Rate Constant at 50 C (d ay1) 0.00262 Calculated Rate Constant at 25 C (day'1) 0.000262 Calculated Half Life at 25 C (years) 7.3 Calculated (2o) Half Life Range at 25 C (years) 5.3 to 11.5 We also monitored the concentration of one of the potential hydrolysis products (perfluorooctane sulfonate, PFOS), but never observed this compound at levels above its limit of quantification (LOQ, equal to 12.8 ng/mL). Assuming PFOS to be the only hydrolysis product of A/-EtFOSE alcohol, this LOQ (and other experimental data) provide a second estimate of the N-EtFOSE alcohol half-life, presented in Table 2. Table 2. Summary of Results Based on PFOS Limit of Quantification Maximum Possible Rate Constant at 50 C ( d a y 1) 6.1 x104 Maximum Calculated Rate Constant at 25 C ( d a y 1) 6.1 x10's Calculated Half Life at 25 C (years) >31 According to the data available from this study, the half-life estimate of Table 2 represents the minimum possible half-life of the compound A/-EtFOSE alcohol under the assumption that it hydrolyzes to form only the compound PFOS. Page 8 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 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 /V-EtFOSE alcohol (or, more generally, its degradation in the presence of H20 ) is addressed in this report. Structures of the "parent" compound A/-EtFOSE alcohol and the potassium salt of possible hydrolysis product perfluorooctane sulfonate (PFOS) are Illustrated in Figure 1. Figure 1. Structures of A/-EtFOSE Alcohol and the Potassium Sait of PFOS N-EtFOSE Alcohol Potassium Salt of PFOS Page 9 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 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 N- EtFOSE alcohol. The first estimate (see Table 1) is based on the observed degradation of the "parent" compound N-EtFOSE alcohol in dilute, appropriately buffered aqueous solutions. Equation 1 describes the estimated half-life (t ^ ) in terms of the estimated total parent hydrolysis rate k p (see Appendix B, Equation B10): Eq. 1 We determined the quantity k pfrom the experimental data as described in Appendix B. The data corresponding to "Day 0" (t = 0) were used to determine the relative concentration ratios (see Equations B8 and B9). The measured concentrations of the potential hydrolysis product PFOS (also obtained during the experiments described here) provide a second estimate (see Table 2) of the parent half-life. During the course of this study, we did not detect PFOS above its limit of quantitation (LOQ), and related studies1show that PFOS is itself hydrolytically stable. Assuming also that PFOS is the only hydrolytic product of the parent compound A/-EtFOSE alcohol, these PFOS analyses provide the following estimate (t ]/2p)2of the minimum A/-EtFOSE alcohol half-life (see Equations B32 and B33): A t [P0]h ( 2 ) A l Q ^PFOS Eq. 2 where [P0]= the initial N-EtFOSE alcohol molar concentration, A t = the time interval over which the study was conducted (49 days), and A ptos = ^ e molar limit of quantitation for the compound PFOS. All the samples used in this study were maintained at a reaction temperature of 50 C. The quoted results, valid for the reaction temperature of 25 C, were calculated from our experimental results according to methods described in Appendix B (Eq. B38 and B39). Page 10 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Materials and Methods Details of the characteristics of the test materials, sample preparation techniques, and analytical methods are presented in Appendix A (ETS-8-179.0, "Preparation of 2-(Nethylperfluoroctanesulfonamido) Ethyl Alcohol (N-EtFOSE Alcohol) Hydrolysis Samples 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 March 13 and October 5,1999. C hem 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 Equations 3 and 6 involve only ratios of the parent and product concentrations, 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 Number3 N-EtFOSE Alcohol 3M Specialty Chemistry S398-332 Physical Description Off-white powder Molecular Weight (gm mole'1) 570.9 PFOS (Potassium Salt) 3M ICP/PCP Division Batch #171 Light colored powder 538 THPFOS ICN Biomedicals Batch # 53406 Brown waxy solid 428 W-MeFOSE Alcohol 3M Specialty Chemistry S398-331 White powder 556.9 a The "S" and "TNA" designations are based on reference numbers in two redundant databases maintained by 3M. Sam ple Preparation We prepared three 1.0-mL aqueous buffer samples (a sample, a duplicate, 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, 21, 28, 35, 42 and 49 days). Buffered solutions containing 455 ng/mL of the analyte A/-EtFOSE alcohol and 403 ng/mL of THPFOS (3, 3 ,4 ,4 , 5, 5, 6, 6, 7, 7, 8, 8, 8tridecafluorooctane sulfonic acid), the latter serving as a surrogate for the compound PFOS, 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 orbital incubator/shaker maintained at 50 (+ 3) C. After at least three minutes of agitation, the "Day 0" samples were spiked (as required) with the PFOS solution, diluted 10:1 with methanol containing the internal standard THPFOS, and refrigerated. After the appropriate incubation times, subsets of the sample vials were removed from the incubator and then spiked, diluted, and stored as described Page 11 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 immediately above. Except during the relatively short periods of time required to prepare them, the samples were shielded from light. Eight calibration standards containing N-MeFOSE alcohol (316 ng/ml), N-EtFOSE alcohol (155 to 932 ng/ml), THPFOS (403 ng/ml) and PFOS (1.3 to 64 ng/ml) served as the quantitative basis of the study. All these standards were prepared at the appropriate pH levels using the buffer solutions described above. Sam ple Analysis The equipment we used for the HPLC/ITMS analysis was a Hewlett Packard model 1100 equipped with a Dionex lonPac NG-1 HPLC column (aqueous ammonium acetate/methanol solvent gradient) and an ALS Model G1322A degassing module. An ALS Model G1315A column heater maintained the column temperature at 40 C, a quaternary pump supplied a column flow rate of 0.3 mL/min, and an ALS Model G1313A auto-sampler provided 5 pL sample injections. The detector was a Hewlett Packard MSD mass spectrometer, operated in negative-mode electrospray ionization mode; anions of PFOS, THPFOS, and acetate adducts of N-MeFOSE alcohol and AMEtFOSE alcohol were detected at the charge-to mass ratios 499,427, 616, and 630 respectively. We processed the resulting data using the computer program HP ChemStation forLC (Rev.A.06.0). Further analytical details, including the gradient elution program, instrument and detector parameters, and performance specifications, are presented in Appendix A. D eviations No deviations from the procedures defined in the analytical method (Appendix A) were noted during the study. As noted in the following sections, some calibration and sample data failed to meet data quality objectives and were rejected. Page 12 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Results and Discussion D ata Q uality O bjectives (DOG'S) Below is a brief description of the data quality objectives applied in this study, a full description is presented in Appendix A. With the exceptions of the anomalous results noted below, all the DQO's were met. Appendix C presents the results for each sample set, organized 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. No more than two points may be rejected from a calibration data set. Data for the high or low calibration standards may be rejected, though this results in a smaller effective calibration range. Continuing Calibration Verification (CCV). Identical calibration samples are examined at the beginning and end of each sample run. Results of the second calibration run may not deviate by more than 25% of the first run for any analyte. The average results of the calibration runs are used to calculate the analyte concentrations. Matrix Spikes. The acceptable percent spike recovery range is 75% to 125%. Analyte specificity is demonstrated by acceptable analyte spike recoveries. Sample Duplicates. Duplicate pairs with relative percent deviation (RSD) greater than 25% may be accepted at the analyst's discretion, but must be noted. Solvent Blanks. Concentration results for solvent blanks may exceed 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 Calibrations. Of the 288 calibration results obtained, 22 individual values failed to meet the stated DQO and were rejected. No more than two values for any compound were rejected for any particular calibration run. Spike Recoveries. Results for three sample pairs (EFA -136 and -137, at pH = 7.0; EFA-31 and -32 at pH = 9.0; and EFA -139 and -140, at pH = 9.0) failed to meet the related DQO and were rejected. Page 13 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 S ta tis tic a l M ethods and C alculations 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, the regression fits were not forced 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, such as these, with Arrhenius heats of activation near 18 Kcal/mole.2 D ata Sum m aiy 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's for A/-EtFOSE alcohol and PFOS were 155 ng/mL and 12.8 ng/mL, respectively Results for the surrogate compound (THPFOS) and the internal standard (A/-MeFOSE alcohol) were very consistent throughout the study. The percent relative standard deviations of the measured values, calculated for each pH level, ranged from 1.8% to 7.4%. Table 4 presents the results of the rate determinations at six pH levels and 50C. Table 4. Observed (50 C) Degradation Rates of Af-EtFOSE Alcohol in Aqueous Buffered Solutions and at Various pH Levels. PH Observed Rate (day1) Percent (2c) Rate Uncertainty (day1) 1.5 0.0028 3.0 0.0024 5.0 0.0027 7.0 0.0030 9.0 0.0022 11 0.0023 66 115 56 36 95 54 These degradation rates are generally only poorly determined; their percent relative 2o (95% confidence) uncertainties range from 36% to 115%. The data do not indicate any dependence of the degradation rate on the sample pH. Page 14 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 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. 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 Af-EtFOSE Alcohol in Aqueous Buffered Solutions Using Data Pooled Over pH Levels. Observed Rate Constant at 50 C ( d a y 1) 0.00262 Percent (2o) Rate Constant Uncertainty at 50 C (d ay1) 37% Calculated Rate Constant at 25 C ( d a y 1) 0.000262 Calculated Half Life at 25 C (years) 7.3 Calculated (2o) Half Life Range at 25 C (years) 5.3 to 11.5 Figure 2. Observed AAEtFOSE Alcohol Degradation for Various pH levels. ............pH 1.5 pH 3.0 ...... -...PH 5.0 ---------- pH 7.0 --------- pH 9.0 11 X Cl I I Page 15 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Figure 3. Pooled Af-EtFOSE Alcohol Data and Slope Regression. We also monitored the concentration of the hydrolysis product periluorooctane sulfonate (PFOS), but never observed this compound at levels above its limit of quantification (LOQ, equal to 12.8 ng/mL). The initial N-EtFOSE alcohol concentration (455 ng/ml) and the PFOS LOQ provide a second estimate of the N-EtFOSE alcohol half-life (see in Appendix B, Equations B32 and B33). The maximum degradation rate is given by Equation 3: ' kP (kpL* = 0 m--i and the minimum half-life is given by Equation 4 (t '), > A t [P,,]ln(2) Al Q -^-PFOS Eq. 3 Eq. 4 Page 16 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 We note that in both Equations 3 and 4, the initial A/-EtFOSE alcohol concentration (P0) and the PFOS LOQ (Aps) are molar quantities. Table 6 presents the results of the calculation. Table 6. Degradation Rate and Half Life of A/-EtFOSE Alcohol in Aqueous Buffered Based on PFOS Limit of Quantification At (days) 49 [P0] (nm/ml) 0.80 a^lPoFOqS (nm/ml) 0.024 Maximum Observed Rate at 50 C (day'1) 6.1 X10-4 Maximum Calculated Rate at 25 C (day'1) 6.1 x 10's Calculated Half Life at 25 C (years) >31 Page 17 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Conclusions We have performed a study of the aqueous hydrolytic degradation 2-(N-- ethylperfluorooctanesulfonamido)-ethyl alcohol (A/-EtFOSE alcohol). Six different pH levels were included in the study, which were carried out at 50C and extrapolated to 25C. Our results based on direct observation of the A/-EtFOSE alcohol concentration indicate no clear dependence of the degradation rate of /V-EtFOSE alcohol on pH. From the data pooled over the six pH levels, we estimate that the hydrolytic half-life of A/-EtFOSE alcohol at 25C lies between 5.3 and 11.5 years, with the most likely value of 7.3 years. The concentration of the compound PFOS, a likely hydrolytic product of A/-EtFOSE alcohol, was monitored throughout the study, but remained undetected above its limit of quantification (LOQ = 12.8 ng/mL). Using the LOQ for PFOS and the initial A/-EtFOSE alcohol concentration (455 ng/ml), and assuming PFOS is the only hydrolytic product of A/-EtFOSE alcohol, the data indicate that the hydrolytic half-life of N-EtFOSE alcohol at 25C is greater than or equal to 25 years. Page 18 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 References 1"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. 