Document 4aMBmk09G9zGrzxqMMb7wNm1N

BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Study Title Hydrolysis Reactions of Perfluorooctanoic Acid (PFOA) Data Requirement: Based on OPPTS: 835.2110 Author Thomas L. Hatfield, Ph.D. Study Completion Date March 30,2001 Performing Laboratory 3M Environmental Laboratory Building 2-3E-09,935 Bush Avenue St. Paul, MN 55106 Project /dentification 3M Laboratory Report No: E00-1851 Total Number of Pages 99 Page 1 of 99 ~ ~~ BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 This page has been reserved for specific country requirements. Page 2 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Statement of Non-Compliance Study Title: Hydrolysis Reactionsof PerfluorooctanoicAcid (PFOA) Study Identification Number: E00-1851 This study does not fully comply with the requirements of the US EPA Good Laboratory Practices (GLP) Standards at 40 CFR Part 792 (TSCA). However, many GLP standards were used in the development of the analytical method (Appendix A), and many of the quality assurance procedures followed in this study were based on the practices described in the GLP documentation. Sbonsor Representative Date Page 3 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Quality Assurance Statement Study Title: HydrolysisReactions of PerfluorooctanoicAcid (PFOA) Study Identification Number: E00-1851 The following table provides details of the audits performed by the 3M Environmental Laboratory Quality Assurance Unit (QAU). Inspection Dates I I I II I 3/2/01 I I I I I 3/26-30/01 Phase Data and Draft Report Date Reported to Management Study Director 3/2/01 3/2/01 Data and Draft Report 3/30/01 3/30/01 QAU Representatid 3/30/0, ' Datd Page 4 of 99 ~ ~~~ BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Table of Contents Statement of Non-Compliance ............................................................................................ 3 Quality Assurance Statement.............................................................................................. 4 List of Tables ........................................................................................................................ 6 List of Figures....................................................................................................................... 6 Study Personneland Contributors....................................................................................... 6 Location of Archives............................................................................................................. 7 Summary.............................................................................................................................. 8 Introduction .......................................................................................................................... 9 Summary of Kinetics Model............................................................................................... 10 Materialsand Methods....................................................................................................... 11 Chemical Characterizations.......................................................................................... 11 Sample Preparation ...................................................................................................... 11 Sample Analysis............................................................................................................ 12 Deviations...................................................................................................................... 12 Results and Discussion ..................................................................................................... 13 Data Quality Objectives (DQO's).................................................................................. 13 Anomalous Analytical Results....................................................................................... 13 Statistical Methods and Calculations ............................................................................ 14 Data Summary and Discussion..................................................................................... 14 Conclusions........................................................................................................................ 18 References......................................................................................................................... 19 Signatures .......................................................................................................................... 20 Appendix A: Analytical Method.......................................................................................... 21 Appendix B: Kinetics Model............................................................................................... 38 Appendix C:Selected Analytical and Kinetics Results ..................................................... 48 Appendix D: Selected Chromatograms............................................................................. 71 Page 5 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 List of Tables Table 1. Summary of Results Based on PFOA Concentrations ........................................ 8 Table 2. Summary of Results Based on the Mean and Precision of PFOA Measurements ..................................................................................................... .8 Table 3. Characterizations of Test and Reference Substances ...................................... 11 Table 4. Observed (50" C) Degradation Rates of PFOA in Aqueous Buffered Solutions and at Various pH Levels.................................................................................... 15 Table 5. Degradation Rate and Half Life of PFOA in Aqueous Buffered Solutions Using Data Pooled Over pH Levels 5.0, 7.0, and 9.0 ................................................... 15 Table 6. Degradation Rate and Half Life of PFOA in Aqueous Buffered Solutions Based on the Concentration Mean and Standard Deviation ......................................... 17 List of Figures Figure 1. Structure of the Ammonium Salt of PFOA.......................................................... 9 Figure 2. Observed PFOA Degradation for Various pH levels. ....................................... 14 Figure 3. Pooled (pH = 5.0, 7.0, and 9.0) PFOA Data and Slope Regression................16 Study Personnel and Contributors Study Director Sponsor Thomas L. Hattield, Ph.D. 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 (651) 778-7863 3M Corporation 3M Environmental Laboratory and Professional Services Contributing Personnel Debra Wright Jan Schultz Joseph J. S. Tokos, Ph.D. (Pace Analytical Services, Inc., 1700 Elm St., Minneapolis, MN 55144) Jill Maloney Karen Johnson (Braun lntertec Corporation, 6875 Washington Ave. South, Minneapolis, MN 55439) Grant M. Plummer, Ph.D. (Rho Squared, P.O. Box 61536, Durham, NC 27715) Page 6 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Location of Archives The 3M Environmental Laboratory will retain the original data documents and digital copies of the original data related to this work for at least 10 years following the effective date of any related final ruling. Information may be obtained through written inquiry addressed as follows: 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Page 7 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Summary We report here the results of our study of the hydrolysisof perfluorooctanoicacid (hereafter, PFOA). Our methods are described below and in Appendix A to this work; our results are based on the observed concentrations of PFOA in buffered aqueous solutions as a function of time. 3M's Environmental Laboratory staff developed the study procedures:they are based on EPAs OPPTS Guideline Document 835.21I O ' but do not fulfill all the requirements of the guideline. Our methods are described below and in Appendix A to this work; our results are based on the observed concentrations of PFOA in buffered aqueous solutions as a function of time. The chosen analyticaltechnique was high performanceliquid chromatography with mass spectrometry detection (HPLC/MS). Table 1 summarizes the results of the study. During this study, we prepared and examined samples at six different pH levels from 1.5 to 11.O over a period of 109 days, and our results indicate no dependence of the degradation rate of PFOA on the sample pH level. Our results based on the PFOA concentrations, pooled over three pH of the six levels (5.0, 7.0, and 9.0), are presented in Tables 1 and 2. Observed Rate Constant at 50" C (day-') 8.1 x IO-' Calculated Rate Constant at 25" C (day''') 8.1 x Calculated Half Life at 250 (years) 235 Calculated (20) Minimum Half Life at 25" C (years) 92 The mean value and precision of PFOA concentration measurements provide a second estimate of t,he PFOA half-life, presented in Table 2. I I I 1 Table 2. Summary of Results Basedon the Mean and Precision of PFOA Measurements Maximum Possible Rate at 50C -4 Maximum Calculated Rate at 25" C Calculated Half Life at 25C (day") (day') (years) 2.0 x 10 2.0 x 10 2 97 Page 8 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Introduction Three primary chemical routes of environmental degradation are hydrolysis, photolysis, and biodegradation. Studies of these routes provide information on the environmental persistence of both the "parent" compounds and their reaction products, and are ideally carried out over the range of chemical conditions pertinent to both environmental and metabolic processes. The hydrolysis of PFOA (or, more generally, its degradation in the presence of bo) is addressed in this report. The structure of the ammonium salt of the PFOA is illustrated in Figure 1. This is the actual test material used in the study. Figure 1. Structure of the Ammonium Salt of PFOA PFOA H H-A+I -H H Page 9 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Summary of Kinetics Model A full mathematicaldescriptionof the kinetics model employed in this study is presented in Appendix 6. The study data allow two independent estimates of the hydrolytic half-life of PFOA. The first estimate (see Table 1) is based on the observed degradation of the "parent" (?vi), compound PFOA in dilute, appropriately buffered aqueous solutions. Equation 1 