2 "Experimental Physical Chemistry", F. Daniels, et al., McGraw Hill Book Co. (New York), p. 131,1962. Page 19 of 83 Signatures BACK TO MAIN 3M Environmental Laboratory Report No. W1872 William K. Reagen, Ph.D., Laboratory Management 0 3 / j/o / Date Page 20 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Appendix A: Analytical Method ETS - 8-179.0, "Preparation o f 2-(N-ethylperfluorooctanesulfonamido) Ethyl Alcohol (NEtFOSE Alcohol) Hydrolysis Samples and Analysis by High Performance Liquid Chromatography with Mass Spectrometry Detection." This Appendix presents the analytical method employed in this study. Page 21 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 3M Environmental Laboratory M ethod P r e p a r a t io n o f 2-(7V-eth y l perfluo ro o ctanesulfo nam id o )-e t h y l A l c o h o l (V-Et FO SE A lco h o l) Hyd r o ly sis Sa m ple s a n d A n a l y sis by H ig h P erform ance Liquid Chromatography w ith M ass Spectrom etry D et e c t io n M ethod N um ber: ETS-8-179.1 Approved by: Laboratory Manager Team Leader Adoption Date: 9/14/00 Effective Revision Date: 3/19/01 0 3/* A / Date Date ETS-8-179.1 Method Page 1 o f 18 Prep, of iV-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 22 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 1.0 Scope and Application_____________________________________________________ 1.1 This procedure defines the steps for analysis of 2-(N-ethyl perfluorooctanesulfonamido)- ethyl alcohol (N-EtFOSE alcohol) hydrolysis samples by high performance liquid chromatography (HPLC) with mass spectrometry (MS) detection and quantitation. It is based on EPA OPPTS: 835.2110 (Reference 18.1). N-EtFOSE alcohol and the potential hydrolysis product perfluorooctane sulfonate (PFOS anion) are detected and quantified by this method. N-EtFOSE alcohol is quantified using N-MeFOSE alcohol (2-(Nmethylperfluorooctanesulfonamido)-ethyl alcohol) as an internal standard. The surrogate THPFOS (the anion of 3 ,3 ,4 ,4 ,5 ,5 ,6 ,6 ,7 ,7 ,8 ,8 ,8-tridecafluorooctane sulfonic acid) is used to quantify PFOS. Representative structures are shown in Attachment A. 1.2 Compatible analytes. 2-(N-ethyl perfluorooctanesulfonamido)-ethyl alcohol (N-EtFOSE alcohol), perfluorooctanesulfonate (PFOS anion), perfluorooctanesulfonamide (FOSA), 2-(N-methylperfluorooctanesulfonamide)-ethyl alcohol (N-MeFOSE alcohol) and the anion o f 3 ,3 ,4 ,4 ,5 ,5 ,6 ,6 ,7 ,7 , 8,8, 8-tridecafluorooctane sulfonic acid (THPFOS). 1.3 Com patible matrices for analysis. Aqueous solutions at various buffered pH levels. 1.4 This is a performance-based method. Target analyte or surrogate matrix spike recoveries (100 *25% ) are used for each sample matrix to evaluate method performance. Refer to Section 10 for the frequency of quality control parameters to be performed in this method. Refer to Section 14 for the quality assurance evaluation criteria for this method. 2.0 Summary of Method_______________________________________________________ 2.1 Aliquots o f N-EtFOSE alcohol stock solution containing THPFOS surrogate are added to vials that contain buffers at pH 1.5,3.0,5.0,7.0,9.0 and 11.0. The vials are then placed in an orbital incubator/shaker set at 50.0 3 C. Sets o f vials are removed at designated intervals and the date and time recorded. The aqueous sample from the hydrolysis o f NEtFOSE alcohol is diluted tenfold with methanol (MeOH) and spiked with N-MeFOSE alcohol internal standard. The parent compound, N-EtFOSE alcohol, and the PFOS hydrolysis product are separated on a Dionex IonPac NG1 reversed-phase HPLC column using an ammonium acetate/MeOH solvent gradient, with detection/quantitation by electrospray ionization m ass spectrometry in the negative m ode. 3.0 Definitions_______________________________________________________^________ 3.1 C alibration Standard. A dilution of various amounts o f a stock, intermediate or purchased standard to achieve standard solutions in a concentration range o f interest. Hydrolytic half-lives resulting from these analyses are calculated based on analytical ratios and not absolute numbers. Therefore, results do not depend on the purity o f the standards used. 3.2 C alibration Curve. The graphical relationship between known values, such as concentration of a series of calibration standards and their instrumental response. 3.3 Internal Standard Calibration. Process of establishing a relationship between the ratio o f the target analyte(s) response to internal standard or surrogate response and a known concentration of the target analyte(s). The ratio o f analyte to internal standard response is used to generate the calibration curve and determine unknown concentrations. E T S -8 -179.1 Method Page 2 o f 18 Prep, o f W-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 23 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 3.4 3.5 3.6 3.7 3.8 3.9 3.10 3.11 3.12 3.13 3.14 Correlation Coefficient (r). A measure of the degree o f correlation between two variables. This term is generally used to evaluate the linearity o f a Least Squares Linear regression. An r value of 0.98 is at the lower bounds of what is considered linear. Values of r may range from -1 to +1. A value o f+1 denotes perfect direct functional relationship between two variables. A value of -1 also denotes a perfect inverse relationship. When r = 0, there is no effect of one variable upon the other variable. Coefficient of Determination (r2). The square of the correlation coefficient. It is the proportion of the variation in the dependent variable that is accounted for by the independent variable. Internal standard. A known amount of a compound or element similar in analytical behavior to the compound(s) or element(s) o f interest, added to all samples and standards, and carried through the entire measurement process (post-hydrolysis, after final dilution). It provides a reference for evaluating and controlling the precision and bias o f the applied analytical method. Surrogate. An organic compound which is similar to the target analyte(s) in chemical composition and behavior in the analytical process, but which is not normally found in the sample(s). In hydrolysis studies, surrogate is added to CCVs, samples, sample duplicates, and matrix spike samples along with the test analyte (pre-hydrolysis). Continuing Calibration Verification (CCV). Standards analyzed during an analytical run to verify the continued accuracy o f the calibration curve. This solution may or may not be prepared from a different source or lot number than the calibration curve standards. Solvent Blank. A sample of analyte-free medium (for example, methanol) that is not taken through the sample preparation process. This blank is used to evaluate instrument contamination. Lim it of Quantitation (LOQ). The lowest concentration that can be reliably measured within specified limits o f accuracy during routine laboratory operating conditions. The LOQ is generally 5 to 10 times the minimum concentration with a 99% confidence limit that the concentration is greater than zero. However, it may be nominally chosen within these guidelines to simplify data reporting. For many analytes, the LOQ is selected as the low est non-zero standard in the calibration curve that is greater than 4 tim es the level o f the solvent blanks. Sample LOQs are highly matrix-dependent. Sample Duplicates. Two samples taken from and representative o f the same sample source and separately carried through all steps o f the extraction and analytical procedures in an identical manner. Duplicate samples are used to assess variance o f the total method, including sampling, extraction, and analysis. Relative Percent Difference (RPD). A measure o f precision defined as the absolute value of the difference of two values divided by the average o f the two values and multiplied by 100. M atrix Spike (MS). Prepared by adding a known mass of target analyte to a specified amount o f a sample matrix prior to analysis. This assumes that an independent estimate o f target analyte concentration is available. Matrix spikes are used to determine the effect o f the matrix on method recovery efficiency. Accuracy. The closeness o f agreement between an experimentally determined value and an accepted reference value. When applied to a set of observed values, accuracy is a ETS-8-179.1 Method Page 3 o f 18 Prep, o f AT-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 24 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 combination o f a random (precision) and a common systematic (bias) component. For purposes of the study, the acceptance criterion is 75% to 125% o f the nominal value. 3.15 Dilution. A step in the hydrolysis study procedure in which a solvent is added to the test analyte/buffer solution to prepare it for instrumental analysis. This step occurs after the vials are removed from incubation and before the samples are analyzed. If the solvent used is miscible with the test analyte/buffer solution, the diluting solvent is merely added and mixed. If the diluting solvent is non-miscible, a liquid-liquid extraction is performed. 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 gloves and proper eyewear at all times. 4.1.2 Handle all solvents in a hood for all parts o f the described sample preparation procedure. Whenever possible and practical, dilute samples with solvent in a hood. 4.1.3 For potential hazards of each chemical used, refer to material safety data sheets, packing materials, and the 3M Environmental Laboratory Chemical Hazard Review. 4.2 Cautions 4.2.1 All glassware in which standards are prepared should be triple-rinsed with 1:1 acetone/MeOH to reduce the possibility o f contamination. 4.2.2 Ensure that the HPLC mobile phases are prepared prior to beginning a run sequence, and that there is sufficient quantity to complete the run. Do not allow the pump to run dry. 4.2.3 Ensure that before starting the run sequence there is ample hard disk space on the computer to save all run data. 4.2.4 Ensure that there is enough nitrogen in the supply tank to complete sequence runs. 5.0 Interference 5.1 C ontam inants in solvents, reagents, glassware, and other sam ple processing or analysis hardware may cause interference. Use the routine analysis o f laboratory method blanks to demonstrate that there is no such interference. 5.2 Contamination from columns, HPLC tubing, and detector components may cause interference at low detection levels. The routine analysis o f solvent blanks must be used to demonstrate that there is no such interference. 6.0 Equipment________________________________________________________________ 6.1 Analytical balance sensitive to 0.1 mg 6.2 Incubator/shaker capable of maintaining temperature at 50.0 3C 6.3 Hewlett-Packard (HP) 1100 HPLC System, or equivalent 6.3.1 Pump, binary, Model G1312, or equivalent 6.3.2 Solvent degasser, Model G1322A or equivalent 6.3.3 Autosampler, ALS Model G1313A, variable injection volume capable 6.3.4 Column heater, Model G 1316A ETS-8-179.1 Method Page 4 of 18 Prep, of 7V-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 25 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 6.4 Dionex IonPac NG1 Guard column, 4 x 3 5 mm, or equivalent 6.5 Mass spectrometer. Hewlett-Packard MSD Model G1946A, or equivalent, operating in Electrospray negative SIM mode 6.6 Clock, digital. Only one clock should be used, to insure unambiguous documentation o f the correct performance of procedures. 6.7 pH meter. Coming Model 308 pH/Temperature Meter with 3-in-l gel-filled combination electrode (pH/reference/temperature), or equivalent 6.8 Refrigerator capable o f maintaining 4 3 C 6.9 Data system. A personal computer capable o f controlling the HPLC system as well as recording and processing signals from the detector, Hewlett-Packard ChemStation Version A.06.01 or later 7.0 Supplies and Materials____________________________________________________ 7.1 Vials, 40 mL, VOA (I-Chem or equivalent) 7.2 Crimp cap autovials, 1.8 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% o f total volume), 10 pL-1000 pL 7.7 Volumetric flasks, various sizes 7.8 Beakers, glass, various sizes 7.9 Automatic pipettor, capable of dispensing 10-5000 pL 8.0 Reagents and Standards___________________________________________________ 8.1 M ethanol (MeOH). HPLC/SPEC/GC grade from EM Science, or equivalent 8.2 Acetone. HPLC/SPEC/GC grade from EM Science, or equivalent 8.3 18.0 M Q w ater. Water with lower resistance must not be used. 8.4 Ammonium acetate, 2 mM in water. This solution is chromatographic solvent A (see S ectio n 12.3.1). (E xam ple: A n acceptable elu en t so lu tio n is m ad e b y a d d in g 0.15 g ammonium acetate crystals to a 1-L volumetric flask containing about 500 mL water, adding 10 mL o f methanol, diluting to the mark with 18.0 M2 water and mixing.) 8.5 Stock, internal standard, surrogate and calibration solutions All weights should be recorded to the nearest 0.0001 g in a standards preparation log: 8.5.1 8.5.2 V-EtFOSE alcohol prepared in acetone. (Example: A stock solution is prepared at a concentration of approximately 30,000 pg/mL by weighing 0.3 g o f V-EtFOSE alcohol in a 10-mL volumetric flask and bringing to the mark with acetone. This solution is diluted in MeOH to make additional, appropriate standards.) /V-MeFOSE-alcohol internal standard prepared in acetone. (Example: A stock solution is prepared at a concentration o f approximately 30,000 pg/mL by weighing 0.3 g of/V-EtFOSE-OH in a 10-mL volumetric flask and bringing to the mark with acetone. This solution is diluted in MeOH to make additional, appropriate standards.) ETS-8-179.1 Method Page 5 o f 18 Prep, o f N-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 26 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 8.5.3 Perfluorooctanesulfonate (PFOS) prepared in methanol. (Example: A stock solution is prepared at a concentration o f approximately 3000 pg/mL by weighing 0.06 g of PFOS in a 20-mL volumetric flask and bringing to the mark with methanol. This solution is diluted in MeOH to make additional, appropriate standards.) 8.5.4 3 ,3 ,4 ,4 , 5, 5 ,6 ,6 , 7,7, 8, 8, 8-tridecafluorooctane sulfonic acid (THPFOS) surrogate prepared in MeOH. (Example: A stock solution is prepared at a concentration of approximately 20,000 pg/mL by weighing 0.2 g o f THPFOS in a 10-mL volumetric flask and bringing to the mark with methanol. This solution is diluted in methanol to make additional, appropriate standards.) 8.6 Buffers for calibration of pH meter Purchased pH calibration standards of pH 4.0, 7.0, and 10.0 (suppliers vary). 8.7 Buffer solutions for hydrolysis study. Prepare buffer solutions o f pH 1.5,3.0,7.0,9.0 and 11.0 using guidelines from CRC Handbook o f Chemistry and Physics (Reference 18.2). Prepare buffer solution o f pH 5.0 using guidelines from Fate, Transport and Transformation Test Guidelines (Reference 18.2). Prepare the buffer solutions in 1-liter quantities. Calibrate a portable pH/temperature meter using purchased pH calibration standards o f pH 4.0,7.0, and 10.0, and measure the pH o f all buffer solutions. Prepare buffer solutions of pH 1.5,3.0, 5.0,7.0,9.0 and 11.0 at ambient room temperature. The concentrations are given below. Record final pH measurements o f all buffers. Store buffers in sealed glass containers. 