describes the estimated half-life in terms of the estimated total parent hydrolysis rate i p(see Appendix 8,Equation BIO): Eq. 1 We determinedthe quantity cpfrom the experimental data as described in Appendix B. To determine the relevant concentration ratios at each pH level (see Equations B8 and B9),we used either the data correspondingto "Day 0" (t = 0) or the earliest available data achieving the data quality objectives of the analytical method. A second half-life estimate (see Equation B37) is available from the mean p and standard deviation CJ of the observed PFOA concentrations, assuming that they were essentially constant over the experimental portion of the study. This estimate is Eq. 2 where A t represents the sample incubation period. All the samples used in this study were maintained at a reaction temperature of 50" (k3") C. The quoted results, valid for the reaction temperature 25" C, were estimated from our experimental results according to methods described in Appendix B (Eqs. B38 and B39). Page 10 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Materials and Methods Details of the characteristics of the test materials, sample preparation techniques, and analytical methods are presented in Appendix A (ETS-8-212.0, "Preparation of PerfluorooctanoicAcid (PFOA) Hydrolysis Samples in BufferedSolutions and Analysis by High Performance Liquid Chromatographywith Mass Spectrometry Detection.") A summary of these items is provided below, as well as a description the known deviations from the procedures of Appendix A. 3M prepared and analyzed the samples included in this study between June 15 and November 12,2000. Chemical Characterizations 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 quantitativestandards used to quantify them. For this reason, and because the related calculations involve only ratios of the compound concentrations (see Appendix B, Equations 88 and B36), the resulting rate and half-life estimates are largely independent of the material purity levels. Table 3. Characterizationsof Test and ReferenceSubstances II Source I I PFOA(Ammonium Salt) P I I 3M ICPlPCP Division PFBS (Ammonium salt) I 3M Specialty Chemicals-] Chemical Lot Numbe? TCR-00930-30, Lot 332 TCR-99030-28, Lot 101 Physical Description White powder White powder Molecular Weight (gm mole-') 431 317 A perfluorobutanesulfonate Sample Preparation We prepared four 5.0-mL aqueous buffer samples (a sample, a duplicate, a triplicate, and a "matrix spike") at each of six pH levels (1.5, 3, 5, 7, 9 and 11) for analysis at eight time intervals (0, 7, 14, 28,42, 64, 84 and 109 days). Buffered solutions containing 5154 ng/mL of the analyte PFOA formed the basis of all these samples. The chosen buffer solutions are described fully in Appendix A. All the samples were prepared simultaneously, and all but the "Day 0 samples were placed in an incubator/orbital shaker maintained at 50"(+ 3")C. One of the "Day 0 samples and a blank were spiked with the PFOA solution, diluted 7:l with methanol containingthe internal standard perfluorobutanesulfonate(PFBS) and frozen. The resulting PFBS concentration in all these samples was 158 ng/ml; the resulting PFOA concentration in the spiked samples was 143 ng/ml above the original sample concentratian. After the appropriate incubationtimes, subsets of the sample vials were removed from the incubator and then spiked (as required), diluted, and frozen as Page 11 of 99 BACK TO MAIN 3M EnvironmentalLaboratoryReport No. E00-1851 described immediately above. Except during the relatively short periods of time required to prepare them, the samples were shielded from light. Nine calibration standards containing PFOA (25 to 999 ng/ml) and PFBS served as the quantitative basis of the study. All these standards were prepared in 1.5 mL of the appropriate pH buffer solution and 8.5 mL of methanol. Sample Analysis The equipment we used for the HPLC/MS analysis was a Hewlett Packard model 1100 equipped with a Dionex lonPac@NG-1 HPLC column (aqueous ammonium acetate/methanolsolvent gradient) and an ALS Model G I322A degassing module. An ALS Model G1316A column heater maintainedthe column temperature at 40C, a quaternary pump supplied a column flow rate of 0.3 mumin, and an ALS Model G1313A auto-sampler provided 10 pL sample injections. The detector was a Hewlett Packard MSD mass spectrometer, operated in negative-mode electrospray ionization mode; the anions of PFBS and PFOA were detected at the mass-to-charge(m/z) ratios 299 and 413, respectively. We processedthe resultingdata using the computer program Target@NT Genie Integrator. Further analytical details, including the gradient elution program, instrument and detector parameters, and performancespecifications, are presented in Appendix A. Deviations No deviations from the proceduresdefined in the analytical method (AppendixA) were noted during the study. All calibration and sample results that failed to meet the data quality objectives of the method (and were excluded from further analysis) are noted in the following sections. Page 12 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Results and Discussion DataQualiiObjectives (DQO's) We briefly describe the data quality objectives applied in this study below. Appendix A describes them in greater detail. With the exceptions of the anomalous results noted below, all the DQO's were met. Appendix C presents the results for each sample set, organized by pH level. Calibrations. The minimum acceptable coefficient of determination (P) for linear fits to calibration data is 0,990. The acceptance criterion for individual calibration points is that their values fall within & 25% of the linear fit value; data outside this range are excluded and the linear fit is recalculated. Data for the high or low calibration standards may be rejected, though this results in a smaller effective calibration range. The average results of calibrations performed before and after the analytical procedures are used to calculate the analyte concentrations. Continuing Calibration Verification (CCV). Selected calibration samples are examined at the beginning of, during, and at the end of each analytical procedure. The results may not deviate by more than k 25% of the known values. Sample Spikes. The acceptable percent spike recovery range is 70% to 130%; recoveries outside this range % place the analysis out of control, and require intervention by the Team Leader or designee. Analyte specificity is demonstrated by acceptable analyte spike recoveries. Identically Prepared Samples. Triplicate sample results with relative standard deviations (RSDs) greater than 25% place the analysis out of control, and require intervention by the Team Leader or designee. Solvent Blanks. Concentration results for solvent blanksmust exceed neither 5% of the highest calibration standard nor 25% of the lowest calibration level. System Suitability. Suitability was demonstrated by either an abbreviated mass-tocharge (m/z) check-tune or performance of a full auto-tune routine. Anomalous Analytical Results With the following exceptions, our analytical results met or exceeded the data quality objectives of` Appendix A. Spike Recoveries. Results for five of the eight sample triplicates for pH = 3.0 failed to meet `this data quality objective. Least squares determinations of a slope and offset from the three remaining data points at this pH would be highly undetermined, so we have excluded all the pH = 3.0 data from further consideration. Similarly, results for seven of the eight sample triplicates for pH = 11.Ofailed to meet this data quality objective. No least squares determinations of a slope are possible in this case, so we have excluded all the pH = 11.O data from further consideration. Finally, the "Day 14" samples at pH = 1.5 (061500-PFOA-075through 061500PFOA-078) failed to meet this spike recovery data quality objective, and we have excluded these data from the following rate and half-life estimates. Page 13 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Statistical Methods and Calculations Using functions provided in Microsoft@Exce@ l ' software, we calculated means, standard deviations, and first-order rate constants (see Appendix B, Equation 88) for various subsets of the acquired data. Our linear regrdssions included the determination of constant terms, that is, we did not force the regression fits to pass through the origin. As described in Appendix B (Equations 838 and B39), rates measured at 50C were extrapolated to 25C by dividing by a factor of 10; this approximation is valid for reactions with Arrhenius heats of activation near 18 Kcal/mole.2 Data Summaryand Discussion The LOQ is defined as the concentration of the lowest (accepted) standard in the calibration set for which the known concentration exceeds 400% of the indicated solvent blank level (see Appendix A). During this study, the LOQ for PFOAwas 25 ng/mL. Results for the internal standard (PFBS) were very consistent throughout the study. The percent relative standard deviations of the measured values, calculated for each of the four pH levels discussed here (1.5, 5.0, 7.0, and 9.0), ranged from 1 to 2%. Figure 2 illustrates the concentration ratios for the four pH levels versus time. Table 4 presents the results of the 50C rate determinations based on these data. Figure 2. Observed PFOA Degradationfor Various pH levels. 0.04 1 -"----I -0.12 -0.14 -0.16 -1 0 -. f.- _ _ 4 1 20 . -.._.: .- I *-- . 1 a I I 40 60 80 Time (days) 1 100 120 Page 14 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 PH Observed Slope (day-') Percent (20) Slope Uncertainty (day') 1.5 1.7 x 597 5.0 -1.5 x 76 7.0 1.8~ 664 9.0 -1.1 x 244 I I The slopes in Table 4 are small in magnitude, of varying sign, and only poorly determined; their percent relative 2ts (95% confidence) uncertainties range from 76% to 664%. The data do not indicate degradation of PFOA at any of the four pH levels. In the absence of a clear trend relating the degradation rate to sample pH, it is appropriate to "pool" the data from all pH levels and to determine the degradation rate using the entire data set. The mean concentrations (ng/ml) at the pH levels 1.5, 5.0, 7.0, and 9.0 are 464, 653, 649, and 657. The pH = 1.5 data are clearly not equivalent to the data at the other three pH levels; this is an effect of ion pairing at the lowest pH level. Under these circumstances, the only reliable data for a pooled estimate are the data at pH levels 5.0, 7.0, and 9.0. Figure 3 illustrates the results of this pooled analysis according to Equation 1, and Table 5 summarizes the results of the analysis. I Table 5. Degradation Rate and Half Life of PFOA in Aqueous Buffered Solutions Using Data Pooled Over pH Levels 5.0,7.0, and 9.0 Calculated Calculated (20) Half Observed Rate Percent (20) Rate Rate Calculated Life Constant at Constant Uncertainty Constant at Half Life Minimum at 50" C at 50" C 25" C at 25C 25" C 8.1 x IO-" (day-') (day1) 8.1 x (years) 235 (years) 92 Page 15 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Figure :3. Pooled (pH = 5.0, 7.0, and 9.0) PFOA Data and Slope Regression. 0.05 0 CI 0 P -B 0.00 - C Solid Line: y = -8.08E-05~+ 1.06E-03 R2 = 7.49E-02 0 Dashed Lines: 2 0 limits (slope and intercept) 0 20 40 60 80 100 120 time (days) The mean and standard deviation of the PFOA data provide an alternative estimate of its half-life. Details of the related calculations are presented below in Appendix B. The maximum degradation rate is given in Equation 3 (see Equation 836): and the miniimum half-life is given in Equation 4 (see Equation 837): Eq. 3 Eq. 4 Page 16 of 99 _ _ _ _ _ _ ~~ ~ ~ BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 In both Equations3 and 4,the mean PFOS concentration(p,)and standarddeviation (op)can be either molar or mass quantities. Table 6 presentsthe results of the calculation. At (days) 109 PP (ng/ml) 653 0, (nglml) 7.0 Maximum Observed Rate at 50" C (day-') 2.0x IO' Maximum Calculated Rate at 25" C (day-I) 2.0 x I O + Calculated Half Life at 25" C (years) 2 97 Page 17 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Conclusions We have performed a study of the aqueous hydrolysis of perfluorooctanoic acid (PFOA) at 50C and extrapolated the results to 25C. We included six different pH levels in the study, though data from two of these pH levels (3.0 and 11) failed to meet the data quality objective for matrix spike recovery. We also rejected the data obtained for pH = 1.5 because ion pairing led to artificially low concentrations for all the incubation periods. Our results for the remaining pH levels (5.0, 7.0, and 9.0) indicate no clear dependence of the degradation rate of PFOA on pH. From the data pooled over these three pH levels, we estimate that the hydrolytic halflife of PFOA at 25C is greater than 92 years, with the most likely value of 235 years. From the mean value and precision of PFOA concentrations, we estimate the hydrolytic half-life of PFOA to be greater than 97 years. Page 18 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 References "Fate, Transport and Transformation Test Guidelines: 835.21I O : Hydrolysis as a Function of pH," U.S. EPA Office of Prevention, Pesticides and Toxic Substances, publication number 712-C-98-057, January 1998. Experimental Physical Chemistry", F. Daniels, et al., McGraw Hill Book Co. (New York), p. 131, 1962. Page 19 of 99 Signatures BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 William K.R.eagen,Ph.D., Laboratory Management Date Page 20 of 99 ~ ~~ BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Appendix A: Analytical Method Method Number: ETS-8-212.0, "Preparation of PerfluorooctanoicAcid (PFOA) Hydrolysis Samples in Buffered Solutions and Analysis by High Performance Liquid Chromatography with Mass Spectrometry Detection." This Appendix presents the analytical method employed in this study. Page 21 of 99 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-1851 I! I - " ~MENVIRONENMTAL LABORATORY METHOD PREPARATIONOF PERnUOROOCTANOICACID (PFOA) HYDROLYSSIASMPLES IN BUFFERESDOLUTIONSAND hJAL,YSISBY HIGHPERFORMANCELIQUID ~ O M A T O G R A P H YWITH MASS SPECTROlMETRYDETECTION Method Number: ETS-8-212.0 Adoption Date: 3/47 1' Effective Revision Date: .n) Approved By: ETS-8-2 12.0 PFOA Hy&oIysis mdAnalysisby W L C / M S Page 1 of 16 Page 22 of 99 BACK TO MAIN I k 3M Environmental Laboratory Report No. E00-1851 1.0 SCOPE AND APPLICATION 1.1 This method describes how to test for possible hydrolysis reactions of perfluorooctanoic acid (PFOA) in buffered solutions of pHs 1.5,3.0,5.0,7.0,9.0, and 11.0. The method is based on EPA OPPTS:835.2110 (Reference 18.1). Hydrolysis products are analyzed by high performance liquid chromatography (HPLC) with mass spectrometry(MS)detection and quantitation. PFOA anion is quantified using the anion of perfluorobutanesulfonate (PFBS) as an internal standard. Representative chemical structures are shown in Attachment A. 1.2 Compatible analytes. PFOA and PFBS samples may be prepared and analyzed by this method. 1.3 Acceptable matrices. Aqueous buffered solutions ranging from pH 1.5 to 11.O are accqtable. 1.4 Method Performance. This method is defined as performancebased (see Section 14). 2.0 SUMMARY OF METHOD 2.1 This method is based on OPPTS:835.2110 and has been modified to give additional infarmation. Specifically, multiple time points over far longer periods of time are used to provide additional information regarding the hydrolytic behavior. Additional pH's are tested to provide insight into acidhase catalysis. Because of the longer time points used, (e.g. 109 days vs. 7) and the multiple time points (7 or 8 vs. 2) the k p e r a t u r e requirement o f f 0.1"C has been relaxed (it is impossibleto hold thistight of temperature and open the incubator to take out samples.) Oxygen is to be excluded (according to the OPPTS methodology) to minimize bacterial growth. However, the 50C temperature used in the present study is forbidding to most mesophillic organisms and the pH dependence for bacterial growthis different thanthat observed for most chemical reactions that occur in water. Aliquots of PFOA solution are added to sample vials that contain 5 mL of buffered solution of pH 1.5,3.0,5.0,7.0,9.0, or 11.0, Appropriate quality control samples are prepared. Sample vials are tightly capped and placed into an orbitalincubator/shaker at 50 f3 "C and 100f50 RPM, except for Day 0 samples, which are immediately refrigerated at 4 rt 3 "C or frozen at -20 f 10 "C. Sample vials are removed fiom the incubatodshaker at designated intervals and refrigerated or fkozen. When analyzed, all samples are allowed to come to room temperature, diluted with approximately 30 mL of methanol containing an internal standard, spiked (for those samples receiving spikes) and mechanically shaken for approximately 15minutes. Samples are aliquoted into separate autovials. Calibration and quality control samples are pxpared. PFOA is separated on a reverse-phase Dionex IonPac"NG-1 HPLC column, using an H,O/MeOH solvent gradient containing ammonium acetate. Analytes are detected and quantified by electrospray ionization mass spectrometry in the negative-ion mode. ETS-8-212.01 PFOA Hydrolysis and Analysis by HPLc/Ms Page 2 of 16 ' Page 23 of 99 BACK TO MAIN I t 3M Environmental Laboratory Report No. E00-1851 . . r . _ ._ -- , - ,- 3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 3.10 3.11 3.12 3.13 3.14 DEFINITIONS Method blank. The method blank determines if there is contaminationof the matrix. It is prepared identically to other samples,but it does not contain analyte (see Section 12.1.1). It is used alone and in conjunctionwith a method spike to detect accidental contamination(see Section 14.3). Method spike. A method spike is a spiked method blank (see Section 12.1.1) used to establish that the sample preparation method and analytical method would quantitatively detect target analyte in the method blank. (see Section 14.6). Solvent (methanol) blank. To isolate instrument contamination, pure methanol is analyzed. If the instrument is contaminated,analyte will be detected in the solventblank. (see section 14.4). Sample triplicates. Samples are prepared in triplicate for each time point and pH, and are analyzed identically (see Section 12.1.1). The averaged result represents the PFOA concentrationfor that time point and pH. Sample spike. A sample spike c o n f i m that the method recovers analyte effectively fiom the sample matrix (see Section 14.6). A known amount of analyte is added to a sample after it is incubated (see Sections 12.1.1). Internal standard (IS). An internal standard is used to evaluate and control the precision (Section 3.7) and bias (Section 3.8) of the analytical process. An analytically similar compound is added to all samples and standards, creating a known, fixed concentrationin all samples and standardsthrough the entire measurement process. Precision. Precisionis the degree of agreementbetween individualsampleresults. It is usually expressed as a standard deviation. Bias. Measurements are biased if they are consistently high or low (a systematic error), as comparedto a known value. Calibration standard. A calibration standard is a solution containing a known concentrationof analyte. A series of calibration standards is used to calibrate analytical instrument response, producing a calibration curve to determine analyte concentrations in samples. Continuing calibrationverification (CCV) or Check standard. M e r the analytical inslmment has been calibrated, a single calibration standard is analyzed at selected time intervals throughout the analytical run. The values are comparedto the calibration curve to ensure that the calibration curve is valid for all samples over time, that the instrument has not drifted out of calibration. Dilution. A miscible solvent is added to all samplesto prepare them for instnunental analysis. Laboratory Water. Water with a measured resistivity of 18.0 MQ-cm (or greater). Limit of quantitation (LOQ). The limit of quantitation&OQ) is equal to the concentration of the lowest standard in the calibration curve that gives a response of more than four times the response of the solvent blanks andor MeOH blanks. Use the solvent blanks andor MeOH blanks that give the highest analyte counts. Residuals. In this method, a residual is the absolute value of the difference between the known,prepared concentration of a calibration standard and its concentrationpredicted by the calibrationcurve, divided by the known,prepared concentration,all multiplied by ETS-8-2 12.0 PFOA Hydrolysis andAnalysis by HPLUMS Page 3 of 16 Page 24 of 99 I/ BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 . " ~ .. - * _ _ 100. Residuals for linear calibration curves can be determined using Excel. For nonlinear calibration curves, the following equation should be used to determine a residual. 