8.7.1 pH 1.5 8.7.1.1 207 mL o f 0.1N HC1 (reagent grade) 8.7.1.2 125 mL of 0.2 M KC1 (reagent grade) 8.7.1.3 Add 18.0 MQ water to about 900 mL total volume 8.7.1.4 Adjust pH to 1.5 with additional 1 N HC1 8.7.1.5 Bring to a final volume o f 1 L with 18.0 MQ water 8.7.2 pH 3.0 8.7.2.1 223 mL o f 0.1 M HC1 (reagent grade) 8.7.2.2 500 m L o f 0.1 M potassium hydrogen phthalate (reagent grade) 8.7.2.3 Add 18.0 MQ water to about 900 mL total volume 8.7.2.4 Adjust pH to 3.0 with 1 N HC1 or 1 N NaOH 8.7.2.5 Bring to a final volume o f 1 L with 18.0 MQ water 8.7.3 pH 5.0 8.7.3.1 Add 3.8777 g ammonium acetate (reagent grade) to 250 mL 18.0 M Q water 8.7.3.2 Add 250 mL 0.052 M acetic acid (reagent grade) 8.7.3.3 Add 18.0 MQ water to about 900 mL total volume 8.7.3.4 Adjust to pH of 5.0 with glacial acetic acid (approximately 0.5 mL) 8.7.3.5 Bring to a final volume of 1 L with 18.0 MQ water 8.7.4 pH 7.0 8.7.4.1 500 mL 0.1 M KH2P 0 4buffer (reagent grade) 8.7.4.2 291 mL 0.1N NaOH (reagent grade) 8.7.4.3 Adjust to pH 7.0 with either 1 N HC1 or 1 N NaOH E T S - 8 - 179.1 Method Page 6 o f 18 Prep, of N-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 27 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 8.7.5 8.7.6 8.7.4.4 Bring to a final volume o f 1 L with 18.0 MQ water. pH 9.0 8.7.5.1 500 mL 0.025 M sodium borate decahydrate (reagent grade) 8.7.5.2 46 mL of 0.1 N HC1 (reagent grade) 8.7.5.3 Add 18.0 MQ water to approximately 900 mL 8.7.5.4 Adjust to pH 9.0 with either 1 N HC1 or 1 N NaOH 8.7.5.5 Bring to a final volume of 1 L with 18.0 MQ water. pH 11.0 8.7.6.1 500 mL 0.05 M NaHC02(reagent grade) 8.7.6.2 227 mL 0.1 N NaOH (reagent grade) 8.7.6.3 Add 18.0 MQ water to approximately 900 mL 8.7.6.4 Adjust pH to 11.0 with IN NaOH 8.7.6.5 Bring to a final volume o f 1 L with 18.0 MQ water 8.8 Test analyte and spike solutions: 8.8.1 IV-EtFOSE alcohol test analyte solution with THPFOS surrogate. [Example: An analyte solution of IV-EtFOSE alcohol at 500 pg/mL and THPFOS at 400 pg/mL is used (a dilution in MeOH of the solutions prepared in Sections 8.5.1 and 8.5.4). A 10-pL aliquot of this solution added to 1 mL buffer (the step performed in Section 12.1.6) results in a final concentration o f 500 ng/mL JV-EtFOSE alcohol and 400 ng/mL THPFOS after MeOH dilution (the step performed in Section 12.1.13)]. 8.8.2 TV-MeFOSE alcohol internal standard solution. [Example: An analyte solution o f IV-MeFOSE alcohol at 30 pg/mL is used (a thousand-fold dilution in MeOH o f the solution prepared in Section 8.5.2). A 100-pL aliquot o f this solution added to 1 mL buffer (the step performed in Section 12.1.14) results in a final JV-MeFOSE alcohol concentration of approximately 300 ng/mL. 8.8.3 Spiking solution. [Example: A spiking solution is prepared by adding 70 pL o f the /V-EtFOSE alcohol stock solution (Section 8.5.1) to a 10-mL volumetric flask and diluting to the m ark w ith m ethanol. A 10-pL aliquot o f this solution added to the 1.0 mL sample (the step performed in Section 12.1.15) results in a final spike concentration of 217 ng/mL o f TV-EtFOSE alcohol after MeOH dilution. 9.0 Sample Handling__________________________________________________________ 9.1 Record times of initial preparation and dilution on the fluorochemical degradation (hydrolysis) analysis sample preparation sheet (Attachment B). 9.2 For Time 0 samples, aliquot only the lmL of buffer into the vials. DO NOT spike with test analyte. Store the vials at room temperature until ready to analyze. Then proceed from Section 12.1.12. 9.3 Once the 9.0 mL of diluting solvent has been added to the hydrolysis mixtures, the samples are ready to be analyzed. Alternatively, aliquots o f the methanol-diluted samples should be refrigerated at 4 3 C or frozen until analysis can be performed. E T S -8 -179.1 Method Page 7 o f 18 Prep, of A-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 28 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7 Q u a lity C on tro l C alibration Standards. Calibration standards (Section 11) used to generate a calibration curve should be prepared in the same type of solvent or matrix as in the study samples. The number o f calibration standards and the concentration levels should be sufficient to encompass the expected concentrations o f the study samples. In general, a minimum of five calibration standards is required for fit of linear regression. Broad calibration ranges (greater that three orders of magnitude between low and high standards), may require use o f a quadratic fit o f the data and requires more points to adequately represent the calibration range. Internal standard (IS). iV-MeFOSE alcohol internal standard is added in a constant concentration to all standards, samples, and matrix spikes. Surrogate. THPFOS surrogate is added in a constant concentration to CCVs, samples, sample duplicates, and matrix spike samples along with the iV-EtFOSE alcohol test analyte (pre-hydrolysis). Continuing Calibration Verification (CCV). A standard analyzed periodically during an analytical run to verify the continued accuracy o f the calibration curve and is run in tandem with the solvent blank. This solution may be prepared from a different source or lot number than the calibration curves standards. Solvent blank. Solvent blanks (or clean method blanks) should be run before and after every calibration curve, CCV, method blank (if contamination is noted), and after batches o f no more than 20 injections. Acceptable values for the blanks are values below the limit of quantitation (LOQ) of the instrument (Section 3.10). If analyte carryover is a problem (see Section 14.5), use back-to-back solvent blanks. Sam ple Duplicates. Prepare and analyze all samples in duplicate to provide a measure of the precision of analysis. M atrix spikes. Prepare a post-hydrolysis matrix spike sample (the step performed in Section 12.1.15) for each interval and pH level used in the study. Concentrations o f the spike should be approximately equal to a mid-range calibration standard. The matrix spike sample should be analyzed immediately following the sample duplicates to which it corresponds. The analyst shall accept percent spike recoveries o f 100 25% . Spike recoveries outside of this range should be noted. Appropriate steps must be taken to correct the problem before analysis is allowed to proceed. Before the analysis is allowed to proceed, consult with the Team Leader or designee for direction and final acceptance or rejection of the analytical run. 11.0 Calibration and Standardization__________________________________________ 11.1 S tandard preparation. Prepare six calibration standards containing V-EtFOSE alcohol, V-MeFOSE alcohol, PFOS and THPFOS in 9:1 MeOH:buffer for each pH level. Standards from approximately 150 ng/mL to 1000 ng/mL o f TV-EtFOSE alcohol and 1 ng/mL to 100 ng/mL of PFOS are suggested. 11.2 C alibration standards. Analyze the calibration standards at the beginning and end o f the run. Individual calibration data points from both sets of calibration standards are used to generate a calibration curve. The calibration curve is then used by the data reduction software program for linear regression calculations to relate the analyte peak area ratio ETS-8-179.1 Method Page 8 o f 18 Prep, o f A'-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 29 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 versus amount ratio, using internal standard calibration. Use JV-MeFOSE alcohol as the internal standard for jV-EtFOSE alcohol and THPFOS surrogate as the internal standard for PFOS quantitation. Quadratic regression may be used if data review shows this to be a consistent and more accurate representation o f the instrument response. Consult with the Team Leader for direction prior to performing the quadratic calibration methodology. 12.0 Procedures________________________________________________________________ 12.1 Sample and spike preparation 12.1.1 Before spiking with any of the stock standards, transfer approximately 1 mL of the solution to an autovial and cap the vial. Use this smaller volume for spiking to minimize the effects o f evaporation from stock solutions and to prevent contamination o f the larger volume o f stock solution. 12.1.2 Determine the number o f time intervals that will be analyzed. Each interval will have three vials for each pH, multiplied by the number of pHs analyzed. One vial at each level will be labeled as sample, duplicate, and spike. 12.1.3 Obtain the appropriate number of 40-mL VOA vials with caps and cardboard boxes. Prepare appropriate sample preparation worksheets, create labels, and affix them to the vials. The labels should include the sample number and I.D., temperature, pH, time interval, test analyte, and date o f preparation. Record the pH of each buffer solution. 12.1.4 Remove the cap o f the VOA vial and add 1 mL of the appropriate buffer solution to all of the pre-labeled vials. Always replace the cap immediately after any addition to minimize evaporation. 12.1.5 Put "Time 0" samples aside at this point. For all other samples, continue on to Section 12.1,6. 12.1.6 To all of the vials, add 10 pL of the mixed V-EtFOSE alcohol analyte and THPFOS surrogate solution (Section 8.8.1) with a 25-pL Hamilton Gastight syringe. 12.1.7 Make sure that the cap has been firmly tightened and place the samples back in the cardboard case. 12.1.8 Place the case into a pre-warmed incubator/shaker for the appropriate time. Record the time, temperature, and rate o f shaking. The temperature is determined by the conditions o f the experiment. Continue to manually monitor the incubator temperature daily during the entire incubation. Record the temperature on the sample preparation sheet (Attachment B). 12.1.9 Store "Time 0" samples at room temperature until the time o f analysis. 12.1.10 Remove each case from the incubator at the designated preset time. 12.1.11 Remove the vials from the case and place in racks. Allow the vials to cool for approximately 15 minutes to room temperature. 12.1.12 While vials are cooling, spike the stored "Time 0" samples with test analyte solution (Section 12.1.5) on Day 7. Then continue on to (Section 12.1.13) with all samples. 12.1.13 Add 9 mL o f methanol to each vial. ETS-8-179.1 Method Page 9 o f 18 Prep, of jV-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 30 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 12.1.14 Using a lOO-pL gas tight syringe, add 100 pL of V-MeFOSE alcohol internal standard solution (Section 8.8.2) to each sample and spike vial. 12.1.15 Using a 25-p.L gas tight syringe, add 10 pL o f spiking solution (Section 8.8.3) to the sample spike vials. Shake the vials for three minutes by hand or Vortex mixer to mix the contents and extract any analytes that may have adsorbed to the vial. 12.1.16 Aliquot approximately 1 mL of each sample to the appropriately labeled autovial, cap, and refrigerate at 4 3 C until analysis. 12.2 Instrum ent set up 12.2.1 Check that the appropriate HPLC column is in the instrument for analysis. 12.2.2 Check that the correct eluent solutions are in bottles to be used and that enough is available to complete the sequence run. 12.2.3 Place the samples in the autosampler tray and construct a sequence table with appropriate calibration standards, calibration check standards and solvent blanks. 12.2.4 Verify that all samples and standards are positioned correctly. Enter sequence information (sample or standard ID, method name). Use one injection per sample. 12.2.5 Save sequence as analysis date and instrument letter (e.g. on March 14,1999, save sequence table as 031499.s). Save all data to a subdirectory labeled with analysis date. (e.g. 031499). 12.2.6 Set post-sequence command macro to shut down system after the run is completed (Example: "STANDBY" on HP1100/MSD systems). 12.3 H PL C set up: 12.3.1 Analysis of jV-EtFOSE alcohol hydrolysis samples in buffers at pH levels 1.5,3.0, 5.0, 7.0, 9.0 and 11.0. Column: Dionex IonPac NG1 Guard column, 4 x 3 5 mm, or equivalent Solvent A: Ammonium Acetate 2mM in water (with 1% MeOH). Solvent B: Methanol Recommended Solvent G radient: T ime (min) %A 0.0 60 1.0 60 4.0 5 11.0 5 Post time: 6 minutes, column temperature: 35C. %B Fl o w Rate 40 0.3 mL/min 40 0.3 mL/min 95 0.3 mL/min 95 0.3 mL/min E T S -8 -179.1 Method Page 10 o f 18 Prep, o f /V-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 31 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 12.4 Recommended mass spectrometer set up*: 12.5 MSD: Ionization mode API-ES Polarity Negative Acquisition mode SIM Gain 1.0 Fragmentor 70 Dwell time 183 msec Capillary voltage 3500 Drying gas Nitrogen Nebulizer pressure 30 psig Drying gas flow 8 L/min Drying gas temp 300 C Example conditions are applicable to HP1100/MSD equipment only. Auto-sampler setup*: A u to -s a m p l e r : ALS Model G1313A A u t o -s a m p l e r P r o g r a m : None In je c t io n v o l u m e : 5.0 pL Example conditions are applicable to Hewlett Packard UOO only 12.6 Ions used for identification and quantification: A pprox. R e t e n t io n T im e (m in ) 8.3 8.6 6.2 5.9 6.3 Component Name MeFOSE-OH EtFOSE-OH PFOS THPFOS FOSA D es c r ip tio n Internal Standard Q u a n t if ic a t io n Io n 616(M+OAc) Test Analyte 630 (M+OAc-) Potential Degradation Product 499 (M-H+) Surrogate 427 (M-H+) Qualitative Purposes Only 498 (M-H*) M o n it o r Io n 617 631 500 No monitor No monitor 12.7 Sample analysis 12.7.1 Enter the standard, sample, and QC information into the sequence table. Analyze calibration standards first, then up to 20 injections, followed by the calibration standards. If more than 20 injections are to be run, analyze a continuing calibration standard (CCV) after every 20 injections and run the calibration E T S -8 -179.1 Method Page 11 o f 18 Prep, o f 7V-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 32 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 standards again at the end of the sequence. Run solvent (or method) blanks after the highest calibration standard, before and after the CCV, and after the set o f samples to check for any analyte carryover. 