4.0 WARNINGS AND CAUTIONS 4.1 Health and safely warnings 4.1.1 Wear the proper lab attire for all parts of thisprocedure. Wear appropriategloves and proper eyewear at all times. 4.1.2 For sample preparation and whenever possible, use solventsin the hood. 4.1.3 For potential hazards of each chemical used, refer to material safety data sheets, packing materials, and 3M Environmental Laboratories Chemical Hazard 1 Review. 4.2 Cautions 4.2.1 Rinse all glassware for standards preparation with MeOH and acetone and dry,to reduce the possibility of contamination. 42.2 Prepare enough fresh HPLC mobile phase to analyze all samples. Do not allow the HPLC pump to run dry. 4.2.3 Ensure that there is ample memory on the computer hard drive to save all run data. 4.2.4 Ensure that there is enough nitrogen in the supply tank to analyze all samples. 5.0 INTERFERENCES 5.1 Contaminants in solvents, reagents, glassware, and other sample preparation or analysis hardware may produce interfiinces. Routinely analyze method blanks to detect contamination fiom these sources (see Section 10.4). 5.2 Contaminants from columns, HPLC tubing, and detector components may cause interference at low detection levels. Routinely analyze solvent blanks (methanol) to detect contamination from these sources (see Section 10.5). 6.0 EQUIPMENT 6.1 Analytical balance sensitive to 0.0001 g 6.2 Sh;dcer/incubator capable of maintaining a temperature of 50 k 3 OC 6.3 Hewlett-Packard (HP) 1100 HPLC System, or equivalent 6.3.1 Quaternary pump, Model G1311A, or equivalent 6.3.2 Solvent degasser, Model G1322A or equivalent , 6.3.3 Autosampler, ALS Model G1313A, variable injection volume capable, or equivalent 6.3.4 Column heater, Model G1316A or equivalent 6.4 Dionex IonPac@NG-1column, 35 mm x 4.0 mm, 10-pn dime& packing, or equivalent ETS-8-212.0 PFOA Hydroiysis and Analysis by H P L U M Page4 of 16 Page 25 of 99 I a . BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 ~. I. " 6.5 Mass spectrometer. Hewlett-PackardLCMSD, or equivalent, capable of operatingin the selected-ion-monitoring mode 6.6 Digital clock. The same clock should be used during any one step of sample preparation, to emure that procedures are performed correctly and documented .accurately. 6.7 Corning Model 308 pH/TemperatureMeter with 3-in-1 gel-filled combinationelectrode - (pH/reference/temperature),or equivalent. buffer standards (e.g. pH 4.0,7.0 and 9.0 The pH meter must be calibrated with suitable Mallinckrodt or equivalent) as recommended by the manufacturer for this broad of a pH range. 6.8 Refrigerator, capable of maintaining 4 f 3 "C, or a freezer capable of maintaining -20 f 10 OC 6.9 Data system. A PC computer capable of simultaneouslycontrollingthe HPLC system and recording and processing signals from the detector 6.10 Data analysis sohare. Hewlett-Packard-ChemStation@V, ersion A 6.03or higher,or Target Software. 7.0 - SUPPLIES AND MATERIALS 7.1 Vials, 40-mL VOA (I-CHEM or equivalent) 7.2 Crimpcap autovials, 1. 5 - d 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 (precisionf 1%of total volume), lo-@ to 1000-pL 7.7 Volumetric flasks,lo-, 2 5 , loo-, 1000-, and 4000-mL. 7.8 Beakers, glass, various sizes 7.9 Automaticpipettor, capable of dispensing 10to 5000 pL 7.10 Miscellaneous equipment as needed 8.0 RE.4GENTSAND SOLUTIONS 8.1 Rewents 8.1..1 Methanol (MeOH). HPLC/SPEC/GC grade from EM Science,or equivalent 8.1.2 Laboratory Water (LW) 8.1.3 Hydrochloric acid (HCl), reagent grade 8.1.4 Sodium hydroxide (NaOH), reagent grade 8.1.5 Sodium borate decahydrate (borax), reagent grade 8.1.6 Sodium bicarbonate (NaHCO,), reagent grade 8.1.7 Potassium dihydrogenphosphate (KHzP04),reagent grade 8.1.8 Potassium acid phthalate (KHP), reagent grade 8.1.9 Ammonium acetate (CH,COz+JH,), reagent grade 8.1.10 Potassium salt of Perfluorooctanoicacid (PFOA) 8.1.11 Potassium salt of Perfluorobutanesulfonate (PFBS) 8.2 &ick Solutions ETS-8-212.0 PFOA Hydrolyssb and Analysis by HPLUMS Page 5 of 16 Page 26 of 99 I,. . BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 ~ ., - 8.2.1 Ammonium acetate stock solution. Dissolve approximately 3.9 g CH3C02;NH, in MeOH to a total volume of 100mL to give approximately 500 mM CH,C02-NH4. 8.2.2 PFOA stock solution. Dissolve approximately 0.1000 g of PFOA in MeOH to a total volume of 10 mL to give approximately 10,000 p g / d PFOA. 8.2-3 PFBS stock solution. Dissolve approximately 0.0500 g of PFBS in MeOH to a total volume of 25 mL to give approximately 2,000 pg/mL PFBS. 8.2.4 Hydrochloric acid (HCI) stock solution. Add approximately 8.6 mL. of concentrated HC1to approximately600 mL LW, dilute to a total volume of 1L to give approximately 0.1 M HC1. 8.2.5 Sodium hydroxide (NaOH) stock solution. Dissolve approximately 4.0 g of solidNaOH in LW to a total volume of 1L to give approximately0.1 M NaOH. 8.2.6 Potassium dihydrogen phosphate stock solution. Dissolve approximately 13.6 g of KH2P0,in LW to a total volume of 1 L to give approximately 0.1 M (KH2P04). 82.7 Borax stock solution. Dissolve approximately9.54 g of N ~ B 4 0 , ~ 1 0 Hi2n0LW to a total volume of 1L to give approximately0.025 M N5t2B40,. 8.2.8 Sodium bicarbonate stock solution. Dissolve approximately 4.2 g of NaHCO, in LW to a total volume of 1 L to give approximately 0.05 M NaHCO,. 8.3 PFOA test analyte solution. Dilute 2 mL of PFOA stock solution (Section 8.2.2) with MeOH to a total volume of 10mL to give approximately2,000 pg/mL, PFOA. 8.4 PFOA spike solution. Dilute 0.5 mL of PFOA stock solution (Section 8.2.2) with MeOH to a total volume of 10mL to give approximately500 p g / d PFOA. 8.5 PFBS diluting solution. Dilute 400 pL of PFBS stock solution (Section 8.2.3) with MeOH to a total volume of 4 L to give approximately200 ng/mL PFBS. 8.6 Chromatographic solvents 8.6.1 Chromatographicsolvent A. Dilute 10mL of ammonium acetate stock solution (Section 8.2.1) LW to a total volume of 1 L to give approximately5 m M CH,CO,*NH,. 8.6.2 Chromatographicsolvent B. Dilute 10mL of ammonium acetate stock solution (Section 8.2.1)with MeOH to a total volume of 1 L to give approximately 5 mM CH,COyNH,. 8.7 Calibration buffers for pH meter. Use commerciallyavailablepH meter calibration buffers of pH 4.0,7.0, and 10.0 (Mallinckrodtor equivalent)as recommended by the manufacturer for this broad of a pH range. 8.8 Hydrolysis buffers. Buffer solutions should be made following EPA and CRC Handbook of Chemistry and Physics guidelines (References 18.1 and 18.2) 8.8.1 Hydrolysis buffer pH 1.5 a) Add 207 mL 0.1 N HCl, 250 mL 0.1 M KC1 to a 1 L volumetric flask. b) Adjust pH to 1.5 with HCl stock solution c) Dilute to mark with LW 8.8.2 Hydrolysis buffer pH 3.0 a) Dissolve approximately 10.2 g of potassium acid phthalate (KHP) with approximately 600 mL of LW water in a 1 L volumetric flask. b) Add approximately223 mL of HC1 stock solution(Section 8.2.4). ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLC/uS Page 6 of 16 Page 27 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 II 8.83 8.8.4 8.8.5 8.8.6 c) Adjust the pH to 3.0 with either HC1 stock solution (Section8.2.4) or NaOH stock solution (Section 8.2.5). d) Bring to a find volume of 1 L with LW. Hydrolysis buffer pH 5.0 a) Dissolve approximately 10.2 g of potassium acid phthalate (KHP) with approximately600 mL of LW in a 1L volumetric flask. b) Add approximately 226 mL of NaOH stock solution (Section 8.2.5). c) Adjust the pH to 5.0 with either HCl stock solution (Section 8.2.4) or NaOH stock solution (Section 8.2.5). d) Bring to a final volume of 1 L with LW. Hydrolysis buffer pH 7.0 a) Add approximately 500 mL of potassium &hydrogen phosphate stock solution (Section 8.2.6) to a 1 L volumetric flask. b) Add approximately 291 mL ofNaOH stock solution (Section 8.2.5). c) Adjust the pH to 7.0 with either HC1 stock solution (Section 8.2.4) or NaOH stock solution (Section 8.2.5). d) Bring to a final volume of 1 L with LW. Hydrolysis buffer pH 9.0 a) Add approximately 500 mL of borax stock solution (Section 8.2.7) to a 1 L volumetric flask. b) Add approximately 46 mL of HCl stock solution (Section 8.2.4). c) Add LW to a total volume of approximately950 mL. d) Adjust the pH to 9.0 with either HCl stock solution (Section 8.2.4) or NaOH stock solution (Section 8.2.5). e) Bring to a final volume of 1 L with LW. Hydrolysis buffer pH 11.0 a) Add approximately 500 mL of sodium bicarbonate stock solution (Section 8.2.8) to a 1 L volumetric flask. b) Add approximately 227 mL of NaOH stock solution (Section 8.2.5). c) Add LW to a total volume of approximately 950 mL. d) Adjust the pH to 11.O with NaOH stock solution (Section8.2.5). e) Bring to a final volume of 1L with LW. 9.0 SAMPm HANDLING 9.1 Retard the times that sampleswere initially prepared, removed fiom the incubator, placed in the fkeezer (when applicable), removed from the hezer (when applicable) and subsequently diluted, using the fluorochemicaldegradation (hydrolysis) analysis sample preparation sheet (AttachmentB). All samplesfor the same pH group should be analyzed together. RefXgerate or freeze them if necessary, and dilute them immediately preceding the analysis. 10.0 QUALITCYONTROL 10.1 Sa:Section 12for directionson preparing quality control samples. ETS-8-2 12.0 PFOA Hydrolysis andAndysis by HPLC/MS Page 7 of 16 Page 28 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 102 10.3 10.4 10.5 10.6 10.7 10.8 11.0 11.1 11.2 Calibration standards. Analyze a complete series of calibration standards before and after each analyticalrunfor use as calibration curve. At the discretion of the analyst, t h i s complete seriesmay be runmore often in the d y t i c a l run. Continuing calibrationvenfiation (CCV). A CCV sample should be analyzedafter no more than20 sampleinjections. A single calibration standard or a complete series of such standards (for use as a calibration curve) will satisfy this requirement. Method blank. Analyze a minimumof one method blank per time point per pH (e.g., Day 42, pH 7.0). Solvent blank. Analyze one solvent blank before and after every calibration curve as well as before and after every CCV. Sample triplicates. Prepare and analyze all hydrolysis samples in triplicate to determine analysis precision. Sample spikes. Prepare a sample spike for each pH and time point used in the study. Final (diluted) spike concentrations should approximate a mid-range calibration standard. The sample spike sample should be analyzed immediately following the sample triplicates to which it corresponds. Internal standards. Aliquots of PFBS stock solution (Section 8.2.3) are added to calibration standards to give a final internal standard concentration of approximately 158ng/mL PFBS. Samples should also contain approximatelythe same concentrationof PFRS. CALIBRATIAONDNSTANDARDIZATION Standard preparation. Prepare at least five calibration standards of approximately25 to 1000ng/mL PFOA,containing approximately 158 ng/mL PFBS internal standard. Standard curve. Relate the ratio of the analyte peak area of the calibration standards to the internal standard peak area, using linear regression software. If calibration ratios are inconsistent, external standard calibration may be used. Consult the Team Leader or designated supervisor for recommendationsbefore using external calibration. 12.0 PROCEDURES ETS8-2 12.0 PFOA Hycirolysisand Analysis by HPLUUY Page 8 of 16 Page 29 of 99 . 1 . . .. ~, ... ..... ... ._ BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 .._....._..._.. . . . . , _ . . _ I ..... . ,. . _ 12.1 Sample preparation and hydrolysis 12.1.1 The following table summarizes sample preparation. Calibration standards Analyte Buffer X X Diluting solution containing internal standard X Spike -- Continued Calibration X X X -- verification (CCV) Methodblanka I -- I X I X I -- Solvent blank -- -- -_ -- Sample X X X -- Duplicate X X X Triplicate I X I X 1 X I . -- Sample spikeb X X X X Method spikeC -- X X X Methanol Incubate only /shake -- I x - Ix -- I x -- X 12.1.2 12.1.3 12.1.4 12.1.5 12.l.6 Determinethe number of time points and correspondingsamplesto be analyzed. Each time point should have six vials per pH: sample, duplicate, triplicate, sample spike, method spik, and method blank. Obtain the appropriate number of 40-mL VOA vials with caps, and the partitioned cardboardbox they were shipped in. It will be helpll to use a separate box to hold the vials for each time point. Prepare sample preparation worksheets (AttachmentB), ahd label the vials with the sample number, pH, time point, and initials of the analyst. Record the pH and buffer ID of each hydrolysis buffer solution. Add 5 mL of the appropriate buffer solutionto all of the labeledvials. Always recap each vial immediately to minimize solvent evaporation. Using a 10-pL Gastight' syringe, add 15 pL ofPFOA test a d * solution (Section 8.3) to the following sample types for each time point and pH: sample, duplicate, triplicate, and sample spike (see Section 12.1.1). ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLUMS Page 9 of 16 Page 30 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 I .~ 12.1.7 Make sure all vials are well-sealed, and place them into a partitioned cardbard case (with cover) to exclude light. It will be helpful to use a separatebox to hold 12.1.8 the vials for each time point. Refrigerate Day 0 samples at 4 * 3 OC, or freeze them at -20 f 10 "C. 12.1.9 Place the remaining samples into a pre-warmed incubator/shaker for the appropriate time. Record the time, temperature, and shaking rate (RPM). Continue to manually monitor the incubator temperature daily during the entire incubation. Record the temperature on the sample preparation sheet (Attachment B). 12.1.10 Remove each case fiom the incubator at the designated time. Refiigmte them at 4 f 3 "C, or fieeze them at -20 f 10 "C, until all samplesh m all time points can be analyzed together. 12.1.11 Before analysis, allow the incubated vials to come to room temperature. 12.1.12 Add 30 mL of PFBS diluting solution (Section 8.5) to all vials. 12.1.13 Using a 10-yL Gastight' syringe, add 10 yL of PFOA spike solution (Section 8.4) to the method spike and sample s p i k vials (see Section 12.1A). Recap the vials tightly, and invert them severaltimes to mix. 12.1.14 Aliquot approximately 1 mL of each sample into the appropriately labeled autovial. Cap the vials. 12.1.15 Transfer the vials to the HPLC autosampler. 12.2 HPLC set-up 123.1 Review instrument method 1101PF0A.M. Note that thefollowing instrumentationset-upprocedures apply to Hewlett-PacbdAgilentHPll 00 equipment only. 12.2.2 For each analysis, ensure the appropriate HPLC column is in the instrument (Dionex IonPacdPNG-l,35mm x 4.0mm, 10-pm diameter packing, or equivalent). 12.23 Ensure the correct type and amount of eluent is loaded in the instrument. Be sure there is enough loaded to completethe analytical sequence. 12.2.4 Place the samples in the autosamplertray and construct a sequencetable with calibration standards, calibration check standards, and solvent blanks. 12.2.5 Verify that all samples and standards are positioned correctly. Enter sequence information: sample or standardID, method name, and one injectionper sample. 12.2.6 Save sequence as analysis date (e.g., on September 14,2000 save sequence as 091400.s). Save data to a subdirectory labeled with analysis date (e.g., 091400). 12.2.7 Set the post-sequence command macro to shut the system down ("STANDBY" on HP systems). - 12.2.8 Use the following solvents (see Section 8.6), gradient, and instrument settings (or equivalent note that the following instrumentation set-up procedures apply to Hewlett-PackardAgilentHpl 100MSD equipment only). 12.2.8.1 Chromatographicsolvent A (Section 8.6.1). 12.2.8.2 Chromatographicsolvent B (Section 8.6.2). 12.2.8.3 Solvent Gradient ETS-8-2 12.0 PFOA Hydrolysis andAnalysis by HPLUM Page 10 of 16 Page 31 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 , 12.2.8.4 Instrument settings 12.3 Mass spectrometer set-up 123.1 Use the following tables (or equivalent) to-set up the mass spectrometer. (Note that the following instrumentation set-up procedures apply to Hewlett- PackardAgilent HP 1100MSD equipment only.) * M-I-I+is the molecular ion with a loss of proton. For example, the molecularweight of PFBS is 300, when it loses a proton, it assumesa negativecharge and has a mass of 299. 12.4 Autosampler set-up 12.#4.1 Use the following parameters (or equivalent) to set up the autosampler. ETS-8-212.0 PFOA Hydrolysis andAnalysis by HPLCXUS' Page 11 of 16 Page 32 of 99 I* ~ BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 . - - . , . ~ - _~ .._ 12.5 Sample analysis 12.5.1 After setting-upthe HPLC, the mass spectrometer, and the autosampler, analyze a CCV after every 20 sample injections, and the calibration standards at the end of the sequence. To check for analyte carry-over, run solvent blanks after the highest calibration standard as well as before and after the ,CCV(see Section 10.0). 12.52 Identify the electronic acquisition files with an appropriateprefix. Do not exceed five characters if the sequence contains more than 99 lines. - 13.0 DATAANALYSIASND CALCULATIONS 13.1 Peak evaluation. Anal@ and internal standardpeaks must be symmetrical if peak tailing is observed, consult team leader or designee for direction. They must be identified by measuring their retention times and by the compo'und-specific ions. When generating a calibration curve, analyte peak heights must be greater than four times the baseline noise and/or solvent blank for that region of the chromatogram. Peak areas are integrated manually or automatically fiom baseline to baseline through the peak. If present, analyte isomers appearing as either a shoulder or a discrete second peak in the chromatogram should be integrated with the analyte peak, unless otherwise indicated. Quantitation data are calculated using PFBS as the internal standard. However, external standard calibration may be acceptable. Consult the Team Leader or designated supervisor before using external calibrationmethodology. 13.2 Calculations involving analyte purity. In calculations where analyte purity ratios cancel each other (e.g., calculation of the hydrolysis rate constant, k based on loss of parent material), purity does not need to be considered. 133 Percent recovery. Calculate the percent of PFOA recovered from each of the sample spikes using the following equation. - % Recovery = [PFOA]dcrecred inm p i espike [PFOA] detected in comspondig~mnpl. x 100% [PFOA] inSompIespike,added vias p ~ e 13.4 Sample triplicates. Use the following equation to calculatethe relative standard deviation (RSD) for the triplicate samples. RSD = Standard Deviation x 100% Mean Concentration The RSD is also known as the coefficient of variation, a measure of the precision. 13.5 Calculation of k. Calculate the PFOA concentrations in each of the pH matrices using the calibration and internal (or external) standard curves. Assuming frrst-order kinetics a rate constant (k)can be determinedby plotting ETS-8-212.0 PFOA Hydolysis and Analysis by H P L U M Page 12 of 16 Page 33 of 99 .I. .. .; .... . . .I BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 .- .. ._,. .. -. . .. , .. . . , , . ,. . , .. . . Ln (E;)versus negative elapsedtime (-0, where the subscriptst and 0 refer to analyteconcentrationsat time t and at r = 0, respectively. The slope of the resulting line is k. I 14.0 METHOD PERFORMANCE 14.1 Calibration curves. An acceptable coefficient of determination (R') for linear curves is 0.9!?0or greater. Accuracy shouldbe verified, particularly at upper and lower calibration limits by calculating the residuals -residuals generated in curve-fittingmust be between 0 and 25%. Alternative methods of curve-fitting (e.g., quadratic) require a coefficient of determination(9)of 0.990 or greater. Record the reason(s) for using quadratic curve- fitting in the raw data.If the quality control parametersare not met, consultteam leader or designee for direction. 14.2 Continuing calibrationverification (CCV). Analyte concentrationmust not differ by more than 25% of its expected value, relative to the initial calibrationcurve. Accept only those samples analyzed before the last accepted calibration verification. Reanalyze remaining samples with a new calibration curve. 