12.7.2 Place standards, samples, and QC (matrix spikes, sample duplicates, and blanks) into the autosampler tray according to the order they are listed in the sequence. 12.7.3 Identify the electronic acquisition files with an appropriate prefix (e.g. EtFOS). Do not exceed five characters if the sequence contains more than 99 lines. 12.7.4 Save sequence as analysis date (e.g. on March 14,1999, save sequence table as 031499.s). Save all data to a subdirectory labeled with analysis date (e.g. 031499). 12.7.5 Start the sequence. 13.0 D a t a A n a l y s is a n d C a l c u l a t io n s 13.1 Peak Evaluation. Peaks must be symmetric in shape and identified by extracting compound-specific ions. Peaks considered for calibration must have peak heights greater than 4 (four) times the baseline noise for that region of the chromatogram. Peak area integration is from baseline to baseline using automatic or manual integration. NEtFOSE alcohol concentrations are calculated using iV-MeFOSE-OH as the internal standards. THPFOS surrogate is used as the "internal standard" to calculate PFOS concentrations. External standard calibration may be acceptable. Consult with the team leader for direction prior to performing the external calibration methodology. Document change in raw data and final report. 13.2 Calculation of Rate Constant (A). Calculate the test analyte concentrations in each of the pH matrices using the curves obtained from the calibrations. Assuming first-order kinetics, a rate constant (k) can be determined by plotting: EtFOSE], Ln EtFOSE] J versus ra*nus elaPse^ time (rO- The subscripts t and 0 refer to analyte concentrations determined at some elapsed time t and at t = 0, respectively. The slope of the resulting line is k. 13.3 T arget analyte concentrations. Calculate the EtFOSE-OH and PFOS concentrations in each o f the pH matrices using the curves obtained from the calibrations 13.4 M atrix spikes. Calculate the percent recovery for each of the matrix spikes. Calculate the matrix spike percent recoveries using the following equation: % Recovery = (observed spiked sample result - observed sample result'! x 100 Actual amount spiked Using the observed matrix spike recoveries, calculate the average spike recovery. E T S - 8 - 179.1 Method Page 12 o f 18 Prep, o f A'-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 33 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 13.5 Sample Duplicates. Calculate the relative percent deviation (%RPD) for the duplicate samples: RPD = lA-Bl x 100% (A+B)/2 Where A = the concentration measured in the sample B = the concentration measured in the duplicate 14.0 14.1 14.2 14.3 14.4 14.5 M ethod Performance______________________________________________________ Coefficient of Determination (r2). The coefficient o f determination (r2) for the calibration curves should be 0.990 or greater. The curves should be examined closely for linearity and intercept, particularly for accuracy o f quantitation at the low and high ends o f the curve. The accuracy of all standards used for calibration must be within 75-125%. On occasion it may be necessary to use exponential or quadratic fits o f the data, usually when broad range curves (greater than 3 orders o f magnitude between the low and high concentration standards) are used. Document in the raw data the technical justification for using quadratic equations. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. C alibration Standards. The acceptance criterion for the calibration standards is that the accuracy o f each standard is 75% to 125% of the nominal value. Calibration standards outside this range are to be considered outliers and excluded from the linear regression. It may be necessary to use exponential or quadratic fits o f the data, usually when broad range curves (greater than 3 orders o f magnitude between the low and high concentration standards) are used. Document in the raw data the technical justification for using quadratic equations. In tern al S tandard (IS) and Surrogate. Review of the internal standard and surrogate performance is performed by averaging the area response throughout the analytical run and calculating % RSD. Inconsistencies in the internal standard peak area may indicate instrumental changes over time. Inconsistencies in the surrogate peak area may indicate instrumental changes, changes in the test-system, or hydrolysis o f the surrogate over time. Consult with the Team Leader or designee for direction and final acceptance or rejection o f the analytical run. Continuing C alibration Verification. If the percent difference for the amount o f quantitated analyte is greater than 25% from the true value relative to the initial standard curve, the Team Leader should be consulted. Only those samples analyzed before the last acceptable calibration check standard will be used. Consult with the Team Leader or designee for direction and for final acceptance or rejection for the data. Solvent Blanks. Solvent blanks should show no more than a 5% carryover from a high standard or calibration check standard. If so, two solvent blanks may be necessary to rule out instrumental contamination. If peaks with greater than 25% of the peak area o f a low standard value are observed in sequential solvent blanks, the run should be stopped. This ETS-8-179.1 Method Page 13 o f 18 Prep, o f A'-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 34 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 is indicative of instrument contamination. The instrument shall be serviced by thoroughly cleaning the electrospray source, and replacing/cleaning columns, tubing, etc. 14.6 Lim it of Q uantitation (LOQ). The LOQ is equal to the lowest standard in the calibration curve that is greater than 4 times the level of the solvent blanks. 14.7 Sample Duplicates. The analyst shall accept %RPD (See Section 13.5) values < 25%. %RPD values > 25% should be noted. Appropriate steps must be taken to correct the problem before analysis is allowed to proceed (e.g. sample re-runs, additional blanks, etc.). Consult with the Team Leader or designee for direction, and for final acceptance or rejection of the analytical run. 14.8 M atrix Spikes. The analyst shall accept percent spike recovery values o f 100 25%. Spike recoveries outside o f this range should be noted. Consult with the Team Leader or designee for direction, and for final acceptance or rejection o f the data. Data that are used in final report that is deemed out o f control will be required to have a technical justification for why the data are being used, documented in the final report and raw data. 14.9 Specificity. Analyte specificity is demonstrated by acceptable post-hydrolysis analyte spike recoveries. 14.10 System Suitability. Without performing a method validation, system suitability can be demonstrated by acceptable instrumental checks (e.g. abbreviated m/z check-tune, or full auto-tune routines. Consult the appropriate instrumental manuals (Reference 18.3). 15.0 Pollution Prevention and Waste Management_____________________________ 15.1 Dispose o f sample waste by placing 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. Empty into the flammable storage drum in the hazardous waste collection area on the 2nd floor. 15.3 Use smaller bore columns when possible to minimize waste generation. 16.0 16.1 16.2 16.3 16.4 16.5 16.6 16.7 16.8 16.9 R e c o r d s _____________________________________________________________________________ Print hard copies of all graphics and data analysis summaries for archiving. Sign and date all graphics and label with instrument ID. Fill out the hydrolysis sample preparation worksheet completely, making sure to include all initials and dates. Print out the sample sequence table, reduce the size with photocopying and tape the photocopy into the instrument log. Keep the original copy for the raw data files package. Print chromatograms and quantification reports for all analyses. Print calibration tables and curve information and store in the raw data file. Store hydrolysis sample preparation worksheets in the raw data file. Enter all standard preparation information in the standards preparation logbook. Make a photocopy o f tire logbook page and include the copy in the raw data file. Archive electronic data to appropriate media when necessary. E T S - 8 - 179.1 Method Page 14 o f 18 Prep, of jV-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 35 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 17.0 Attachments_____________________________ 17.1 Attachment A. Representative chemical structures 17.2 Attachment B. Hydrolysis sample logsheet 18.0 References 18.1 Fate, Transport and Transformation Test Guidelines Office o f Prevention, Pesticides and Toxic Substances (OPPTS) 835.2110 Hydrolysis as a Function o f pH, EPA 712-C-98057, January 1998. 18.2 C R C H andbook o f Chemistry and Physics, 1s t Student Edition, "Buffer Solutions Operational Definitions o f pH," Robert C. Weast, Ph.D., 1988, p. D-87. 18.3 Hewlett Packard 1100/MSD instruction CD/ROM 19.0 Affected Documents 19.1 None. ETS-8-179.1 Method Page 15 o f 18 Prep, o f jV-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 36 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 20.0 Revisions Revision number 001 Reason for revision Resizing of graphics and re-formatting to remove page orphans Date of Revision 03/19/01 E T S -8 -179.1 Method Page 16 o f 18 Prep, o f W-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 37 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Attachment A. Representative Chemical Structures N-MeFOSE alcohol FW = SSTt THPFOS FW = 427 (an io n i PFOS (FW =499 (anioni F N-EtFOSE alcohol fFW - 5261 OH Counter cation = K* in this study, but may also b e Li*, Ca*2, or DEA (diethanolam ine) E T S - 8 - 179.1 Method Page 17 o f 18 Prep, o f N-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 38 of 83 3M Environmental Laboratory Report No. W1872 Attachment B: Hydrolysis Sample Logsheet TEST ANAYLTE: Lab Request Num ber: N om inal interval: Date: Time: initials: Rop let Temp pH rt 1.5 r? 1.5 1.5 1.S bite 1.5 3 T? 3 3 3 blk 3 r1 5 r? 5 r3 5 5 blk 5 rt 7 crZt 7 7 7 blk 7 rt B r2 9 r3 9 ms B bft S rl 11 1t rt 11 11 blk I t Buffer Fiuorochemlcal Degradation (Hydrolysis) Analysis Incubator 1D;_ Start D ate:_ Stop Date: Incubation In te r v a l:_______ days _ Freezer ID :_ Time:_ Start D ate:_ Time: Stop D ate;_ . h o u rs____ . min Test Analyte S pike S olution Dilution S olvent Internal S tandard Am ounr S o futren I | itiL) Amount S o lution ID IpM Amount Solution ID IpL) ** -- - Solution (mL} Solution ID (MU - -_ ~- -- -- - -- -- _-- .. -~ ** -- --- - -.. -- .. Component .... - Cone. (pg/m L) Com ponent cone. Cone. {pg/m L) Com ponent {pgfmL) Com ponent Cone. {p g /m L ) C o m m en ts: T im e: T im e: Comm ent . .. BACK TO MAIN ETS-8-179.1 Method Page 18 of 18 Prep, of W-EtFOSE Alcohol Hydrolysis Samples and Analysis by HPLC/MS Page 39 of 83 k. BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Appendix B: Kinetics Model This Appendix includes a mathematical description of the kinetics model employed in the study. 4 Page 40 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 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 kpm(fr the parent) and k Am(for the parent's hydrolysis products). P + H20 o n mA ra+Y ml (m= 1toN) (B1) A m+ H20 Yn (m= 1toN) (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 (B3) which is equivalent to the separable differential equation (B4) Equation B4 may be directly integrated to obtain the general solution ln[P]= - nmkPmt +C With the initial condition P(t = 0 ) s P o, the specific solution to Equation B4 is P = Po exp n m k Pmt s P 0 e -kpt using the additional definition of the total parent hydrolysis rate (B5) (B6) Page 41 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 k p (B7) Equation B6 can be re-written in a form that allows a least-squares estimate of the total parent hydrolysis rate: k pt = - In (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 [ - In (P/P0)] 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 (B9) A least squares estimate f ^ of the parent hydrolysis half-life is therefore available from (B10) B3. Product Compound Concentrations The pseudo-first order differential changes in the product concentrations Am (using Equations B2 and B6) are d A m= ( n mk PmP - k AmA m) dt = ( n mk PmP0 e~kp * - k AmA m) dt (B11) and the (first order, non-separable) differential equation governing the product concentrations is d A n +k AmA m = nrak PmPo e' -kpt dt The "standard form" of Equation B12 is (B12) Page 42 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 A m+ S ( t ) A m =Q(t) where the "function" S (t) is actually a constant: S(t) = k a,, and Q(t) = nmk PmP0 e`M . The general solution A mto Equation B12 is contained in (B13) (B14) (B15) eJS(t)dt = J q(.) eJS(t')dt' dt + C (B16) where e JS(t)dt _ e JS (t')dt' _ e k AmJdt __g^Am^ (B17) and JJ q M. JS (t')d t' dt + C = n kpmPo e k Am* e'kp,dt + 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 ^ = k P) A mekpt = nmk PmP0 1+ C (B19) and, using the initial condition A m(t = 0 ) = A ^ , the specific solution to Equation18 is (for kAm= kp) A m= (nmkPmP0 t + A m0)e'kpt (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 43 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 A-m~ -^mO (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 A ekAmt _ imkpmPo ^ (k^-kp^ _j_Q k-Am kp (B22) and the specific solution to Equation B18 with the initial condition A ra(t = 0 )= A ra0 is n 1/ p Am0+A ,, = A _L_ U m iV P m j r 0 kp k a n m k p m f i l e -kp t kp --k Am (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) k _ V n k _ kP y ( A m- A m0) KP " m K Pra m=l f V1 C ) i-- ' T Po (B25) Page 44 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 so that or (for hydrolytically stable products) -XJN (A ra- A m0) m=l (for hydrolytically stable products) (B26) IN (Am~ A m0) k Pt = - ] n `- Xm=I (B27) If the changes in the product concentrations are all small compared to the original parent concentration, that Is, if (B28) we may use the expression (valid for -1 < X < 1 ) ln(l + X ) = X - - X 2 + - X 3 - - X 4 + V' 234 and Equation B23 becomes (for hydrolytically stable products and k (B29) (B30) Page 45 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 or (for hydrolytically stable products and k p (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 " 0 (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 ra0 = 0 and 2) at time t = A t , the product concentrations have increased to the values A m= A ^ 0Q. 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 < ( k . L . = ^r 0rA-1Xm=i A TMQ (B32) 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 ,/2p)mjnas follows: (for hydrolytically stable products at concentrations below the limits of quantitation) 1-1 A l Q t ' p 2 (T U , = f t r f - = A t p >'<2> VK P / max m=l (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)maxin 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 46 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 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 a m - jn mto the value o m + imat 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 2 o 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 amor 2) concentrations below the limits of quantitation) 1 k P < (kP)max = P0 A t Below LOQ +5>. Cons tan t (B34) Under these circumstances and assumptions, the experimental data indicate that the parent half-life T 1^ is greater than the value (t ^ )minas follows: (for hydrolytically stable products at either 1) constant measured concentrations with standard deviation cmor 2) concentrations below the limits of quantitation) 2 (T , ; L = 7 r f - = A < r 2) L \K P W Below LOQ + Constan t (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. B6. Parent Haif-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 47 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 that the product concentration increased from the initial value p p - a P to the value |iiP+ a 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 a p) 2Gp k p" < (' kPp/)max = Pp A t ' (B36) Under these circumstances and assumptions, the experimental data indicate that the parent half-life T l/2 is greater than the value (t ^ ) as follows: F x P /min (for essentially constant parent concentrations with mean value | i pand standard deviation a P) T P > (VsM _ in(2) p ' p'min (k P) pP Ath(2) 2a P ' (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 61 provides the following relationship between the hydrolysis rates (k, and k2) for that reaction at two different absolute temperatures (T, and T2): n H __i k, AH, ' 1 11 [ R LTA2 T,_ (B38) where R - 1.99 x 10'3 Kcal mole'1K'1is the ideal gas constant. Using the value62 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 --k j = exp-^[ ------1-8---- - 1 k 2 | l . 9 9 x l 0 ' 3 .323 = exp(-2.35) = 0.095 (B39) Page 48 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 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). B2 F. Daniels, et al., "Experimental Physical Chemistry", McGraw Hill (New York), p.131 (1962). Page 49 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Appendix C: Selected Analytical and Kinetics Results This Appendix includes selected sample data and their related kinetics results. Page 50 of 83 N-EtFOSE Alcohol Buffer Hydrolysis Study at 50 C. 3M Environmental Laboratory Report No. W1872 All concentrations in ng/ml. pH Time (Days) 1.5 0 1.5 7 1.5 14 1.5 21 1.5 28 1.5 35 1.5 42 1.5 49 Cone. 490 474 469 415 439 420 438 427 ln([PM Plo) 0.000 -0.033 -0.043 -0.165 -0.110 -0.154 -0.112 -0.137 SUMMARY OUTPUT R epression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.77717 0.60399 0.53799 0.04167 8 ANOVA Regression Residual Total df 1 6 7 SS 0.01589 0.01042 0.02631 Intercept X Variable 1 % 2c Slope Uncertainty 66% C oefficients -0.02631 -0.00278 Standard E rror 0.02690 0.00092 pH Time (Days) Cone. in([P]t/[P]o) 3.0 0 461 0.000 3.0 7 409 -0.118 3.0 14 393 -0.158 3.0 21 362 -0.240 3.0 28 380 -0.191 3.0 35 379 -0.196 3.0 42 396 -0.151 3.0 49 388 -0.170 N-EtFOSE Alcohol @ 50 C SUMMARY OUTPUT R egression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.57897 0.33521 0.22441 0.06292 8 ANOVA Regression Residual Total df 1 6 7 SS 0.01198 0.02375 0.03573 Intercept X Variable 1 C oefficients -0.09378 -0.00241 Standard E rror 0.04061 0.00139 % 2c Slope Uncertainty 115% I BACK TO MAIN Page 51 of 8: N-EtFOSE Alcohol Buffer Hydrolysis Study at 50 C. 3M Environmental Laboratory Report No. W1872 All concentrations in ng/ml. pH Time (Days) 5.0 0 5.0 7 5.0 14 5.0 21 5.0 28 5.0 35 5.0 42 5.0 49 Cone. 477 456 472 416 430 432 428 410 ln([P]t/[Pjo) 0.000 -0.044 -0.009 -0.136 -0.104 -0.099 -0.108 -0.149 N-EtFOSE Alcohol @ 50 C SUMMARY OUTPUT R egression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.82601 0.68230 0.62935 0.03444 8 ANOVA Regression Residual Total df SS 0.01528 0.00712 0.02240 Intercept X Variable 1 % 2a Slope Uncertainty 56% C oefficients -0.01422 -0.00273 Standard E rror 0.02223 0.00076 pH Time (Days) Cone. lnffPjt/fPjo) 7.0 0 468 0.000 7.0 7 456 -0.026 7.0 14 454 -0.029 7.0 21 421 -0.104 7.0 28 421 -0.105 7.0 35 422 -0.103 7.0 42 414 -0.122 7.0 49 410 (A) SUMMARY OUTPUT R egression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.92903 0.86309 0.83571 0.02002 7 ANOVA Regression Residual Total df 1 5 6 SS 0.01263 0.00200 0.01464 Intercept X Variable 1 % 2a Slope Uncertainty 36% C oefficients -0.00609 -0.00303 Standard E rror 0.01364 0.00054 (A) Data in Italics have been rejected from the fits on the basis of the data quality objectives (see text). BACK TO MAIN Page 52 of 83 N-EtFOSE Alcohol Buffer Hydrolysis Study at 50 C. 3M Environmental Laboratory Report No. W1872 All concentrations in ng/ml. pH Time (Days) 9.0 7 9.0 49 9.0 0 9.0 14 9.0 21 9.0 28 9.0 35 9.0 42 Cone. 365 392 438 437 394 406 399 408 ln([P]t/[P]o) (A) (A) 0.000 -0.002 -0.106 -0.078 -0.095 -0.072 0.05 N-EtFOSE Alcohol @ SOC pH 9.0, Rate constant graph 0 .0 0- t_________ -0.05 - 1Cm - 0 .1 0 -0.15 - -0.20 - ^ T y = -2.23E-03X - 6.80E-03 -0.25 0 10 20 30 40 50 Time (days) pH Time (Days) Cone. ln([PMPjo) 11.0 0 412 0.000 11.0 7 419 0.015 11.0 14 413 0.002 11.0 21 378 -0.087 11.0 28 385 -0.069 11.0 35 392 -0.051 11.0 42 387 -0.064 11.0 49 367 -0.118 N-EtFOSE Alcohol @ 50 C SUMMARY OUTPUT R epression Statistics Multiple R R Square Adjusted R Square Standard Error Observations 0.72644 0.52771 0.40964 0.03564 6 ANOVA Regression Residual Total df 1 4 5 SS 0.00568 0.00508 0.01076 Intercept X Variable 1 % 2cr Slope Uncertainty 95% C oefficients -0.00680 -0.00223 Standard E rror 0.02858 0.00105 SUMMARY OUTPUT R egression S tatistics Multiple R R Square Adjusted R Square Standard Error Observations 0.83358 0.69485 0.64399 0.02836 8 ANOVA Regression Residual Total d f___________ 1 6 7 SS 0.01099 0.00483 0.01581 Intercept X Variable 1 % 2o Slope Uncertainty 54% C o e ffic ie n ts 0.01012 -0.00231 Standard E rror 0.01830 0.00063 (A) Data in Italics have been rejected from the fits on the basis of the data quality objectives (see text). BACK TO MAIN Page 53 of 83 3M Environmental Laboratory Report No. W1872 EtFOSE Alcohol Hydrolysis Study 50C; pH 1.5 Reprocessed data on 9-5-00 using internal standard quantitation. N-EtFOSE Alcohol Sampie 1.D. MeOH Blank EtFOSOOZD V ia l# 91 Ret Time 8.5 Cone. (ngfrnl) 0 !!li||^ a n d a rd : IliS ls D % Spike Recovery tlm eR oln Ret Time 6.2 Area 0 Cone. (ng/ml) 0 L1 1.5,155.40 EtFOS003.D 1 8.5 505275 160 L2 1.5, 310.80 EtFOS004.D 2 8.5 957739 312 L3 1.5,466.20 EtFOS005.D 3 8.5 1396926 461 L4 1.5,621.60 EtFOS006.D 4 8.5 1869709 18066 L5 1.5,777.00 EtFOS007.D 5 8.5 2347115 789 L6 1.5,932.40 EtFOS008.D 6 8.5 2911551 947 103% 100% 99% (B) 102% 102% 6.2 5973 6.2 42481 6.2 88723 6.2 112072 6.2 167565 6.2 210524 2 13 28 36 (A) 66 MeOH Blank EtFOS009.D 91 8.6 MeOH Blank EtFOSOIO.D 91 8.6 0 0 0 0 6.2 0 6.2 0 0 0 EFA-001 EFA-002 E FA-003 EFA-019 EFA-020 E FA-021 EFA-037 EFA-038 EFA-039 EFA-055 E FA-056 E FA-057 EFA-073 EFA-074 EFA-075 EtFOSOH.D 11 8.6 1389788 487 EtFOS012.D 12 8.6 1373031 492 EtFOS013.D 13 8.6 1966742 709 EtFOS014.D 14 8.6 1363242 474 EtFOS015.D 15 8.5 1358878 473 EIFOS016.D 16 8.5 1810324 642 EtFOS017.D 17 8.5 1317957 473 EtFOS018.D 18 8.5 1327970 466 EtFOS019.D 19 8.6 2009905 703 EtFOS020.D 20 8.5 1295532 409 EtFOS021.D 21 8.6 1393108 421 EtFOS022.D 22 8.6 2057602 616 EtFOS023.D 23 8.6 1332265 449 EtFOS024.D 24 8.6 1282648 429 EtFOS025.D 25 8.6 1805236 613 1% 0% 1% 3% 5% 101% 77% 108% 93% 80% Day 0 Day 0 DayO Day 7 Day 7 Day 7 Day 14 Day 14 Day 14 Day 21 Day 21 Day 21 Day 28 Day 28 Day 28 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 MeOH Blank EtFOS026.D 91 8.6 0 0 L4 1.5, 621.60 EtFOS027.D 4 8.6 1932192 191348 MeOH Blank EFOS028.D 91 8.6 0 0 (B) 6.2 0 6.2 113170 6.2 0 0 36 0 EFA-091 EFA-092 E FA-093 EFA-109 EFA-110 EFA-111 EFA-127 EFA-128 E FA-129 EtFOS029.D 26 8.6 1287115 430 EtFOS030.D 27 8.6 1200913 409 EtFOS031.D 28 8.6 1954046 649 EtFOS032.D 29 8.6 1284635 435 EtFOS033.D 30 8.6 1298904 441 EtFOS034.D 31 8.6 2002610 667 EtFOS035.D 32 8.6 1295601 433 EtFOS036.D 33 8.6 1236840 421 EtFOS037.D 34 8.6 2094856 694 5% 2% 3% 105% 105% 123% Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 0 0 0 0 O 0 0 0 0 0 0 0 0 0 0 0 0 0 MeOH Blank EFOS049.D 91 8.6 MeOH Blank EIFOS050.D 91 8.6 0 0 0 0 6.2 0 6.2 0 0 0 L1 1.5,155.40 L2 1.5, 310.80 L3 1.5, 466.20 L4 1.5, 621.60 L5 1.5,777.00 L6 1.5,932.40 EtFOS051.D EtFOS052.D EtFOS053.D EtFOS054.D E1FOS055.D EtFOS056.D 1 8.6 494514 164 2 8.6 949495 310 3 8.6 1416444 459 4 8.6 1838575 16370 5 8.6 2308742 777 6 8.6 2764328 912 106% 100% 98% (B) 100% 98% 6.2 5778 6.2 41998 6.2 83340 6.2 110610 6.2 164483 6.2 209470 1 13 26 34 (A) 64 Curve averaged. Linear,include origin. Calibration range; 155-932 ng/ml (A) Exluded on te basis of data quality objectives; see text (B) Excluded - no internal standard added. Curve averaged, Linear.include origin. Calibration range: 1.28-64 ng/ml %Standard 124% 104% 111% 93% 103% 94% 114% 98% 103% 90% 101% Ret Time 5.9 Area 0 5.9 465165 5.9 456303 5.9 447867 5.9 451811 5.9 (A) 5.9 460976 5.9 0 5.9 0 5.9 455518 5.9 451940 5.9 449589 5.9 466460 5.9 465414 5.9 458389 5.9 443144 5.9 460883 5.9 459552 5.9 458151 5.9 471750 5.9 468384 5.9 464774 5.9 456350 5.9 464731 5.9 0 5.9 453100 5.9 0 5.9 464732 5.9 454761 5.9 459221 5.9 458673 5.9 457220 5.9 466294 5.9 460311 5.9 452048 5.9 454032 5.9 0 5.9 0 5.9 5.9 5.9 5.9 5.9 5.9 mean S.D. %S.D. 485811 474209 456592 461931 (A) 469641 460164 8224 1.8% Cone. 0 403 403 403 403 403 403 0 0 403 403 403 403 403 403 403 403 403 403 403 403 403 403 403 0 403 0 403 43 403 403 403 403 403 403 403 0 0 403 403 403 403 403 403 Area 8.3 0 8.3 880788 8.3 873132 8.3 868287 8.3 (B) 8.3 856724 8.3 887024 8.3 0 8.3 0 8.3 817105 8.3 799340 8.3 797895 8.3 823152 8.3 822557 8.3 811296 8.3 798883 8.3 816320 8.3 822562 8.3 904583 8.3 946257 8.3 959312 8.3 848397 8.3 855992 8.3 846072 8.3 0 8.3 (B) 8.3 0 8.3 855890 8.3 838230 8.3 865946 8.3 845709 8.3 842379 8.3 863388 8.3 855846 8.4 840371 8.4 868271 8.4 0 8.4 0 8.4 8.4 8.4 8.6 8.4 8.4 mean S.D. %S.D. 841210 871122 883822 (B) 855704 874479 854060 36597 4.3% 0 316 316 316 316 316 316 0 0 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 0 316 316 316 316 316 316 316 316 316 0 316 316 316 316 316 316 BACK TO MAIN Page 54 of 83 Bk 3M Environmental Laboratory Report No. W1872 EtFOSE Alcohol Hydrolysis Study 50C; pH 3 Reprocessed data on 8-31-00 using internal standard quantitation. MeOH Blank EtFOS058.D V ial# 91 RetUm b 8.6 0 Cone. fn l 0 ;^|S |;f!B dard or %R&D = L1 3.0,155.40 EtFOS059.D 41 8.6 100572 31 L23.0, 310.80 EtFOS060.D 42 8.6 993993 332 L3 3.0, 466.20 EtFOS061.D 43 8.6 1469637 478 L4 3.0, 621.60 EtFOS062.D 44 8.6 1837884 581 L5 3.0,777.00 EtFOS063.D 45 8.6 2351584 763 L6 3.0,932.40 EtFOS064.D 46 8.6 2880052 932 (A) 107% 103% 93% 98% 100% MeOH Blank EtFOS065.D 91 8.6 MeOH Blank EFOS066.D 91 8.6 0 0 0 0 EFA-004 EFA-005 EFA-006 EFA-022 EFA-023 EFA-024 EFA-040 EFA-041 EFA-042 EFA-058 EFA-059 EFA-060 EFA-076 EFA-077 EFA-078 EtFOS067.D 51 8.6 1348761 461 EtFOS068.D 52 8.6 1306963 460 EtFOS069.D 53 8.6 1981411 702 EtFOS070.D 54 8.6 1219370 402 EtFOS071.D 55 8.6 1235031 417 EtFOS072.D 56 8.6 1672756 594 EtFOS073.D 57 8.6 1066222 376 EtFOS074.D 58 8.6 1134902 410 EtFOSQ75.D 59 8.6 '1643131 567 EtFOS076.D 60 8.6 1150307 380 EtFOS077.D 61 8.5 1102935 344 EtFOS078.D 62 8.5 1706690 525 EtFOS079.D 63 8.5 1113117 371 EtFOS080.D 64 8.6 1146209 389 EtFOS081.D 65 8.5 1622872 560 0% 4% 9% 10% 5% MeOH Blank L4 3.0, 621.60 MeOH Blank EtFOS082.D EtFOS083.D EtFOS084.D 91 8.6 0 0 44 8.6 1854835 612 91 8.6 0 0 98% E FA-0 94 EFA-095 EFA-096 EFA-112 EFA-113 EFA-114 EFA-130 EFA-131 EFA-132 EtFOS085.D EtFOS086.D EtFOS087.D EtFOS088.D EtFOS089.D EtFOS090.D EtFOS091.D EtFOS092.D EtFOS093.D 66 8.6 1130406 378 67 8.6 1142643 380 68 8.6 1775042 597 69 8.6 1191578 394 70 8.5 1208645 398 71 8.6 1824457 595 72 8.5 1235171 397 73 8.6 1172642 380 74 8.6 1932230 638 0% 1% 4% MeOH Blank EtFOS105.D 91 8.6 MeOH Blank EtFOSl06.D 91 8.6 0 0 0 0 L1 3.0 155.40 EIFOS107.D 41 8.6 100153 31 L2 3.o' 310.80 EFOS108.D 42 8.6 957828 314 L3 3.0, 466.20 EtFOS109,D 43 8.6 1450723 469 L4 3.0,621.60 BFOS110.D 44 8.6 1815257 612 L5 3.0, 777.00 E tF O S m .D 45 8.6 2282741 770 L6 3.0, 932.40 EFOS112.D 46 8.6 2876504 967 Method ID: 830D00.M Curve averaged, Linear,include origin. Calibration range: 155-932 ng/ml (A) Exluded on te basis of data quality objectives; see text (A) 101% 101% 98% 99% 104% % Spike Recovery 111% 85% eo% 75% 83% 100% 91% 115% Time P oint Ret Time 6.2 Area 0 Coria. : ; (ng/mQ ;; 0.00 %Standard 6.2 11759 6.2 46340 6.2 84849 6.2 125379 6.2 211732 6.2 198183 2.15 13.14 25.75 38.71 68.08 63.05 (A) 103% 101% 101% (A) 99% 6.2 0 6.2 0 0.00 0.00 Day 0 DayO Day 0 Day 7 Day 7 Day 7 Day 14 Day 14 Day 14 Day 21 Day 21 Day 21 Day 28 Day 28 Day 28 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 0 0 0 0 0 0 0 0 O 0 0 0 0 0 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 6.2 0 6.2 124667 6.2 0 0.00 29.10 0.00 102% Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 0 0 0 0 0 0 0 0 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 6.2 0 6.2 0 0.00 0.00 6.2 14073 6.2 46697 6.2 83364 6.2 119432 6,2 199387 6.2 197627 3.02 13.67 25.78 38.69 65.17 63.60 (A) 107% 101% 101% (A) 99% Curve averaged, Linear,include origin. Calibration range: 12.8-64 ng/ml Ret Time 5.9 Area 0 5.9 450603 5.9 457139 5.9 451913 5.9 453343 5.9 443115 5.9 447053 5.9 0 5.9 0 5.9 456498 5.9 444095 5.9 440492 5.9 466273 5.9 453856 5.9 432375 5.9 442557 5.9 435689 5.9 447337 5.9 432112 5.9 445253 5.9 436986 5.9 442336 5.9 450543 5.9 429690 5.9 0 5.9 446589 5.9 0 5.9 443433 5.9 445791 5.9 439114 5.9 454153 5.9 435430 5.9 445709 5.9 447667 5.9 435779 5.9 431328 5.9 0 5.9 0 5.9 439145 5.9 444646 5.9 443376 5.9 432006 5.9 435449 5.9 442026 S.D. %S.D. 8328 1.9% N-MeFOSE Alcohol Cone. 0 403 403 403 403 403 403 0 0 403 403 403 403 403 403 403 403 403 403 403 403 403 403 403 0 403 0 403 403 403 403 403 403 403 403 403 0 0 403 403 403 403 403 403 R e fttm e s - -v/Area.