14.3 Method blank. If the contaminationlevels are greater than 5% for any particular target, consult the Team Leader or designated supervisor for recommendations. For example, if PFOA were targeted at 500 ppb, contamination should be less than 25 ppb. In those instances where the 5% level would be below the lowest point of the calibration curve, a 25% value is used rather than the 5% (as 5% cannot be quantified and the 25% level brings this in line with the LOQ definition, see section 14.8). 14.4 Solvent blanks. Solvent blanks should show no more than a 5% carry-over from a high standard or CCV. If they do, two solvent blanks should be analyzed to rule out instrument contamination. If solvent blanks are still showing more than 5% carry-over, or are adversely af3Fectingthe LOQ (see Section 14.8), the runshould be stopped. This indicates that the instrument is contaminated and should be thoroughly cleaned. Pay particular attention to the electrospray source. The column and tubing may need to be replaced. W h e n the solvent blanks are improved, reanalyze the sequence beginning at the last acceptable CCV or calibration curve, starting with a new calibration curve. 14.5 Sample triplicates. If RSD precision values are 25% or greater, consult the Team Leader or designated supervisor for recommendations. 14.6 Sample spikes. If sample spike recoveries are less than70% or greater than 130%, conlsult the Team Leader or designated supervisor for recommendations. 14.7 Residuals. The acceptancecriterionfor the residuals is less than or equal to f 25%. If the residuals are higher thanthis, consult team leader or designee for direction. No calibration curve will be accepted with residuals outside this range. 14.8 Limit of Quantitation. The limit of quantitation (LOQ) is equal to the lowest standard in the calibrationcurve that gives a response of more than four times that of the test anadyte in the solvent blanks. 14.9 Method Spike. If method spike recoveries are less than 70% or greater than 130%, corlsultthe Team Leader or designated supervisorfor recommendations. ETS-8-212.0 PFOA Hydrolysis anddnalysis by H P L U M Page 13 of 16 Page 34 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 .- 15.0 POILUTIOPNREVENTIOANND WASTMEANAGEMENT 15.1 Dispose of sample waste by placing it in high or low BTU containers as appropriate. Use broken glass containersto dispose of glass pipettes. 15.2 Collect HPLC solvent waste in the satellite accumulationcan. When the satellite can is full, empty it into the flammable storage drum in the hazardous vvaste collection area on the second floor. 16.0 RECORDS 16.1 Print out hard copies of all graphics and data analysis summaries for archiving. 16.2 Sign and date all graphics, and label with the instrument ID. 16.3 Immediately fill out the hydrolysis sample preparation worksheet completely, including all initials and dates. 16.4 Print chromatograms and internal standard reports for all analyses. 16.5 Print calibrationtables and curve information,and store them in the raw data file. 16.6 Store hydrolysis sample preparation worksheets in the raw data file. 16.7 Enter all standard preparation informationin the standardsprepmationlogbook. Make a photocopy of the logbook page and include the copy in the raw data file. 16.8 Archive electronic data to appropriate media when necessary. 17.0 ATTACHMENTS 17.1 Attachment A. Representative Chemical Structures 17.2 Attachment B. Hydrolysis Sample Log sheet 18.0 REFERENCES 18.1 Fate, Transportand TransformationTest Guidelines OPPTS 83.i.21IO: Hydrolysis as a Function ofpH; EPA 712-C-98-057;U.S.EnvironmentalProtectionAgency, Office of Prevention, Pesticides and Toxic Substances,U.S. GovernmentPrinthg Office: Washington,DC, 1998. 18.2 CRC Handbook of Chemistry and Physics, 1st Student Edition; We&, R. C., Ed., CRC Press: Cleveland, OH, 1988; p. D-87. 19.0 AFWECTEDDOCUMENTS None. 20.0 REVISIONS & i s i o n Number Reason for Revision ETS-8-212.01 PFOA Hydolysis andAnalysisby HPLUMS Page 14 of 16 Page 35 of 99 BACK TO MAIN I. 3M EnvironmentalLaboratoryReport No. E00-1851 Attachment A. Representative Chemical Structures R' =NH,' inthis study, but may also be Li', Na', K+,H'. 1. PFOA (Perlluorooctanoic Acid) h4W (anion) = 413 2. PFBS (?erlluorobutanesulfonate) M W (anion) = 299 ETS-8-212.0 PFOA Hydrotysis anddnalysis by HPLC/US Page 15 of 16 Page 36 of 99 BACK TO MAIN I/ 3M Environmental Laboratory Report No. E00-1851 Attachment B. Sample Preparation Sheet Fluorochemlcal Degradation (Hydmiysls) Aniilysb ETS-8-212.0 PFOA Hydrolysis and Analysis by HPLUMS Page 16 of 16 Page 37 of 99 - BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Appendix B: Kinetics Model This Appendix includes a mathematicaldescription of the kinetics m'odelemployed in the study. Page 38 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Kinetics Model B1. Reaction Components and Rates The arguments below are based on the following idealized set of reactions representing the hydrolysis of a parent compound P and its hydrolysis products A,, which number N. The actual hydrolysis reactions that occur under neutral, acidic, and basic conditions are subsumed in these equations, and are assumed to proceed with pseudo-first order rates k,, (for the parent) and k,, (for the parent's hydrolysis products). P + H20 k, @ n, A, + Yd (m = 1 toN) (81) kh A, +H,O Ym2 (m= 1toN) (82) where the general symbols Y, and Ym2represent all the other hydrolysis products. B2. Parent Compound Concentrations Equation B I indicates that the pseudo-first order differential change in the parent concentratioln P is given by which is equivalent to the separable differential equation dPp=($ nmkpm]dt Equation 84 may be directly integratedto obtain the general solution With the initial condition P(t = 0) = Po,the specific solution to Equation B4 is P = Po exp [- n, k,, t)- Po e-kp using the additional definition of the total parent hydrolysis rate Page 39 of 99 - BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-1851 N k, nmk,, . m 1 Equation BE;can be re-written in a form that allows a least-squares estimate of the total parent hydrolysis rate: k,t =-In [9) Using the initial(t =0) measured value of the parent concentration Poand later values P measured at later times t , one can calculate and plot the (linear) quantity [- In 1 (P/Po versus time and obtain a least -squares estimate of the slope of the line. The resulting slope is the least-squares estimate f, of the total parent hydrolysis rate. Equation B6i indicates that over a period of time T1'i (the parent hydrolysis half-life) the parent concentration P is reduced through hydrolysis by a factor of two, where 2) = k, A least squares estimate ?q;of the parent hydrolysis half-life is therefore available from B3. Product Compound Concentrations The pseudo,-firstorder differential changes in the product concentrations 4, (using Equations 82 and B6) are dA, = ( n,kpmP- kAmAm)d=t( nmkPmPeO-kp - kAmA,)dt (B11) and the (first order, non-separable)differential equation governing the product concentrations is %+ k,Am = nmkPmPeO-kpt. dt The "standard form" of Equation B12 is Page 40 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 AA+S(t)Arn=Q(t) where the "function"S (t) is actually a constant: s (`1 and Q(t) =nmkPmPeO-kpt . The general solution A, to Equation 612 is contained in where eIS(t)dt -- e IS(t')dt' -- e k h l d t -- e k b t and IQ(t)dS(t')ddt't + C = n,kprnPo~ekht e-kptdt + C There are two cases of Equation B18 to consider. In the circumstance that k,, = k, , which occurs only when the hydrolysis rate of the mthproduct is identical to the total parent hydrolysis rate, the general solution to Equation B18 is (for k, = k,) A, + ekpt= nmkPmPtO C and, using the initial conditionA,(t = 0) = A, , the specific solution to Equation18 is (for k, = k,) A, =(nmkPmPtO+ A , o ) e - k p t . We note that when k, = k, = 0 (that is, when both the parent and potential product are hydrolytically stable), Equation B7 requires (also) that k,, =0, so Equation 820 becomes Page 41 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 indicating, as required, that the product concentration does not change with time. The circumstance k,, = kp 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 kpand the product hydrolysis ratek, approach each other. In the more probable case, for which ,k, # kp (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 and the specific solution to Equation B18 with the initial condition A,(t = 0 ) = A,, is 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 hydrolyticallystable products) A, = A m O+ nrnkF'mPO kP (~-~-k~t) B4. Relationships Between the Parent and Compound Concentrations Equations 87 and 824 can be combined to obtain (for hydrolyticallystable products) Page 42 of 99 so that or BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 (for hydrolytically stable products) (for hydrolytically stable products) If the changes in the product concentrations are all small compared to the original parent concentration, that is, if we may use the expression (valid for -1 I X I1 ) h ( l + X ) = X - -1x2+ -1 x 3 -1- x 4 +..... L 3 4 and Equation B23 becomes (for hydrolyticallystable products and m I Page 43 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 or lzflrn (for hydrolyticallystable productsand Im << Po I kPt g m=l 85. Parent Half-Life Estimates Based on Limits of Quantification of the Products In every experimental determination of k, ,there is some set of values AfQ (the "limits of quantitation") below which the product concentrations A, cannot be reliably measured. If during an experiment carried out over the period of timeA t all the product concentrations A, remain below their limits of quantitation, then the maximum possible value of the rate k, is obtained by assuming (for all the products) that 1) A,, = 0 and 2) at time t =: A t , the product concentrations have increased to the values A, = A f Q . With these assumptions, the experimental data indicate that the reaction rate k, is less than some maximum value (kp)- as follows: (for hydrolytically stable products at concentrations below the limits of quantitation) Under the same circumstances and assumptions, the experimental data indicate that the parent half-life T1'i (see Equation B9) is greater than the value (TI/:) . as follows: min (for hydrolytically stable products at concentrations below the limits of quantitation) The reader should note that Equations B32 and B33 are valid only when both 1) the products art?hydrolytically stable and 2) the concentrationsof all the potential products are measured. Otherwise, the quantity (kp)- in Equation 832 may not actually represent the maximum possible value of the rate constant k, , and the related result in Equation B33 for (TI/:)m.in is also questionable. Page 44 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 B6. Parent Half-Life Estimates Based on Limits of Quantification and Experimental Precision of Product Concentrations In certain ex:periments, 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, . If the set of concentrations measuredfor the mthproduct have the mean value p,,, and standard deviation o m ,the data do not exclude the possibility that the product concentration increased from the initial value om-p, to the value O, + 11, at time t = A t . Taking this possibility to be the actual case for the measured products, the maximum value of the quantity (A,,,-A,, ) is 20,. 