^ 8.3 0 8.3 796488 8.3 BQ7861 8.3 831972 8.3 858143 8.3 837174 8.3 839951 8.3 0 8.3 8.3 791432 8.3 769975 8.3 766604 8.3 821287 8.3 801078 8.3 764158 ,8.3 766340 8.3 748177 8.3 786346 8.3 817457 8.3 864520 8.3 881726 8.3 809837 8.3 795653 8.3 785909 8.3 0 8.3 823651 8.3 8.3 808420 8.3 813785 8.3 806848 8.3 817322 8.3 820921 8.3 831848 8.3 841331 8.3 834320 8.3 821524 8.3 0 8.3 8.3 790968 8.3 821694 8.3 837999 8.3 804635 8.3 805556 8.3 808753 S.D. %S.D. 28775 3.5% 0 316 316 316 316 316 316 0 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 0 316 316 316 316 316 316 316 316 0 316 316 316 316 316 316 Page 55 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 EtFOSE Alcohol Hydrolysis Study 50C; pH 5 Reprocessed data on 8-31-00 using internal standard quantitation. NEtFOSE Alcohol ___________ ________________ ' Sample i.O, MeOH Blank Dale File EtFOS002.D I S m : M Rat Time 91 8.6 Area 0 pC onc. in s ta ll" 0 Recovery L1 5.0, 155.40 L2 5.0,310.80 L3 5.0,466.20 L4 5.0, 621.60 L5 5.0, 777.00 L6 5.0, 932.40 EtFOS003.D EtFOS004.D EtFOS005.D EtFOS006.D EtFOS007.D EtFOS008.D 1 8.6 403311 155 2 8.6 835089 321 3 8.6 1242363 458 4 8.6 1685478 637 5 8.6 2022413 765 6 8.6 2447180 937 99% 103% 98% 102% 98% 101% MeOH Blank EtFOS009.D 91 8.6 MeOH Blank EtFOSOIO.D 91 8.6 0 0 0 0 EFA-007 EFA-QQ8 EFA-009 EFA-025 EFA-026 EFA-027 EFA-043 EFA-044 EFA-045 EFA-061 EFA-062 EFA-063 EFA-079 EFA-080 EFA-081 EtFOS011.D 11 8.6 1134978 485 EtFOS012.D 12 8.6 1131090 468 EtFOS013.D 13 8.6 1672237 700 EIFOS014.D 14 8.6 1147480 461 EtFOS015.D 15 8.6 1100973 451 EtFOS016.D 16 8.6 1642451 680 EtFOS017.D 17 8.6 1098638 468 EtFOS018.D 18 8.6 1111964 476 EtFOS019.D 19 B.6 1595846 659 EtFOS020.D 20 8.6 1057199 411 E1FOS021.D 21 8.6 1073533 421 EtFOS022.D 22 8.6 1872384 633 EtFOS023.D 23 8.6 1057738 421 E1FOS024.D 24 8.6 1047642 438 EFOS025.D 25 8.6 1615792 643 4% 2% 2% 2% 4% 103% 103% 86% 100% 98% MeOH Blank E1FOS026.D 91 8.6 0 0 L4 5.0, 621.60 EtFOS027.D 4 8.6 1595911 602 MeOH Blank EIFOS028.D 91 8.6 0 0 97% EFA-097 EtFOS029.D 26 8.6 1053254 434 1% EFA-098 EtFOS030.D 27 8.6 1065586 429 EFA-099 EtFOS031.D 28 8.6 1619591 638 95% EFA-115 EtFOS032.D 29 8.6 1060903 426 1% EFA-116 EtFOS033.D 30 8.6 1040839 429 EFA-117 EIFOS034.D 31 8.6 1639828 651 103% EFA-133 EtFOS035.D 32 8.6 1001513 402 4% EFA-134 E1FOS036.D 33 8.6 1026623 418 EFA-135 EIFOS037.D 34 8.6 1701880 680 124% MeOH Blank EtFOS049.D 91 8.6 MeOH Blank EtFOS050.D 91 8.6 0 0 0 0 L1 5.0,155.40 L2 5.0, 310.80 L35.0, 466.20 L4 5.0, 621.60 EtFOS051.D EtFOS052.D EtFOS053.D EtFOS054.D 1 8.6 368386 147 2 8.6 763938 311 3 8.6 1174479 463 4 8.6 1571631 628 L5 5.0, 777.00 L6 5.0, 932.40 Method ID: 0B30A00.M EtFOS055.D EtFOS056.D 5 8.6 20043Q6 776 6 8.6 2360319 927 internal Standard quant: r2 -0.999 Curve averaged, Linear,include origin. Calibration range: 155-932 ng/ml (A) Exluded on te basis of data quality objectives; see text. 95% 100% 99% 101% 100% 99% PFOS ___________________________ ,, _______ THPFOS__________________________ N-MeFOSE Alcohol Tim e P oint Ret Urne H-re' 6.1 0 Cone. (ncj/ml) 0.00 %Standard Ret Time 5.9 0 Cnc. 0.00 RtTim e T?:" Area 8.3 { 0 6.1 9925 (A) 6.2 40365 12.83 6.2 85079 26.71 6.2 119421 37.32 6.2 162768 51.42 6.2 198997 65.61 101% 105% 97% 97% 103% 5.9 463166 402.60 8.3 * 762610 5.9 459954 402.60 8.3 757407 5.9 464019 402.60 8.3 787573 5.9 465570 402.60 8.3 767532 5.9 460220 402.60 8.3 766958 5.9 440802 402.60 8.3 756833 6.2 0 6.2 0 0.00 0.00 5.9 0 5.9 0 0.00 8.3 0.00 8.3 0 0 Day 0 Day 0 Day 0 Day 7 Day 7 Day 7 Day 14 Day 14 Day 14 Day 21 Day 21 Day 21 Day 28 Day 28 Day 28 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.9 450402 402.60 5.9 460158 402.60 5.9 455075 402.60 5.9 471566 402.60 5.9 471165 402.60 5.9 463772 402.60 5.9 464470 402.60 5.9 464484 402.60 5.9 457576 402.60 5.9 461557 402.60 5.9 473678 402.60 5.9 516735 402.60 5.9 456157 402.60 5.9 457475 402.60 5.9 454552 402.60 8.3 678947 8.3 702308 8.3 692884 8.3 722196 8.3 709296 8.3 700710 8.3 681111 8.3 677627 8.3 702137 8.3 746995 8.3 741107 8.3 858002 8.3 729455 8.3 695006 8.3 729303 6.2 0 6.2 122855 6.2 0 0.00 37.69 0.00 99% 5.9 0 0.00 8.3 0 5.9 474181 402.60 8.3 769377 5.9 0 0.00 8.3 0 Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 62 6.2 62 6.2 6.2 6.2 6.2 6.2 6.2 0 0 0 0 0 0 0 0 0 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 5.9 467618 402.60 8.3 704694 5.9 458821 402.60 8.3 720938 5.9 455327 402.60 8.3 736712 5.9 457873 402.6Q 8.3 722797 5.9 460032 402.60 8.3 704234 5.9 464180 402.60 8.3 730256 5.9 448743 402.60 8.3 722905 5.9 461024 402.60 8.3 712643 5.9 445353 402.60 8.3 726449 6.2 0 6.2 0 0.00 0.00 5.9 0 5.9 0 0.00 8.3 0.00 8.3 0 0 6.2 12848 6.2 43154 (A) 13.86 6.2 76798 24.22 6.2 116168 37.44 6.2 153191 49.42 6.2 184840 63.88 tntemai Standard quant: r2 = 0.999 Curve averaged, Unear.indude origin. Calibration range: 12.8-64 ng/ml 109% 95% 98% 93% 100% 5.9 5.9 5.9 5.9 5.9 5.9 mean S.D. %S.D. 461447 455083 462085 451392 450735 420520 460188 13657 3.0% 402.60 402.60 402.60 402.60 402.60 402.60 8.4 8.4 8.4 8.4 8.4 8.4 mean S.D. %S.D. 733167 714671 735880 726280 748759 737916 730099 34464 4.7% Cone, 0 316 316 316 316 316 316 0 0 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 0 316 0 316 316 316 316 316 316 316 316 316 0 0 316 316 316 316 316 316 Page 56 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 EtFOSE Alcohol Hydrolysis Study 50C; pH 7 Reprocessed data on 8-31-00 using internal standard quantitation. Sample 10 MeOH Blank Data File EtFOS058.D V la f# 91 I RATillW 8.6 0 Com, k o f Standard or (ng/ml>____ /. RSD 0 L1 7,0,155.40 L2 7.0, 310.80 L37.0, 466.20 L4 7 .0,621.60 L5 7.0, 777.00 L6 7.0, 932.40 EtFQS059.D EtFOS060.D EtFOS061.D EtFOS062.D EtFOS063.D EtFOS064.D 41 8.6 480449 173 42 8.6 820775 308 43 8.6 1195458 474 44 8.6 1158453 457 45 8.6 1970492 739 46 8.6 2451486 951 111% 99% 102% (A) 95% 102% MeOH Blank EtFOS065.D 91 8.6 MeOH Blank EtFOS066.D 91 8.6 0 0 0 0 EFA-010 EFA-011 EFA-012 EFA-028 EFA-029 EFA-030 EFA-046 EFA-047 EFA-048 EFA-064 EFA-065 EFA-066 EFA-082 EFA-083 EFA-084 EtFOS067.D 51 8.6 1152415 462 EtFOS068.D 52 8.6 1143301 474 EtFOS069.D 53 8.6 1745528 700 EIFOS070.D 54 8.6 1107418 452 EtFOS071.D 55 8.6 1098715 459 EtFOS072.D 56 8.6 1678444 681 EtFOS073.D 57 8.6 1100624 450 BFOS074.D 58 8.6 1116212 458 EtFOS075.D 59 8.6 1622694 692 EtFOS076.D 60 8.6 1085190 430 EtFOS077.D 61 8.6 1055654 412 EtFOS078.D 62 8.6 1643724 636 E1FOS079.D 63 8.6 1056770 422 EtFOS080.D 64 8.6 1074530 420 EtFOS081.D 65 8.6 1619857 660 3% 1% 2% 4% 0% MeOH Blank EtFOS082.D 91 8.6 0 0 L4 7.0, 621.60 EtFOS081.D 44 8.6 1153406 467 MeOH Blank EIFOS084.D 91 8.6 0 0 (A) EFA-100 EFA-101 EFA-102 EFA-118 EFA-119 EFA-120 EFA-136 EFA-137 EFA-138 EtFOS085.D 66 8.6 1054195 418 EtFOS086.D 67 8.6 1057309 425 EtFOS087.D. 68 8.6 1578463 648 E1FOS088.D 69 8.6 1054100 420 EtFOS089.D 70 8.6 1061878 408 EIFOS090.D 71 8.6 1629040 629 EtFOS091.D 72 8.6 1043657 408 EtFOS092.D 73 8.6 1041709 412 EtFOS093.D 74 8.6 1729685 729 2% 3% 1% MeOH Blank EtFOS105.D 91 8.6 MeOH Blank EtFOS106.D 91 8.6 0 0 0 0 U 7.0,155.40 BFOS107.D 41 8.6 486234 177 L2 7.0,310.80 EtFOS108.D 42 8.6 810866 313 L3 7.0,466.20 EtFOS109.D 43 8.6 1178478 468 L4 7.0, 621.60 EFOS110.D 44 8.6 1140569 448 L5 7.0, 777.00 EtFOS111.D 45 8.6 1936040 769 L6 7.0, 932.40 EtFOS112.D 46 8.6 2364608 941 114% 101% 100% (A) 99% 101% Curve averaged, Unear.indude origin. Calibration range; 155-932 ng/m! (A) Exluded on te basis of data quality objectives; see text % Spike Recovery 107% 104% 110% 99% 110% 104% 99% (A) Tim e Point Ret Time 6.2 Area 0 C.bric-..(ng/ml) 0 6.2 11467 6.2 38240 6.2 111921 6.2 117460 6.2 157029 6.2 191758 4 12 36 39 51 63 6.2 7938 6.2 0 0 0 Day 0 DayO DayO Day 7 Day 7 Day 7 Day 14 Day 14 bay 14 Day 21 Day 21 Day 21 Day 28 Day 28 Day 28 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 0 0 0 0 0 0 0 9782 10000 9278 0 0 0 0 0 0 0 0 0 0 0 0 3 3 3 0 0 0 0 0 6.2 0 6.2 113680 6.2 0 0 38 0 Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 6.2 0 6.2 0 0 0 6.2 6766 6.2 37598 6.2 119963 6.2 117083 6.2 152954 6.2 184423 (A) 12 40 40 51 63 Curve averaged, Linear,include origin. Calibration range: 12.8-64 ng/mI %Standard (A) 98% (A) 101% 96% 99% 100% 97% 157% 104% 97% 99% Ret Time 5.9 Area 0 5.9 451663 5.9 453588 5.9 461481 5.9 454013 5.9 463358 5.9 454355 5.9 0 5.9 0 5.9 457166 5.9 457511 5.9 471437 5.9 457174 5.9 460597 5.9 465446 5.9 458934 5.9 468514 5.9 461270 5.9 453289 5.9 446052 5.9 455047 5.9 450095 5.9 455593 5.9 451026 5.9 0 5.9 447307 5.9 0 5.9 449888 5.9 447436 5.9 446563 5.9 451243 5.9 453084 5.9 470642 5.9 441948 5.9 451166 5.9 445912 5.9 0 5.9 0 5.9 5.9 5.9 5.9 5.9 5.9 mean S.D. %S.D. 438170 448318 449708 442333 446823 438757 453655 8350 1.8 % ;. Cone. 0 403 403 403 403 403 403 0 0 403 403 403 403 403 403 403 403 403 403 403 403 403 403 403 0 403 0 403 403 403 403 403 403 403 403 403 0 0 403 403 403 403 403 403 Alcohol 8.4 0 8.4 706921 8.4 725999 8.4 709796 8.4 711675 8.4 767139 8.4 748395 8.3 0 8.3 0 8.3 701483 8.4 679580 8.3 716153 8.3 687125 8.3 672434 8.3 706387 8.3 685975 8.3 684580 8.3 672527 8.3 705473 8.3 714354 8.3 738802 8.3 699469 8.3 714231 8.3 702764 8.3 8.3 695268 8.3 0 8.3 703676 8.3 695096 8.3 697321 8.3 700866 8.3 725550 8.3 739763 8.3 712663 8.3 705068 8.3 682117 8.3 8.3 0 8.3 8.3 8.3 8.3 8.3 8.3 mean S.D. %S.D. 701583 707107 708259 714457 725954 729327 708376 20821 2.9% 0 316 316 316 316 316 316 0 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 0 316 316 316 316 316 316 316 316 316 0 316 316 316 316 318 316 BACK TO MAIN Page 57 of 83 Bk EtFOSE Alcohol Hydrolysis Study SOC; pH 9 Reprocessed data on 8-29-00 __________________ _____ N-EtFOSE Alcohol__________________ ____________________________ ____________ PFOS Cone Sample t D MeOH Blank Data File EtFOS002.D V # ... 91 8.5 0 MO RSD % Spike Time Point R eturn 6.1 L1 9.0,155.40 EtFOS003.D 8.5 409224 144 L2 9 .0 ,310.80 EtFOS004.D 2 8.5 892538 324 L3 9.0,466.20 EtFOS005.D 3 8.6 1348314 482 L4 9.0, 621.60 EIFOS006.D 4 8.5 1769188 631 L5 9.0,777.00 EtFOS007.D 5 8.5 2119590 763 L6 9.0,932.40 EtFOS008.D 6 8.5 2618151 949 93% 104% 103% 102% 98% 102% 6.1 6.2 6.2 6.2 6.2 6.2 MeOH Blank EtFOS009.D 91 8.5 MeOH Blank EtFOSOIO.D 91 8.5 0 0 0 0 6.2 6.2 EFA-013 EFA-014 EFA-015 EFA-031'' EFA-032 EFA-033 EFA-049 EFA-050 EFA-051 EFA-067 EFA-068 EFA-Q69 EFA-085 EFA-086 EFA-087 EtFOSOH.D EIFOS012.D EtFOS013.D EtFOSOH.D EFOS015.D EtFOS016.D EtFOS017.D EIFOS018.D EtFOS019.D EtFOS020.D EtFOS021.O EtFOS022.D EtFOS023.D EtFOS024.D EIFOS025.D 11 8.5 1143422 435 12 8.5 1142252 441 13 8.5 1685734 640 14 8.5 1134663 426 15 8.5 809137 304 16 8.5 1640714 632 17 8.5 1119730 438 18 8.5 1118496 437 19 8.5 1650519 642 20 8.5 1099106 394 2f 8.5 1102692 394 22 8.5 1658623 602 23 8.5 1092118 398 24 8.5 1088786 413 25 8.5 1619682 621 1% 33% 0% 0% 4% 93% (A) 94% 96% 99% DayO DayO DayO Day 7 Day 7 Day 7 Day 14 Day 14 Day 14 Day 21 Day21 Day 21 Day 28 Day 28 Day 28 6.2 6.2 8.2 6.2 6.2 62 62 6.2 6.2 62 6.2 6.2 6.2 6.2 6.2 MeOH Blank EtFOS026.D 91 8.5 0 0 L4 9.0, 621.60 EtFOS027.D 4 8.5 1678694 638 MeOH Blank EtFOS028.D 91 8.5 0 0 103% 6.2 6.2 62 EFA-103 EFA-104 EFA-1Q5 EFA-121 EFA-122 EFA-123 EFA-139 EFA-140 EFA-141 EtFOS029.D 26 8.5 1079749 404 EtFOS030.D 27 8.5 1067069 393 BFOSQ31.D 28 8.5 1655168 611 EtFOS032.D 29 8.5 1095265 421 EIFOS033.D 30 8.5 1026620 395 EIFOS034.D 31 8.5 1593121 577 EIFOS035.D 32 8.5 1058111 390 EtFOS036.D 33 8.5 1080272 394 EtFOS037.D 34 8.5 1114214 424 3% 7% 1% 97% 78% (A,B) Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 6.2 6.2 6.2 62 6.2 6.2 6.2 6.2 6.2 MeOH Blank EtFOS049.D 91 8.5 MeOH Blank EtFOS050.D 91 8.5 0 0 0 0 6.2 6.2 L1 9.0,155.40 L2 9.0,310.80 EtFOSQ51.D EFOS052.D 1 8.5 406650 148 2 8.5 832823 320 L3 9.0,466.20 EtFOS053.D 3 8.6 1278664 475 L4 9.0, 621.60 EtFOS054.D 4 8.6 1637356 623 L5 9.0,777.00 EtFOS055.D 5 8.5 2035025 756 L6 9.0, 932.40 EtFOS056.D 6 8.5 2422983 920 Method ID: 08289is.m Internal Standard quant r2 = 0.999 Curve averaged, linear, include origin Calibration range : 155-932 ng/ml (A) Exluded on te basis of data quality objectives; see text 95% 103% 102% 100% 97% 99% (B) Excluded - no internal standard added. 