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 standarddeviation Om or 2) concentrations below the limits of quantitation) r 1 Under these circumstances and assumptions, the experimental data indicate that the parent half-life TI': is greater than the value (T . as follows: rnin (for hydrolytically stable products at either 1) constant measured concentrations with standard deviation om or 2) concentrations below the limits of quantitation) Tv2 2 P =-- (k, 1- - At r 1-1 Po In(2) A r Q+ Z 2 o r n ] . Below LOQ Cons tan 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. B7. - Parent Half-Life Concentrations Estimates Based o n the Experimental Precision of Parent In certain experiments, the hydrolytic parent remains at an essentially constant concentraticin 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 ppand standard deviation op, the data do not exclude the possibility Page 45 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 that the product concentration increasedfrom the initial value pp -opto the value pp+opat time t = A t . This reasoning suggests that the following estimate of the maximum parent hydrolysis rate is appropriate: (for esseritiallyconstant parent concentrationswith mean value ppand standard deviation (5,, ) k p I(kp),, = -.2% CLp A t v i ) Under these circumstances and assumptions, the experimental data indicate that the parent half-life TI'; is greater than the value (T . as follows: rnm (for essentiallyconstant parent concentrationswith mean value ppand standard deviation (5 ,,) 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 B' provides the following relationship between the hydrolysis rates (kland k2)for that reaction at two different absolute temperatures (T, and T2): where R = 'I.99x Kcal mole-' K-' is the ideal gas constant. Using the valueB2 AH,=18 KcaVmole, the rate ratio k,/k, at the corresponding temperatures TI=298 K [ L]} and T2=323K is = exp{ 18 1- = exp(-2.35) = 0.095 :k 1 . 9 9 ~ 1 0 "323 298 Page 46 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Equation 639 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 50"C, and the hydrolysis half-life estimates reported here for 25C sarnples are ten times longer than those calculated from the 50C experimental data. References to Appendix B: B1 I. N Levine, "Physical Chemistry," McGraw-Hill (New York), pp. 498-501 (1978). 82 F. Daniels, et al., "Experimental Physical Chemistry", McGraw Hill (New York), p.131 (1962). Page 47 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Appendix C: Selected Analytical and Kinetics Results This Appendix includes selected sample data and their related kinetics results. Page 48 of 99 BACK TO MAIN 0 Z BACK TO MAIN 0, 0, z 0 BACK TO MAIN z 0 00000 m> % m % m mA % m 00000 r-lclcr-t. m* ma m> m> m* 00000 BACK TO MAIN tn tn rc 0 (v 10 z 0 ~~m NNNNN mx xm xm xm xm 00000 m2 2m2 2 2 xm xm xm xm xm 00000 %$%%% xm xm >m .mx mx 00000 E E mae r m 7 0 m BACK TO MAIN z 0 s m BACK TO MAIN % m BACK TO MAIN Q) Q) Y- O In In z 0 mmwww NNNNN m% m. Xm%m XmX 00000 NNNNN PP*** m% m% mA m% m% oonnn - z ul - z m r z N BACK TO MAIN z r m d 0 W z 0 mmmmm """00 >>w..xz. nm om nm nm om - z z 2 r N ""n"""nnn""t"ttnn~""~nn~mnffnn"""""""~~~ mmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmma BACK TO MAIN Y dv) W r w 0 z 0 00000 m% m% % m % m % m 00000 r-r-r-r-1C > m . m> .m%mA % m oooon gg z P: r r f s r r z 0 BACK TO MAIN a, a, c 0 Eroo z 0 mmmmm NNNNN m= - m. %m%m% m% 00000 N v uN eN m% =m- . =m- . 000 8721$%%% m% hm %m %m%mhm% m 0000000 f m 1rl 1 BACK TO MAIN z 0 $$$$$ mX Xm >m. >m . Xm 00000 mmmmm :Po?:! m> .m> .mXmX Xm 00000 zs s r r r BACK TO MAIN aQ, c 0 0 (0 z 0 00000 mx mx mx mx mx ooaoa r-r-r.t.rmx mx mx mx mx 00000 ZZZZZ mx xm xm xm . m2 00000 gm . $- $r fr s: gN Em BACK TO MAIN r v) 03 r d 0 W z 0 E m BACK TO MAIN N (0 z 0 $$ mP mPImZ $ mZ mZ $ X m X m X m A m X m >m . ?m . Am >m. %m 00000 00000 2 x 2 s x -m E s 0 m 2 ae I z r BACK TO MAIN 6 0 w z 0 00000 xm 2m. xm zm. >ml 00000 r-r-bbl. 2m .mx xm Im. 2m. 00000 ZPPff mx xm xmz m. 2m. 00000 ae I BACK TO MAIN z 0 A mmmmm NNNNN xm mx mx mx mx 00000 N * *N-Nr Ne *N mx mx mx mx mx noon0 z z z z E r 7 r m z 0 ae BACK TO MAIN z 0 t m BACK TO MAIN z 0 m s m BACK TO MAIN z 0 9 9 9 9 9 ^ A ^ ^ ^ z z m r MZ Pa, 1 BACK TO MAIN a3 W z 0 nnnnnnnn*nnn*n***nnn****nnnn**nnnnnnnnnu mmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmmo BACK TO MAIN 0 Z Io ' O ' m 0 0; II x 0 b I 0 C 'd I dl Ul I- != 'E 5 0 r v) 00 r d w 0 2z0 r 0 a ..Q) nmc, h BACK TO MAIN Q) a0 m) BACK TO MAIN 3M EnvironmentalLaboratoryReport No. E00-1851 Appendix D: Selected Chromatograms A representative set of chromatograms from the present study is included in this Appendix. Page 71 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOO45.D Report Date: 08-Nov-2000 14:14 Page 1 3 M Environmental Lab Data file : \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOO45.D Lab Smp Id: Inj Date : 04-NOV-2000 00:37 Operator : DDW Inst ID: hil1ary.i Smp Info : MeOH Misc Info : Comment : Method : \\Etshillary\D\Data\HllO3OO\HllO3OOa\PFOAllO3.m Meth Date : 08-Nov-2000 14:12 Wright Quant Type: ISTD Cal Date : 03-NOV-2000 15:20 Als bottle: 100 Cal File: HILL0015.D D i l Factor: 1.00000 Integrator: HP Genie Target Version: 4.04 Compound Sublist: all.sub Processing Host: WW19507 Page 72 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data Fils: \\Etshillary\D\Data\Hil030OW110300s\HILLOO45.D Page 2 \~t~hi1lary\D\Data\H110300\H110300a\HILL00 1 2.0; 1.9; 1.8: 1.7: 1.61 1.5: 1.4: i: i 1.3: ; . , 1.2: 1.1: 1.0: 0.9: 1 0.8: 0.7: :J. . . . i . . . . i . ' ' ` i . . . . i i . . 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Hin Page 73 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOQ46.D Report Date: 08-Nov-200014:14 Page 1 x 3M Environmental Lab Data file : \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOO46.D Lab Smp Id: Inj Date : 04-NOV-20000 0 : 5 5 Operator : DDW Inst ID: hil1ary.i Smp Info : 00028-97-00 pH7 Mise Info : Comment : Method \\Etshillary\D\Data\HllO3OO\HllO3OOa\PFOAllO3.m Meth Date : 08-Nov-200014:12 Wright Quant Type: ISTD Cal Date : 03-NOV-2000 15:20 Cal File: HILL0015.D Als bottle: 1 Dil Factor: 1.00000 Integrator: HP Genie Target Version: 4 . 0 4 Com-pound Sublist: all.sub Processing Host: WW19507 Page 74 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File$ \Vtshill~rj\MData~ii0300VO3~a\HILLOO46,D 8.81 8.41 8.0: 7.6: 7.21 6.8: 6.41 6.0: 5.64 5.21 ; 4.8: i 4*4i '- 4.0: . 3.6: 3.2: 2.8: 2.4; 2.01 1.6i 1.21 0.8: 0.44 \\Etshillary\D\Data\Hl'lO3OO\HllO3OOaWILLW46.D Y iPFBs Ion 299.00- 6.0; $ A 6.0; 4.0; ~ 3.0; P.Oj .- 7.0 . . . . . , . . ., . . .. , . . . . 7.0 8.0 8.5 9.0 fl Page 2 Page 75 of 99 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-1851 Data File: \\Etshi~lary\D\Data\HllO3OO\HllO3OOa\HILLOO47.D Report Date: 08-Nov-2000 14:14 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\Hl~O3OO\HllO3OOa\HILLOO47.D Lab Smp Id: Inj Date : 04-NOV-200001:14 Operator : DDW Inst ID: hil1ary.i Smp Info : 00028-97-01 pH7 Misc Info : Comment : Method : \\Etshillary\D\Data\HllO3OO\HllO3OOa\PFOAllO3.m Meth Date : 08-Nov-2000 14:14 Wright Quant Type: ISTD Cal Date : 03-NOV-2000 15:20 Cal File: HILL0015.D . Als bottle: 2 Calibration Sample, Level: 11 Dil Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 campounds WANT SIG MASS AMOUNT8 CAL-AMT ON-CQL RT EXP RT REL RT RBSPONSB (ng/mL) (ng/mL) Page 76 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshi11ary\D\Data\H110300\H110300a\HILL0047.D 8.8: 8.41 8.0; 7.6: 7.21 6.8: 6.4; 6.0; 6.6: 5.2: , 4.8{ i 4.4+ :. 4.01. 3.6: 3.21 2.a: 2.4; 2,o: 1.6; 1.2: 0,8( 0.4; Day0 SUI-pH7 . . ... .. i I) 1 . .- ~ Ion 299.00 6.01 2-01 i.0: ,... .,... ., . ... , .. .. , . ... 7.0 7 3 8.0 8.5 9.0 Hin 75 PFOR 5.0; " 3.01 >2.01 1.0: . . . . . I . . . , . . . , . . . . , . . . . , . . 8.5 9.0 , 9.5 10.0 10.5 Hin P-e 2 Tt% I> It 1 Page 77 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOO55.D Report Date: 08-Nov-2000 14:15 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOO55.D Lab Smp Id: Inj Date : 04-NOV-200003:42 Operator : DDW Inst ID: hi1lary.i Smp Info : 00028-97-09 pH7 Misc Info : Comment : Method : \\Etshillary\D\Data\HllO3OO\HllO3OOa\PFOAllO3.m Meth Date : 08-Nov-2000 14:15 Wright Cal Date : 04-NOV-200003:42 Quant Type: ISTD Cal File: HILL0055.D Als bottle: 10 Calibration Sample, Level: 19 Dil Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 Page 78 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data FI1.t \\Etshill.r~VKData\Hl~O3OOW110300.\HILLOO55.D \\Etshi11ary\I)\Data\H110300\HllO3OOaWILLOQ65.D Page 2 0.8; 0.71 0.6; 0.0: 0.4; 0.2; . . .I . . . . .1 . . . . . . . . . . . . . . . . 6 . . . i ' i' i. 4 ' i ' Hin 1 A'"' I 6I " ' ' io' 1. . . 78 PFOA nin I o n 413.Wm 0.2: . . , . . . . , . . . . , . . . . , . . . . 8.5 9.0 9.1 10.0 d.4' Hin Page 79 of 99 ~~ BACK TO MAIN 3M EnvironmentalLaboratoryReport No. E00-1851 Data File: \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOO27.D Report Date: 08-Nov-200014:13 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOO27.D Lab smp Id: I n j Date : 03-NOV-200019:03 Operator : DDW Inst ID: hil1ary.i Smp Info : 061500-PFOA-019 Misc Info : Comment : Method : \\Etshillary\D\Data\HllO3OO\HllO3OOa\PFOAllO3.m Meth Date : 08-Nov-200014:12 W r i g h t Quant Type: ISTD Cal Date : 03-NOV-2000 15:20 Ala bottle: 11 C a l File: HILL0015.D Dil Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4 . 