6.2 6.2 6.2 6.2 6.2 6.2 Internal $ Curve av Calibrato 3M Environmental Laboratory Report No. W1872 e rea 0 Cone. infittii) 0.0 7965 39881 74208 112382 147683 181333 1.4 14.1 28.3 41.3 54.4 65.1 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 110233 0 0.0 35.1 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 0 0.0 9371 0.9 42306 12.2 78648 24.6 112614 37.0 147384 47.8 180489 60.4 standard quant i2- 0.995 eraged, linear, include origin 3n range : 12.8-64 ng/ml THPFOS ________________ N-MeFOSE Alcohol %Standard 110% 111% 111% 108% 107% 102% 94% (A) 96% 96% 97% 94% 95% Ret Time 5.86 Area 0 : Conci 0.0 5.9 303076 5.9 338869 5.9 338620 5.9 358974 5.9 362649 5.9 374889 402.6 402.6 402.6 402.6 402.6 402.6 5.9 0 5.9 0 0.0 0.0 5.9 392100 5.9 388527 5.9 401788 5.9 398631 5.9 304032 5.9 398182 5.9 407818 5.9 400267 5.9 402785 5.9 401387 5.9 403133 5.9 402836 5.9 402632 5.9 401613 5.9 406718 402.6 402.6 402.6 402.6 402.6 4Q2.6 402.6 402.6 402.6 402.6 402.6 402.6 402.6 402.6 402.6 5.9 0 5.9 400498 5.9 0 0.0 402.6 0.0 5.9 414779 5.9 402920 5.9 416468 5.9 400033 5.9 400713 5.9 404666 5.9 401817 5.9 409040 5.9 (B) 5.9 0 5.9 0 402.6 402.6 402.6 402.6 402.6 402.6 402.6 402.6 402.6 0.0 0.0 5.9 5.9 5.9 5.9 5.9 5.9 Mean S.D. %S.D. 414987 407028 407820 399211 410184 401194 391136 28476 7.3% 402.6 402.6 402.6 402.6 402.6 402.6 Ret Time 8.3 Area 0 8.3 714775 8.3 720711 8.3 739101 8.3 744916 8.3 739652 8.3 736444 8.3 0 8.3 0 8.3 692760 8.3 683190 8.3 699902 8.3 701801 8.3 694599 8.3 689954 8.3 674255 8.3 675759 8.3 683372 8.3 733563 8.3 736476 8.3 731089 8.3 722324 8.3 694410 8.3 692520 8.3 0 8.3 699217 8.3 0 8.3 704303 8.3 713838 8.3 719832 8.3 685534 8.3 684709 8.3 732430 8.3 713040 8.3 720879 8.3 693569 8.3 0 8.3 0 8.3 8.3 8.3 8.3 8.3 8.3 Mean S.D. %S.D. 694298 680556 712130 697612 717132 703103 702521 17720 2.5% Cone. 0.0 316 316 316 316 316 316 0 0 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 0 316 0* 316 316 316 316 316 316 316 316 316 0 0 316 316 316 316 316 316 Page 58 of 8c BACK TO MAIN EtFOSE Alcohol Hydrolysis Study SOC; pH 11 Reprocessed data on 8-31-00 using internal standard quantitation. N-EtFOSE Alcohol I Cone MeOH Blank BFOS058.D 91 8.6 0 0 L1 11.0,155.40 EtFOS059.D 41 8.6 446561 145 L211 .0,310.80 EtFOSOfiO.D 42 8.6 926265 347 L 3 1 1 . 0 , 466.20 EtFOS061.D 43 8.6 1283574 467 L 4 1 1 . 0 , 621.60 EtFOS062.D 44 8.6 1726739 631 L5 11.0, 777.00 EIFOS063.D 45 8.6 2146734 774 L611.0, 932.40 EIFOS064.D 46 8.6 2634375 911 MeOH Blank EtFOS065.D 91 8.6 MeOH Blank EtFOS066.D 91 8.6 0 0 0 0 EFA-016 EFA-017 EFA-018 EFA-034 EFA-035 EFA-036 EFA-052 EFA-053 EFA-054 EFA-070 EFA-071 EFA-072 EFA-088 EFA-089 EFA-090 EtFOS067.D EtFOS068.D EtFOS069.D EtFOS070.D EtFOS07l.D EtFOS072.D EtFOS073.D EtFOS074.D EtFOS075.D EtFOS076.D E1FOS077.D EtFOS078.D EtFOS079.D EtFOS080.D EtFOS081.D 51 8.6 1101922 399 52 8.6 1115067 426 53 8.6 1618557 624 54 8.6 1097421 416 55 8.6 1135383 421 56 8.6 1607415 630 57 8.6 1103015 413 58 8.6 1082138 413 59 8.6 1675149 632 60 8.6 1079072 378 61 8.6 1104263 378 62 8.6 1611497 579 63 8.6 1046583 392 64 8.6 1064303 378 65 8.5 1652545 613 MeOH Blank L4 9.0. 621.60 MeOH Blank EtFOS082.D EtFOS083.D EtFOS084.D 91 8.5 0 0 44 8.5 1748022 636 91 8.5 0 0 EFA-106 EFA-107 EFA-108 EFA-124 EFA-125 EFA-126 EFA-142 EFA-143 EFA-144 EtFOS085.D EFOS086.D EtFOS087.D EtFOSOSS.D EtFOS089.D EtFOS090.D EtFOSD91.D EtFOS092.D EtFOS093.D 66 8.5 1049049 392 67 8.5 1083945 392 68 8.5 1604358 584 69 8.5 1087655 391 70 8.5 1046304 383 71 8.5 1605607 586 72 8.5 1042824 364 73 8.5 1019110 369 74 8.5 1655321 597 MeOH Blank EtFOS105.D 91 8.5 MeOH Blank EtFOS106.D 91 8.5 0 0 0 0 L 1 11.0,155.40 EtFOS107.D 41 8.5 453167 148 L211.0, 310.80 EtFOS108.D 42 8.5 899458 335 L311.0, 466.20 EtFOS109.D 43 8.5 1289183 460 L411.0, 621.60 EtFOSHO.D 44 8.5 1730293 625 L511.0, 777.00 E tF O S m .D 45 8.5 2150602 767 L611.0, 932.40 EtFOS112.D 46 8.5 2594308 941 Method ID: 0S30A00.M Internal Standard quant'. r2 = 0.998 Curve averaged, Linear,include origin. Calibration range: 155-932 ng/ml (A) E lu d e d on te basis of data quality objectives; see text. * ~ f i ' n c D r`i ' ' r ,l Spike Recovery 93% 112% 100% 101% 100% 98% 6% 1% 0% 0% 3% 102% 0% 2% 1% 97% 97% 100% 92% 105% 88% 92% 106% 95% 108% 99% 101% 99% 101% 3M Environmental Laboratory Report No. W1872 PFQS_______________ _____________________________THPFOS _______________ N-MeFQSE Alcohol Tim e P o in t Ret Urne ..Area: 6.2 0 Gone. (ng/ml) : 0 %Standard 6.2 17657 62 48588 6.2 87017 6.2 116706 6.2 149347 6.2 194601 2 13 27 37 48 63 (A) 100% 105% 97% 90% 98% 6.2 11457 6.2 0 0 0 Day 0 DayO Day 0 Day 7 Day 7 Day 7 Day 14 Day 14 Day 14 Day 21 Day 21 Day 21 Day 28 Day 28 Day 28 6.2 0.0 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 0.0 6.2 6.2 6.2 6.2 16162 0 13427 13137 8862 8220 12032 11113 16343 13652 0 16288 8544 13507 13263 2 0 1 0 0 0 0 0 1 1 0 1 0 1 0 6.2 0 6.2 113172 6.2 14915 0 35 0 91% Day 35 Day 35 Day 35 Day 42 Day 42 Day 42 Day 49 Day 49 Day 49 6.2 6.2 6.2 6.2 6.2 6J2 62 6.2 6.2 16449 16564 12770 9498 14181 13628 17403 18320 15319 2 2 0 0 1 1 2 2 1 6.2 15463 62 16895 0 0 6.2 22157 4 6.2 55912 15 62 92925 28 6.2 126498 39 6.2 162546 52 6.2 196851 64 Internal Standard quant r2 = 0.995 Curve averaged, Linear,include origin. Calibration range: 12.8-64 ng/ml (A) 118% 111% 103% 99% 100% Ret Time 5.9 Area 0 5.9 430913 5.9 446510 5.9 433489 5.9 43B329 5.9 442757 5.9 448236 5.9 0 5.9 0 5.9 440185 5.9 452518 5.9 442063 5.9 458756 5.9 473828 5.9 445182 5.9 461084 5.9 449074 5.9 473317 5.9 458391 5.9 460771 5.9 459247 5.9 456132 5.9 458997 5.9 464442 5.9 0 5.9 450159 5.9 0 5.9 451843 5.9 462459 5.9 460398 5.9 467646 5.9 453505 5.9 453474 5.9 449375 5.9 437907 5.9 436689 . 5.9 5.9 0 0 5.9 5.9 5.9 5.9 5.9 5.9 Mean S.D. %S.D. 439507 451746 441567 447483 443873 443604 450958 10675 2.4% *'rtC;v.'; RetTme0 8.3 .Area 0 403 8.3 705152 403 8.3 665610 403 8.3 697751 403 8.3 704137 403 8.3 717974 403 8.3 751856 0 8.3 0 0 8.3 0 403 8.3 694734 403 8.3 661592 403 8.3 666969 403 8.3 666079 403 8.3 680123 403 8.3 656395 403 8.3 672829 403 8.3 660257 403 8.3 681695 403 8.3 715527 403 8.3 733086 403 8.3 712998 403 8.3 671926 403 8.3 706016 403 8.3 692615 0 8.3 0 403 8.3 705958 0 8.3 0 403 8.3 672663 403 8.3 695241 403 8.3 704039 403 8.3 700030 403 8.3 685689 403 8.3 7Q1982 403 8.3 716622 403 8.3 691579 403 8.3 711998 0 8.3 0 0 8.3 0 403 8.3 702584 403 8.3 667702 403 8.3 710837 403 8.3 711341 403 8.3 726151 403 8.3 717471 Mean 695600 S.D. 22615 %S.D. 3.3% Cone; 0 316 316 316 316 316 316 0 0 316 316 316 316 316 316 316 316 316 316 316 316 316 316 316 0 316 0 316 316. 316 316 316 316 316 316 316 0 Q 316 316 316 316 316 316 Page 59 of 83 BACK TO MAIN BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Pooled N-EtFOSE Alcohol Data and Slope Regression SUMMARY OUTPUT Regression Statistics Multiple R 0.640148735 R Square 0.409790403 Adjusted R Sq 0.396064598 Standard Erro 0.049834563 O bservations 45 ANOVA R e gression R e sid u a l Total df SS 1 0.074145584 43 0.1067898 44 0.180935383 Intercept X Variable 1 Coefficients Standard Error -0.023015945 0.013609243 -0.002617852 0.000479108 % 2<s S lo pe U ncertainty 37% MS 0,074145584 0.002483484 F Significance F 29.85547405 2 .1 8 8 0 8 E -0 6 tS ta t -1.691199513 -5.464016293 P-vaiue 0.098035439 2 .1 8 8 0 8 E-06 Lower 95% -0.050461581 -0.003584064 Upper 95% 0.00442969 -0.00165164 Lower 95.0% -0.050461581 -0.003584064 Upper 95.0% 0.00442969 -0.00165164 Page 60 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Appendix D: Selected Chromatograms A representative set of chromatograms from the present study is included in this Appendix. Page 61 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 2 of 56 . Data Pile C:\HPCHEM\l\DATA\092899\EtFOS002.D . Sample Name: MeOH Blank Injection Date : 9/28/99 3:10:02 PM Seq. Line : 2 Sample Name : MeOH Blank Vial : 91 Acq. Operator : MTM _ Inj : l Acq. Instrument : Instrument 1 . ' Acq. Method : C:\HPCHEM\1\METH0DS\F0SESIM.M Last changed : 9/28/99 2:49:57 PM by MTM Analysis Method : C:\HPCHEM\l\METHODS\0824_lIS.M Last changed : 9/5/00 8:28:58 AM by kej (Results are from a previously saved Batch) SIM Analysis (ES-) for Et-FQSE-OH, MeFOSE-OH, THPFOS, and PFOS using 4mmx35tnm Dionex IonPac NG1 column, S/N 12879. MTM Page 62 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch. Run # 2 of 55 ' Data File C:\HPCHEM\l\DATA\092899\EtFOS002.D Sample Name : MeOH Blank Internal Standard Report Sorted By : Calib. Data Modified .: Multiplier : Dilution .: Sample ISTD Information: ISTD ISTD Amount Name # ppb {ng/ml Retention Time Tuesday, September 05, 2000 8:28:55 AM 1.0000 1.0000 . 1 402.60000 'THPFOS 2 315.60000 MeFOSE-OH Signal 1: MSD1 427, EIC=426.5:427.5 Signal 2: MSD1 499, EIC=498.5:499.5 Signal 3: MSD1 616, EIC=615;5 :616.5 Signal 4: MSD1 630, EIC=629.5:630.5 RetTime Sig Type [min] 5.940 6.221 8.355 8.586 1 2 3 4 Area - '- Amt/Area ratio '- Amount Grp . Name ppb (ng/ml 11 THPFOS - PFOS - MeFOSE-OH EtFOSE-OH Totals without ISTD(s) : 0.00000 1 Warnings or Errors : . ' .Warning : ISTD compound(s) not found Area Percent Report Sorted By Calib. Data Modified Multiplier Dilution Retention Time Tuesday, September 05, 2000 8:28:56 AM 1.0000 1.0000 Peak RetTime Sig Type # [min] 1 5.940 1 2 6.221 2 3 8.355 3 4. 8.586 4 I I Totals : 1 Warninas or Errors : Area 0.00000 0.00000 0.00000 0.00000 0.00000 Area %' Name 0.0000 THPFOS 0.0000 PFOS 0.0000 MeFOSE-OH 0.0000 EtFOSE-OH Page 63 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 3 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS003, Sample Name: LI 1.5, 155.40 Injection Date 9/28/99 3:28:12 PM Seq. Line : 3 Sample Name LI 1.5, 155.40 Vial : 1 Acg. Operator MTM Inj : 1 Acq. Instrument Instrument 1 . Acq. Method C :\HPCHEM\1\METH0DS\F0SESIM.M Last changed 9/28/99 2:49:57 PM by MTM Analysis Method C:\HPCHEM\1\METHODS\0824_1IS.M Last changed 9/5/00 8:28:58 AM by kej . (Results are from a previously saved Batch) SIM Analysis (ES- ) for Et-FOSE-OH, MeFOSE-OH,' THPFOS, and PFOS using 4mmx35mm Dionex IonPac NG1 column, S/N 12879. MTM "MSDT'S!t6',' EIC=BT5:5":6iy .51D9ZS39\fcTFOSU03.Di"'Alal-t{> Negative 30000 : 40000 30000 20000 10000 - 0 Page 64 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 3 of 56 Data Pile C:\HPCHEM\l\DATA\092899\EtFOS003.D Sample Name: LI 1.5, 155:40 Internai Standard Report Sorted By : Calib. Data Modified : Multiplier ' : Dilution ' Sample ISTD Information: ISTD ISTD Amount Name # ppb (ng/ml Retention Time Tuesday, September 05, 2000 8:28:56 AM 1.0000 . 1.0000 1 402.60000 THPFOS 2 315.60000 MeFOSE-OH Signal 1: MSD1 427, EIC=426.5:427.5 Signal 2: MSD1 499, EIC=498.5:499.5 Signal 3: MSD1 616, EIC=615.5 :616.5 Signal 4: MSD1 630, EIC=629.5:630.5 RetTime Sig Type [min] Area Amt/Area ` Amount Grp Name ratio ppb (ng/ml 5.925 6.207 8.313 8.538 1 PB 2 MM 3 PB 4 PB I 4.65165e5 1.00000 5973.06250 3.07266e-l I 8.80788e5 1.00000 5.05275e5 8.83244e-l 402.60000 1.58847 315.60000 159.90937 THPFOS PFOS MeFOSE-OH EtFOSE-OH Totals without ISTD(s) 161.49784 *** End of Report *** Page 65 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 4 of 56 . Data File C:\HPCHEM\l\DATA\092899\EtFOS004.D ' ' Sample Name: L2 1.5, 310.80 Injection Date : 9/28/99 3:46:24 PM Seq. Line : Sample Name : L2 1.5, 310.80 Vial : Acq. Operator : MTM ' inj : Acq. Instrument : Instrument 1 ' Acq. Method : C:\HPCHEM\l\METHODS\FOSESIM.M Last changed : 9/28/99 2:49:57 PM by MTM Analysis Method : C:\HPCHEM\1\METHODS\0824_1IS.M Last changed : 9/5/00 8:28:58 AM by kej (Results are from a previously saved Batch) SIM Analysis (ES-) for Et-FOSE-OH, MeFOSE-OH, THPFOS, and PFOS using 4mmx35mm Dionex IonPac NG1 column, S/N 12879.i MTM ~MBUfT2 A rb lC ^ 2 g .5 :4 2 /.5 {09Zagg\Ei FaS0Q4.DFA^S~Negatlve-----% TTTJTTTqnm ooooooooo OOOOOQOO Vo 8rt ortW| 8N 5T-i 8 S rjn irju 1 J 11 ijt ------- -----* * w o rn 4yy, tio= ^B .o;4yy.otuy*B yy\fcJhU i>uu4.uii A t-i-ts Negative 1 ' ' 1'0 ' min 3500 3000 2500 2000 1500 1000 500 . i MisUI tjltj, 110 = 6 1 ^ 9 2 Q 9 9 \t I PU55UU4.JJJ API-tS Negative ' : ' . ' O ' min 50000 40000 30000 20000 10000 0- '$ '4 ' 1 Mi01 630, hlU" e29.5:63U.i>(oy^Byy\fci ^ 0 5 0 0 4 . l>j Ah*i-fci$ Negative 60000 . ' _ ' ' ' X 50000 40000 30000 - 20000 10000 n 0 - _________________________________________________________________________________/ i ' '' ' i ' ' ' ' 'a V. ' ' Vo ' min Page 66 of 83 BACK TO MAIN IIIII 3M Environmental Laboratory Report No. W1872 Batch Run # 4 of 56 Data File O:\HPCHEM\l\DATA\092899\EtFOS004.D Sample Name:. L2 1.5, 310.80 Internal Standard Report Sorted By .: Retention Time Calib. Data Modified : Tuesday, September 05, 2000 8:28:56 AM Multiplier : 1.0000 Dilution : 1.0000 Sample ISTD Information: ISTD ISTD Amount Name # ppb (ng/ml ___ I1 j_________ 1 402.60000 THPFOS 2 315.60000 MeFOSE-OH Signal 1: MSD1 427, EIC=426.5 :427.5 Signai 2 : MSD1 499, EIC=498.5 :499.5 Signal 3: MSD1 616, EIC=615.5 :66.5 Signal 4: MSD1 630, EIC=629.5 :630.5 RetTime Sig Type Area Amt/Area Amount Grp Name [min] . ratio ppb (ng/ml 1I _ 1l __ 1__________ j _______ J j_ _______ 5.92 7 1 BV I '4.56303e5 1.00000 ' 402.600001 THPFOS 6.218 2 PB 4.24807e4 3.52850e-l 13.22520 PFOS 8.320 3 BB I 8.73131e5 1.00000 315.60000 MeFOSE-OH 8.545 4 PB 9.57739e5 9.01077e-l 311.93664 EtFOSE-OH Totals 'without ISTD(s) : 325.16184 *** End of Report *** Page 67 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 5 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS005.D Sample Name: L3 1.5, 466.20 Injection Date 9/28/99 4:04:35 PM Seq. Line : 5 Sample Name L3 1.5, 466.20 Vial : 3 Acq. Operator MTM Inj : 1 Acq. Instrument Instrument 1 Acq. Method C :\HPCHEM\1\METH0DS\F0SESIM.M Last changed 9/28/99 2:49:57 PM by MTM Analysis Method C:\HPCHEM\1\METHODS\0824_1IS.M Last changed 9/5/00 8:28:58 AM by kej ' ' ^ 4 (Results are from a previously saved Batch) SIM Analysis (ES-) for Et-FOSE-OH, MeFOSE-OH, THPFOS, and PFOS using 4mmx35mm Dionex lonPac NG1 column, S/N 12879. MTM ~MS01 427,T=IC=426.fa:42/.fa (UBiaBMb ri-USTO5.UP^reS'Neptlve- 40000 ; 35000 -j 30000J 25000 -i 20000-j 15000 10000J 5000- 0-j- 7~ > ' ' ' 4 ' : f ~H SD T409, BIC=iytJ.5:4y9y{09289tJM: rFOSOCOTJAPl-ta Negative 7000 H 6000 4 5000 4000 ' 3000 20004 1000- Tv)SD`rBTBrETCHST53:6Te^92a^1ETFaSO T5XrrAPFESn 5) 10 50000 40000 \ 30000 4 20000 10000- _03lC ' MSLH B30,'t;IC=5Z3.5:'B3Cnr(D923g91ETFOS005.L)) 'Pi-fca Negative 80000J I70000 -I60000 50000i 40000J 30000J |20000 10000 4 0-t I T juas Page 68 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 5 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS005.D .. Sample Name: L3 1.5, 466.20 Internal Standard Report Sorted By Calib. Data Modified Multiplier Dilution Sample ISTD Information: ISTD ISTD Amount Name # ppb (ng/ml Retention Time Tuesday, September 05, 2000 8:28:56 AM 1.0000 1.0000 >r 1 402.60000 THPFOS 2 315.60000 MeFOSE-OH Signal 1: MSD1 427, EIC=426.5 :427.5 signal 2: MSD1 499, EIC=4.98.5 :499.5 Signal 3: MSD1 616, EIC=615.5 :616.5 Signal 4: MSD1 630, EIC=629.5 :630.5. RetTime Sig Type . Area [min] Amt/Area Amount Grp Name ratio ppb (ng/ml 5.928 6.217 8.322 8.546 1 BB 2 BB 3 PB 4 PV I 4.47867e5 8.87226e4 I 8.68287e5 1.39693e6 1.00000 3.56716e-l 1.00000 9.07298e-l 402.60000 28.44993 315.60000 460.67730 THPFOS PFOS MeFOSE-OH EtFOSE-OH Totals without ISTD(s) 489.12723 *** End of Report *** Page 69 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 6 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS006.D Sample Name: L4 1..5, 621.60 Injection Date 9/28/99 4:22:47 PM Seq. Line : 6 Sample Name L4 1.5, 621.60 Vial : 4 Acq. Operator MTM Inj : 1 Acq. Instrument Instrument 1 ' Acq. Method C:\HPCHEM\l\MBTHODS\FOSESIM.M Last changed 9/28/99 2:49:57 PM by MTM Analysis Method Last changed C :\HPCHEM\1\METHODS\0824_11S.M 9/5/00 8:28:58 AM by kej (Results are from a previously saved Batch) V#M**/ I SIM Analysis (ES-> for Et-FOSE-OH, MeFOSE-OH, THPFOS, and PFOS using 4mmx35mm Dionex lonPac NG1 column, S/N 12879. MTM MSU1 4 2 /, fci0=4^tj.b:42/.b (UiteS99\t 11-OSUOij.uj 4000035000-i 30000 -i 25000 20000 \ 1500010000^ 5000- Negative h ' ' ' T" nasm 499. blC^9B3T4^ 1 P g 2S99'[ETFO'SgOK:U) 'AFir-ESTIegairve~ 8000 6000 4000 2000- 1 ' 'T TflSDT 616,^IC=tri5:t:6153'(OS23S9U;,rFOiSOOB.DJ- API::ESrNegWr 1800 1600 1400 -i 1200 1000-i 800600-i 400 -i 200 4 ? 