0 4 Processing Host: WW19507 Page 80 of 99 ~~ BACK TO MAIN 3M EnvironmentalLaboratory Report No.E00-1851 Data Film: \\Etrhillary\OV)atrW10300\HllO3OOa\HILL0027,D 8.8: 0.4: : 8.0: D8yO MMixBlpnk-pH7 \~tshi11ary\D\Data\HllO3OO\HllO3OOaWIUC I I t 7.6: ~ .... > 7.21 6.8: 6,4{ 6.01 6.6{ 5.2: .. 3.61 t 3.21 2.8: 2.4: Page 2 9 10 11 12 Page 81 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOO28.D Report Date: 08-Nov-2000 14:13 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOO28.D Lab Smp Id: In] Date : 03-NOV-2000 19:22 Operator : DDW Inst ID: hil1ary.i Smp Info : 061500-PFOA-020 Misc Info : Comment : Method : \\Etshillary\D\Data\HllO3OO\HllO3OOa\PFOAllO3.m Mqth Date : 08-Nov-2000 14:12 Wright Quant Type: ISTD Cal Date : 03-NOV-2000 15:20 Cal File: HILL0015.D Als bottle: 12 Dil Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 compouod. 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I . , O . 0 . .I.d b' u " Page 2 Page 83 of 99 BACK TO MAIN 3M EnvironmentalLaboratory Report No.E00-1851 -. . . ,,_- - "."_.I - Data File: \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOO29.D Report Date: 08-Nov-200014:13 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\HllO3OO\HllO3OOa\HILLOO29.D Lab Srnp Id.: I n j Date : 03-NOV-200019:40 Operator : DDW Inst ID: hil1ary.i Smp Info : 061500-PFOA-021 Misc Info : Comment : Method : \\Etshillary\D\Data\HllO3OO\HllO3OOa\PFOAllO3.m Meth Date : 08-Nov-200014:12 Wright Quant Type: ISTD Cal Date : 03-NOV-200015:20 Cal File: HILL0015.D Ale bottle: 13 Dil Factor: 1.00000 Integrator': HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 Page 84 of 99 ~~ BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\EtrhillaryU)\DataWll0300\HlO3OOa\HILLOOZ9.D 1.6; .--. . .. .. 1.64 1.4: 1.3; 1.24 1.1: 1.0; ;: 0.7; 0.6f 0.5; 0.4: 0.3; 0+2{ 0.1; II I pace 2 c II 11 \I Page 85 of 99 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\HllO3OO\Hl1O3OOc\HILLOlO3.D Report Date: 08-Nov-2000 13:56 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\HllO3OO\HllO3OOc\HILLOlO3.D Lab Smp Id.: Inj Date : 04-NOV-2000 18:33 Operator : DDW I n s t ID: hil1ary.i Smp Info : MeOH Misc Info : Comment : Method : \\Etshillary\D\Data\HllO3OO\HllO3OOc\PFOAllO3.m Meth Date : 08-Nov-2000 13:54 Wright Quant Type: ISTD C a l Date : 04-NOV-2000 11:08 Cal File: HILL0079.D Als bottle: 100 Dil Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 CwrpoundS QUANT BIG MASS -TIOI?S ON-COLKlW3 FINAL RT EXP RT REL RT RESWNSE (ng/mC) (ng/mL) Page 86 of 99 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-1851 Data File: \Vtrhi1laryVr\Data\H11030OW1lO3OOcWILLOl~3.D 1.9. 0: D a y 109 MeOH SolventBlank __.-- .__ _ _ I.?! 1.6: \\Etshillary\D\Dati\HllO~OO\HllO3OOc\HILLOlO3 Page 2 Page 87 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\HllO3OO\HllO3OOc\HILLOlO4.D Report Date: 08-Nov-2000 13:56 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\HllO3OO\HllO3OOc\HILLOlO4.D Lab Smp Id: In] Date : 04-NOV-2000 18:51 Operator : DDW Inst ID: hil1ary.i Smp Info : 00028-97-00 pH7 Misc Info : Comment : Met hod : \\Etshillary\D\Data\HllO3OO\HllO3OOc\PFOAllO3.m Meth Date : 08-Nov-2000 13:54 Wright Quant Type: ISTD Cal Date : 04-NOV-2000 11:08 C a l F i l e : HILL0079.D Ale bottle: 1 Dil Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Vexsion: 4.04 Processing Host: WW19507 cornpounde QUANT SI0 MASS CENTR RATIONS ON-COLUMN FINAL RT EXP RT RXL RT RESWNSE (W/mL) (ng/mL) Page 88 of 99 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-1851 Data File: \\EtshillaryU)\Data~liO3O~~ilO3OOcW~LLO~O4.D 7.5; - 7.3; 7.0; -, 6.8: 6.5; 6.3; 6.0; 5.q 5.5; 0.3; 5.0i 4.8; , 4.5; 4.3; ' 4.0: i 3.ai '3 4 n - 3.34 3.0; 2.81 24 2,3: 2.0: Le! 1.5; 1.3: i.oi 0.0; 0.5: 0.3: I / 1 I I L, Page 89 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File:: \\Etshillary\D\Data\HllO3OO\HllO3OOc\HILLOlO5.D Report Date: 08-Nov-2000 13:56 Page 1 3 M Environmental Lab Data file : \\Etshillary\D\Data\HllO3OO\HllO3OOc\HILLOlO5.D Lab Smp Id: Inj Date : 04-NOV-2000 19:lO Operator : DDW Inst ID: hil1ary.i Smp Info : 00028-97-01 pH7 Misc Info : Comment : Method : \\Etshillary\D\Data\HllO3OO\HllO3OOc\PFOAllO3.m Meth Date : 08-Nov-2000 13:56 Wright Cal Date : 04-NOV-2000 11:08 Quant T y p e : ISTD Cal File: HILL0079.D Als bottle: 2 Calibration Sample, Level: 11 Dil Factor: 1.00000 Integrator : HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 CaapoundO ~........~1.~.....11.1.11~ * 1 PFBS 7 5 PEQA QUA" SIG MASS 1.11 299 413 R-_ T__ 8.248 9.479 EXP RT REL RT -=s=DP ===I-. 8.248 (1.000) 9.479 (1.149) .-RESWNSB ....=. 933019 84002 AMOUNTS CAL-AMT ON-COL (ng/mL) (ng/mL) 1--11.. . - 1 . 158.000 15.0000 27.59 Page 90 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data F i l e : \\Etshi1laryVI\Data\Hll0300\H110300o\HILLolo5.D 7+5t 7.3; 7.0: 6.8; 6.5; 6.3; 6.0; 5.8; 5.6; 9.3: 5.0: 4.8: 4.5: mym sui-pn7 L \\Etshi1lary\D\Drtr:Hll0300\HllO3OOo\HIUO~~ $ 3.6: 4 3.3; 3.0; 2.8:; 2.53 2.3j 2.0; 1.8j 1.6; 1.3; 1.0; 0.8; 0.0; 0.3: 1 1 !Ion 299.00 7.0: 6.0; 5.0; 4.01 3.0: 2.0; 1.0: L ......................... 7-11 8.0 8.5 9.0 9.5 75 PFOCI Page 2 Page 91 of 99 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\HllO3OO\HllO3OOc\HILLOll3~D Report Date: 08-Nov-2000 13:57 Page 1 3M Environmental Lab 5 . Lab Smp Id: Ini Date : 04-NOV-2000 21:38 OpGratoi : DDW Inst ID: hil1ary.i Smp Info : D0028-97-09 pH7 Misc Info : Comment : Method : \\Etshillary\D\Data\HllO3OO\HllO3OOc\PFOAllO3.m Meth Date : 08-Nov-2000 13:57 Wright Quant Type: ISTD Cal Date : 04-NOV-2000 21:38 Cal File: HILL0113.D Als bottle: 10 Calibration Sample, Level: 19 Dil Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: WW19507 compounas 1 PFBS 75 Pma QUANT SI0 MASS 299 413 RT EXP RT REL RT RESWNSE 8.230 9.479 8.230 (1.000) 9 . 4 7 9 (1.152) 927764 3050552 zlMouNTs ' CAL-AMP ON-COL (ng/laL) (ng/mL) 158.000 999.000 1012 Page 92 of 99 - BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 1 . 2.4: 2.3: 2.2: 2.1: 2.0< 1.9: 1.8: 1.7; 1.6; 1.0; 1.4: ; 1.33 j : 1.2; 1.1; 1.0: 0.9: 0.8: 0.7; 0.6: 0.6; 0.4: 0.3; 0.2:: 0.1: 67.,00'< Day109 Std9-pH7 . _ _ - -- --- = -__* I! P r i-, 5.0: 4.0: 3.0: 2.0: 1.0; ......................... 7.0 7.1 8,O 8.6 9.0 in 75 P r n II> 0.8: 0.6.i 0.4: . 0.21 , .- . ;.i.S9.OHi 9.5. 10.0 10.5 .. Page 93 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \\Etshillary\D\Data\HllO3OO\HllO3OO~\HILLOO97.D Report Dat.e: 08-Nov-2000 13:55 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\HllO3OO\HllO3OOc\HILLOO97.D Lab Smp Id: In] Date : 04-NOV-2000 16:41 Operator : DDW I n s t ID: hil1ary.i Smp Info : 061500-PFOA-271 Misc Info : Comment Met hod : : \\Etshillary\D\Data\HllO3OO\HllO3OOc\PFOAllO3.m Meth Date : 08-Nov-2000 13:54 Wright Quant T y p e : ISTD Cal Date : 04-NOV-2000 11:08 Cal File: HILL0079.D Als bottle: 53 Dil Factor: 1.00000 Integrator.: HP Genie Compound Sublist: all-sub Target Version: 4.04 Processing Host: WW19507 WANT SI0 _---HRSS 299 413 --... RT EXP RT REL RT RESFONSS .51 ==.E== =/..11 1-- 8.250 8 . 2 4 9 (1.000) 927163 Compound N o t Detected. CONCBIJTPRTIONS OI?-cOLmlu FINAL (ng/U&\L) (ng/mL) 11-1-.1 ..---I11 158.000 Page 94 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data File: \~Etshill~ry\MData\Hii0300W110300c\HILLOO~7.D 7.0; 7.5; 7.31 7.0; 6.8; 6.5; 6.3: 6.0; 5.0; 5.5; 5.3; 5+0j 4.8: 4.5; 4.3i 4.04 ! 3.0: 3.5: 3.3; 3.01 2.8; 2.5: 2.3i 2.0; Le: 1.5; 1.3: 1.0: 0.8; 0.5; 0.3: , DsylO9 M.trixBI.ak-pH7 __ . \\Etshillary\D\Data\HllO3~O\Hll~3OOo~HIU~O 1 4 t Ion 299.Wd Pagr 2 Hn Page 95 of 99 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E00-1851 Data File: \\Etshi~lary\D\Data\HllO3OO\HllO3OOc\HILLOO98.D Report Date: 08-Nov-2000 13:55 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\HllO3OO\HllO3OOc\HILLOO98.D Lab Smp Id: Inj Date : 04-NOV-2000 17:OO Operator : DDW Inst ID: hi1lary.i Smp Info : 061500-PFOA-272 Misc Info : Comment : Met hod : \\Etshillary\D\Data\HllO3OO\HllO3OOc\PFOAllO3.m Meth Date : 08-Nov-2000 13:54 Wright Quant Type: ISTD C a l Date : 04-NOV-2000 11:08 Als bottle: 54 C a l File: HILL0079.D Dil Factor: 1.00000 Integrator: HP Target Vexsion :Gen4i- e04 Processing Host: WW19507 Compound Sublist: all.sub ....--__..._. C ~ O U n d S * 1 PWS .11..-_---1-111 75 PFOA QUANT S I 0 MASS 299 413 RT == 8.249 9 499 EXP RT REL RT ===I-- 8 2 4 9 (1.000) 9 4 9 9 (1.151) RESPONSE I.------ 924895 602602 W-TIONS ON-COLUMN (ng/mL) 111111.1 158.000 167.470 FINAL (ng/mt) *1*.1-. 167.5 Page 96 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 Data F i l e : \\EtahillaryU1\D~ts\HllO3~\H110300c\HILL~O7~.D 7.8; 7.5; , 7.3; 7.01 6.8i 6.51 6.31 6.0i 5.8; 5.5; 5.3: 5.01 4.81 4.5: , 4.31 ' 4.0: ! 3.8: ' 3.51 ' 3.3; 3.06 2.84 2.5; 2.3: 2.0: 1.8: 1.5: 1.3: 1.0; 0.8: 0.5: 0.3; Dny109 MatrixBlnnkSpSpilrcd-PH7 \\Etshi1l~ry\D\D~ta\H110300\Hll03~c\HILL0098.D 2 -c I> ! i P r, 11 k , PaLR 2 75 PFOA " 2.0; 1.5; 1.0: 0.5:. . .,, . . ". , . . . . , . . . . , . . . . , . . 8.5 9.0 9.5 10.0 10.5 Page 97 of 99 BACK TO MAIN 3M EnvironmentalLaboratory Report No. EOO-1851 Data File: \\Etshillary\D\Data\HllO3OO\HllO3OOc\HILLOO99.D Report Date: 08-Nov-2000 13:56 Page 1 3M Environmental Lab Data file : \\Etshillary\D\Data\HllC13OO\HllO3OOc\HILLOO99.D Lab Smp Id: In] Date : 04-NOV-2000 17:19 Operator : DDW Inst ID: hil1ary.i Smp Info : 061500-PFOA-273 Misc Info : Comment : Method : \\Etshillary\D\Data\HllO3OQ\HllO3OOc\PFOAllO3.m Meth Date : 08-Nov-2000 13:54 Wright Quant Type: ISTD Cal Date : 04-NOV-2000 11:08 Cal File: HILL0079.D Als bottle: 55 Dil Factor: 1.00000 Integrator: HP Genie Compound Sublist: all.sub Target Version: 4.04 Processing Host: W 1 9 5 0 7 Canpounaa ~ . 1 1 . . . . . 1 ~ 1 . 1 . . . . . 1 I . 1 I - I - p c 1 PFBS I5 PPOA WANT SIG MASS --=_ 299 413 RT == E 250 9 500 EXP RT =I=--- 8 249 9.499 REL RT ==---(1.000) (1.152) -TION6 ON-COW ----... RBSPOUSE 1 (ng/mL) - . 1 1 . . 1 - 925297 158.000 2146703 651.301 FINAL (ng/mC) --(..-I- 651.3 Page 98 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00-1851 i Data File: \~Et~illary~\D~ta\t1110300\HllOJ00cWILLO09~.~ Pqe 2 1.7; 1.6: . -. 1.8f 1.4; 1.3; 1.2; 1.1; 1.0: I . 78 PFOA p 1.2: 1.0: ~ 0.6: 0.4; 0.2: ..,.... ~ ....,.... .... 6.8 9.0 9.5 Id.0 id.5' Hln Page 99 of 99