1 1 "J raSDr630,HIC=629.5:630.5 (0328530; rFDS006.D)'AR-tSTlgative' 100000 80000 60000 40000 20000 - 0- 10_____ min 1.0 -miri 10 _mio Page 70 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 6 of 56 ' Data File C:\HPCHEM\l\DATA\092899\EtFOS006.D Sample Name: L4 1.5, 621.60 . Internal Standard Report s 3 s s s a s = 3 s & s a 8 s a B B B B e = a s = s s s s ; = a s s ' s 8 B n t s s a s B s s s s s n s B s 's a s s B s iS T s s s s s s s B s s B B s Sorted By : Calib. Data Modified : Multiplier : Dilution : Sample ISTD Information: ISTD ISTD Amount Name # ppb (ng/ml ___ I 1______ Retention Time Tuesday, September 05, 2000 8:28:56 AM 1,0000 1.0000 . 1 402.60000 'THPFOS 2 315.60000 MeFOSE -OH Signal 1: MSDl 427, EIC=426.5:427.5 Signal 2: MSDl 499, EIC=498.5:499.5 Signal 3: MSDl 616, EIC=615.5 :616.5 Signal 4: MSDl 630, 'EIC=629.5:630.5 RetTime Sig Type [min] Area Amt/Area Amount Grp Name ratio ppb (ng/ml 5.926 6.215 8.534 8.546 r BB 2 VB 3 BB 4 PP I 4.5181165 1.120.72e5 I 3.00592e4 1.86971e6 1.00000 402.60000 3.57406e-l 35.69254 1.00000 315.60000 9.20283e-l 1.80657e4 THPFOS , PFOS MeFOSE-OH EtFOSE-OH Totals without ISTD(s)' : ... 1.81014e4 *** End of Report *** Page 71 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 7 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS007.D Sample Name: L5 1.5, 777.00 Injection Date 9/28/99 4:41:01 PM Seq. Line : 7 Sample Name Acq. Operator L5 1.5, 777.00 MTM ' Vial : 5 Inj : 1 Acq. Instrument Instrument 1 Acq. Method Last changed Analysis Method C:\HPCHEM\l\METHODS\FOSESIM.M 9/28/99 2:49:57 PM by MTM ' C :\HPCHEM\1\METHODS\0824_1IS.M . Last changed 9/5/00 8:28:58 AM by kej (Results are from a previously saved Batch) SIM Analysis (ES-) for Et-FOSE-OH, MeFOSE-OH,.THPFOS, and PFOS using 4mmx35mm Dionex IonPac NG1 column, S/N 12879. MTM 1 ' 1' ' 4 -wsm 4 iWrEIC>498.5:498^ IJgZBgS^ETFOBCO/.Dl'APl^ESTlegatlve ' 14000 12000 10000 8000 6000 4000 4 2000 0 ''5' ' 'I ' ' ' TOSDT6167"EIC=B16.5:616l5(092899\fc I l-,OS0U7.TJ) APl-ESNegawe soooo40000 - 30000 20000 - 10000 --- '-- ' i ' l -w sc rrta u. hlC=B2a.S:630.fa'(0tf^ S9\ETFOS007.D>~A'PI-ES'Nle9a1lv 140000 120000 100000 80000 60000 40000 mic 1 9......-.mic 10 ...miq Page 72 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 7 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS007.D Sample Name: L5 1.5, 777.00 =S3S=S8SSSS:S; Internal Standard Report Sorted By : Calib. Data Modified : Multiplier : Dilution : Sample ISTD Information: ISTD ISTD Amount Name # ppb (ng/ml Retention Time Tuesday, September 05, 2000 8:28:56 AM 1.0000 1.0000 1 402.60000 THPFOS 2 315.60000 MeFOSE-OH Signal 1: MSD1 427, EIC=426.5:427.5 Signal 2: MSD1 499, EIC=498.5:499.5 Signal 3: MSD1616, EIC=615.5 :616.5 Signal 4: MSD1 630, EIC=629.5:630.5 RetTime Sig Type Area [min] 1__ I______ 1_________ 5.940 6.213 8.318 8.544 1 2 BB 3 PB 4 PB 1.67565e5 I 8.56724e5 2.34711e6 Amt/Area Amount Grp Name ratio ppb (ng/ml 1 -----11 1_ J___________ ' THPFOS' 0.00000 0.00000 PFOS 1.00000 315.60000 MeFOSE-OH 9.12800e-l 789.23438 EtFOSE-OH Totals 'without ISTD(s) : 789.23438 2 Warnings or Errors : . Warning : ISTD compound(s) not found Warning : Negative results set to zero (cal. curve intercept), (PFOS) *** End of Report *** Page 73 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 8 of 56 .' Data File C:\HPCHEM\l\DATA\092899\EtFOS008.D Sample Name: L6 1.5, 932.40 Injection Date : 9/28/99 4:59:12 PM Seq. Line : Sample Name : L6 1.5, 932.40 Vial ; Acq. Operator : MTM Inj : Acq. Instrument : Instrument 1 Acq. Method : C:\HPCHEM\1\METH0DS\F0SESIM.M Last changed : 9/28/99 2:49:57 PM by MTM Analysis Method .: C:\HPCHEM\1\METHODS\0824_1IS.M' Last changed : 9/5/00 8:28:58 AM by kej {Results are from a previously saved Batch) SIM Analysis (ES-) for Et-FOSE-OH, MeFOSE-OH, THPFOS, and PFOS using 4mmx35mm Dionex IonPac NG1 column, S/N 12879. i MTM "M SDi'427; ETC=426.H:42ra"(U92B99,i: IVO60o8.O) A P l-ts Negative 40000 i 35000 \ 30000- 25000J 20000J 15000J 10000-; 5000 - ~i ^ I MSDT"499, Klt34S875:4SSjb1092fS91HTFOsoy8.iJJ AKi-tS Negative 18000 16000- 14000-i 1200010000-j 8000 6000- 4000^ 2000-i 0- i r'i BIS01'b'T8,'HfC=6T5^:8153"(US2899\ETFOSOO8.U) AHI-bS Negativa 10 10 50000 40000 \ 30000 20000 -j 10000- 14 TVSDTS30, tiC=t2a.5:t3tT5IO923S91FrF0S'ffua.L)) AHi-tB Negative 160000H 140000^ 120000-j 100000-i 80000-i 60000 -j 40000 - 20000-j 0- lb mir -mio Page 74 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 8 of 56 Data Pile C:\HPCHEM\l\DATA\092899\EtFOS008.D Internal Standard Report Sample Name: L6 1.5, 932.40 \. Sorted By : Calib. Data Modified : Multiplier : Dilution : Sample ISTD Information: ISTD ISTD Amount Name # ppb (ng/ml Retention Time Tuesday, September 05, 2000 8:28:56 AM 1.0000 1.0000 1 402.6000 THPFOS 2 315.60000 MeFOSE-OH signal 1: MSD1 427, EIC=426.5:427.5 Signal 2: MSD1 499, EIC=498.5:499.5 Signal 3: MSD1 616, EIC=615.5: 616.5 Signal 4: MSD1 630, EIC=629.5 :630.5 RetTime S'ig Type [min] Area Amt/Area Amount Grp Name . ratio ppb {ng/ml 5.927 6.215 8.323 8.546 1 BB 2 VB 3 PB 4 BV I 4.60976e5 2.10524e5 I 8.87024e5 2 . 91155e6 1.00000 3.58656e-l 1.00000 9.14094e-l 402.60000 65.94394 315.60000 946.92850 THPFOS PFOS MeFOSE-OH EtFOSE-OH Totals without ISTD{s) : ' 1012.87244 *** End of Report *** BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 9 of 56 . Data File C:\HPCHEM\l\DATA\092899\EtFOS009.D Sample Name: MeOH Blank Injection Date : 9/28/99 5:17:26 PM Seq. Line : 9 Sample Name : MeOH Blank Vial : 91 Acq. Operator : MTM Inj : 1 Acq. Instrument : Instrument 1 Acq. Method : C:\HPCHEM\1\METH0DS\F0SESIM.M ' Last changed : 9/28/99 2:49:57 PM by MTM Analysis Method : C:\HPCHEM\1\METHODS\0824_1IS.M Last changed : 9/5/00 8:28:58 AM by kej . (Results are from a previously saved Batch) SIM Analysis (ES-) for Bt-FOSE-OH, MeFOSE-OH, ,THPFOS, and PFOS using 4mmx35mm Dionex IonPac NG1 column, S/N 12879. . Page 76 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 9 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS009.D Sample Name: MeOH Blank Internal Standard Report Sorted By : Calib. Data Modified : Multiplier :' Dilution : Sample ISTD Information: ISTD ISTD Amount Name # ppb (ng/ml . Retention Time Tuesday, September 05, 2000 8:28:56 AM 1.0000 . 1.0000 1 402.60000 THPFOS 2 315.60000 MeFOSE-OH Signal 1: MSD1 427, EIC=426.5:427.5 Signal 2: MSD1 499, EIC=498.5:499.5 Signal 3: MSD1 616, EIC=615.5 :616.5 Signal 4: MSD1 630, EIC=629.5:630.5 RetTime Sig Type [min] Area Amt/Area Amount Grp Name ratio ppb (ng/ml 5.940 6.221 8.355 8.586 1 2 3 4 THPFOS PFOS MeFOSE-OH EtFOSE-OH Totals without ISTD(s) : ' 0.00000 1 Warnings or Errors : Warning : ISTD compound(s) not found Area Percent Report Sorted By Calib. Data Modified Multiplier Dilution Retention Time Tuesday, September 05, 2000 8:28:56 AM 1.0000 1.0000 Peak RetTime Sig Type Area Area Name # [min] % 11 ____ I11__ I1______ |1_ ______ __ 1._______ 1 ____ __ 1 5.940 1 I o. ooooo' 0.0000 THPFOS 2 6.221 2 0.00000 0.0000 PFOS 3 8.355 . 3 I 0.00000 0.0000 MeFOSE-OH 4 8..586 4 0.00000 0.0000 EtFOSE-OH Totals : 0.00000 1 W a m in a s o r E r r o r s : Page 77 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 2 3 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS023.D Sample Name:. EFA-073 Injection Date 9/28/99 9:32:40 PM Seq. Line : 23 Sample Name EFA-073 Vial : 23 Acq. Operator MTM Inj : 1 ,Acq. Instrument Instrument 1 Acq. Method C:\HPCHEM\1\METH0DS\F0SESIM.M Last changed 9/28/99 2:49:57 PM by MTM Analysis Method C :\HPCHEM\l\METHODS\0824_IIS.M Last changed 9/5/00 8:28:58 AM by kej (Results are from a previously saved Batch) SIM Analysis (ES-) for Et-FOSE-OH, MeFOSE-OH, THPFOS, and PFOS using 4mmx35mm Dionex IonPac NG1 column, S/N 12879. MTM fasci 42/, 11u=4^::42V.5(O^s^TFC'Suz^) APi-^SNegative 40000-j 350002 30000-i 25000J 20000 150004 100002 SS 5000- 02 . .i 5 1 j r~~~ 1WSU1499, tl0=498.5:499.0(Uy2899\bH-US023.U) AP1-LSNegativa t 10 mir 900- 8002 7002 ' 6002 5002 4002 3002 i ' 4 TSSSETTBIB,tic=ei5.5:616.5{0928ay\fclrOoU23.U) AHl-ts Negative _____________i - ..... mir 50000 40000 30000 fei 20000 10000 0ma'l 830',"EIC='629;6i:630.b''(0928S'9\ETfOd234.uJ AKi-ts Negative s-- -- -- -- r aoooo70000 60000 50000 40000 30000 20000 10000 0- ' ' ' 2 ' ' 4 ' ' ` . ' 8n 10 min Page 78 of 83 BACK TO MAIN KKIIIk 3M Environmental Laboratory Report No. W1872 Batch Run # 23 of 56 . Data File C:\HPCHEM\l\DATA\092899\EtFOS023.D . Sample Name: EFA-073 Internal Standard Report . Sorted By : Calib. Data Modified Multiplier : Dilution. : Sample ISTD Information: ISTD ISTD Amount Name # ppb (ng/ml Retention Time Tuesday, September 05 1.0000 1.0000 2000 8:28:56 AM 1 402.60000 THPFOS 2 315.60000 MeFOSE-OH Signal 1: MSD1 427, EIC=426.5:427.5 Signal 2: MSD1 499, EIC=498.5:499.5 Signal 3: MSD1 616, EIC=615.5:616.5 Signal 4: MSD1 630, EIC=629.5:630.5 RetTime Sig Type [min] . ' Area 5.926 6.221 8.326 8.550 1 BB 2 3 VB 4 BB I 4.64774e5 - I 8.48397e5 1.33227e6 Amt/Area Amount Grp Name ratio ppb (ng/ml 1.00000 402.60000 1.00000 315.60000 9.0697le-l 449.49185 THPFOS. PFOS MeFOSE-OH EtFOSE-OH Totals without ISTD(s) 449.49185 1' Warnings or Errors : . . Warning : Calibrated compound(s) not found *** End of Report *** Page 79 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 24 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS024.D Sample Name: EFA-074 Injection Date 9/28/99 9:50:54 PM Seq. Line 24 Sample Name EFA-074 ' Vial 24 Acq. Operator MTM Inj 1 A c q . Inst rument Instrument 1 Acq. Method C:\HPCHEM\1\METHODS\FOSESIM.M Last changed 9/28/99 2:49:57 PM by MTM Analysis Method C :\HPCHEM\1\METHODS\0824_1IS.M Last changed 9/5/00 8:28:58 AM by kej (Results are from a previously saved Batch) SIM Analysis (ES-) for Et-FOSE-OH, MeFOSE-OH, THPFOS, and PFOS using 4mmx35mm Dionex IonPac NG1 column, S/N 12879. MTM Page 80 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 Batch Run # 24 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS024.D Sample Name: EFA-074 Internal Standard Report Sorted By : Calib. Data Modified : Multiplier ' : Dilution ' : Sample ISTD Information: ISTD ISTD Amount Name # ppb (ng/ml Retention Time Tuesday, September 05, 2000 8:28:56 AM 1.0000 1.0000 1 402.60000- THPFOS 2 315.60000 MeFOSE-OH Signal 1: MSD1 427, EIC=426.5:427.5 Signal 2: MSD1 499, EIC=498.5:499.5 Signal 3: MSD1 616, EIC=615.5 :616.5 Signal 4: MSD1 630,1 EIC=629.5:630.5 RetTime Sig Type Area Amt/Area Amount Grp Name [min] ratio ppb (ng/ml __ '____I1-- 11______ 1 ____ 1____ 1______ __ 1---------- !|__jJ__________. 5.925 1 BB I 4.56350e5 1.00000 402.60000 THPFOS 6.221 2 - . - - PFOS. 8.329 3 BB I 8.55992e5 1.00000 315.60000 . MeFOSE-OH 8.555 4 PB 1.28265e6 9.06316e-l 428.60235 EtFOSE-OH Totals without ISTD(s) 428.60235 1 Warnings.or Errors : Warning : Calibrated compound(s) not found *** End of Report *** Page 81 of 83 BACK TO MAIN 3M Environmental Laboratory Report No. W1872 itch Run # 25 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS025.D Sample Name: EFA-075 Injection Date 9/28/99 10:09:06 PM Seq. Line : 25 Sample Name EFA-075 Vial : 25 Acq. Operator MTM . Inj : 1 Acq. Instrument Instrument 1 Acq. Method C :\HPCHEM\1\METHODS\FOSESIM.M Last changed 9/28/99 2:49:57 PM by MTM Analysis Method C:\HPCHEM\1\METHODS\0824_1IS.M Last changed 9/5/00 8:28:58 AM by kej % (Results are from a previously saved Batch) SIM Analysis (ES-) for Et-FOSE-OH, MeFOSE-OH, THPFOS, and PFOS using 4mmx35mm Dionex IonPac NG1 column, S/N 12879. MTM "Risen 427, IC=426.5:42/.S (09289S4:1 l-OS(K!b.L>) API-fcTfNegative 40000 -I 35000 ] 30000- 25000 -i 20000\ 15000 -i 10000 i ' 5000 \ Oh 'S-- .-- , . J .-- -- -- l MSDl 4ya'rH C ^B li3S S ;3"((fS 2ea9\t l HS02&.U) AH-EiTNegative...... 10 JWE 1 - r "TOSDTBTb, hlC=6l5.5T5T(S.5 (US2B9SAfc I l-USOZb.UJ AHI-ES Negative 50000 -j 40000 30000 20000 10000- oJ1 1' 'T " MSOT 530, ElC=S29'.'5IB303T Og2899\ETFDS02S;D I703l-ES'NeigaSve'~ 120000 - 100000- 80000 60000 40000 20000 - 10 min -19....mia Page 82 of 83 BACK TO MAIN IIIII 3M Environmental Laboratory Report No. W1872 Batch Run # 25 of 56 Data File C:\HPCHEM\l\DATA\092899\EtFOS025.D Sample Name: EFA-075 . Internal Standard Report Sorted By : Calib. Data Modified : Multiplier : Dilution : Sample ISTD Information: ISTD ISTD Amount Name # ppb (ng/ml Retention Time Tuesday, September 05, 2000 8:28:56 AM 1.0000 1.0000 1 402.60000 THPFOS 2 315.60000 . MeFOSE-OH Signal 1: MSD1 427, EIC=426.5 :427.5 Signal 2: MSD1 499, EIC=498.5 :499.5 Signal 3: MSD1 616, EIC=615.5 :616.5 Signal 4: MSD1 630, EIC=629.5:630.5 RetTime Sxg Type [min] Area Amt/Area Amount Grp Name ratio ppb (ng/ml 5.923 6.221 8.332 8.559 1 BB 2 3 PB 4 MM I 4.64731e5 I 8.46072e5 1.80524e6 1.00000 1.00000 9.10577e-l 402.60000 315.60000 613.16914 THPFOS PFOS MeFOSE-OH EtFOSE-OH Totals without ISTD(s) 613.16914 1 Warnings or Errors : Warning : Calibrated compound(s) not found *** End of Report *** Page 83 of 83