3M Environmental Laboratory Report No. E00 1851 Study Title Hydrolysis Reactions of Perfluorooctanoic Acid (PFOA)

Data Requirement: Based on OPPTS: 835.21 10 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 /den tifica tion 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 Reactions of Perfluorooctanoic Acid (PFOA) Study Identification Number: E00 1851 This study does not fully comply with the requirements of the US EPA Good Laboratory Practices (GLP) Standards at 40 CFR Part 792 (TSCA). However, many GLP standards were used in the development of the analytical method (Appendix A), and many of the quality assurance procedures followed in this study were based on the practices described in the GLP documentation.

Sbonsor Representative Date Page 3 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 Inspection Dates Quality Assurance Statement Date Reported to Management I Study Director Phase Study Title: Study Identification Number: E00 1851 Hydrolysis Reactions of Perfluorooctanoic Acid (PFOA)

The following table provides details of the audits performed by the 3M Environmental Laboratory Quality Assurance Unit (QAU).

I 3/ 2/ 0 1 I Data and Draft Report I 3/ 2/ 01 I 3/ 2/ 01 I I 3/ 26 30/ 01 I Data and Draft Report I 3/ 30/ 01 I 3/ 30/ 01 I 3/ 30/ 0, QA U Representatid ' 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 Personnel and Contributors ....................................................................................... 6 Location of Archives ............................................................................................................. 7 Summary .............................................................................................................................. 8 Introduction .......................................................................................................................... 9 Summary of Kinetics Model ............................................................................................... 10 Materials and Methods ....................................................................................................... 11 Chemical Characterizations .......................................................................................... 11 Sample Analysis ............................................................................................................ 12 Deviations ...................................................................................................................... 12 Results and Discussion ..................................................................................................... 13 Sample Preparation ...................................................................................................... 11 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 ...................................... 1 1 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 Observed Rate Constant at 50" C 8.1 x IO ' (day ') Summary Calculated Calculated (20) Calculated Rate Half Life Minimum Half Constant at 25" C at 250 Life at 25" C (day''') (years) (years)

8.1 x 235 92 We report here the results of our study of the hydrolysis of perfluorooctanoic acid (hereafter, PFOA). Our methods are described below and in Appendix A to this work; our results are based on the observed concentrations of PFOA in buffered aqueous solutions as a function of time. 3M's Environmental Laboratory staff developed the study procedures: they are based on EPAs OPPTS Guideline Document 835.21 I 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 analytical technique was high performance liquid chromatography with mass spectrometry detection (HPLC/ MS). Table 1 summarizes the results of the study.

During this study, we prepared and examined samples at six different pH levels from 1.5 to 1 1 .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.

The mean value and precision of PFOA concentration measurements provide a second estimate of t, he PFOA half life, presented in Table 2.

Table 2. Summary of Results Based on the Mean and Precision of PFOA Measurements Maximum Maximum Calculated Possible Rate at Calculated Half Life I 50° C 4 I I 1 Rate at 25" C at 25° C 2.0 x 10 2.0 x 10 2 97 (day") (day') (years)

Page 8 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 I n t rod uct ion 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+ H I H Page 9 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 Summary of Kinetics Model A full mathematical description of the kinetics model employed in this study is presented in Appendix 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" compound PFOA in dilute, appropriately buffered aqueous solutions. Equation 1 describes the estimated half life (? vi), in terms of the estimated total parent hydrolysis rate ip (see Appendix 8, Equation BIO):

Eq. 1 We determined the quantity cp from the experimental data as described in Appendix B. To determine the relevant concentration ratios at each pH level (see Equations B8 and B9), we used either the data corresponding to "Day 0" (t = 0) or the earliest available data achieving the data quality objectives of the analytical method.

A second half life estimate (see Equation B37) is available from the mean p and standard deviation 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" (k 3") 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 Chemical Lot Numbe? Physical Description Materials and Methods TCR 00930 30, Lot 332 TCR 99030 28, Lot 101 White powder White powder Details of the characteristics of the test materials, sample preparation techniques, and analytical methods are presented in Appendix A (ETS 8 212.0, "Preparation of Perfluorooctanoic Acid (PFOA) Hydrolysis Samples in Buffered Solutions and Analysis by High Performance Liquid Chromatography with Mass Spectrometry Detection.") A summary of these items is provided below, as well as a description the known deviations from the procedures of Appendix A. 3M prepared and analyzed the samples included in this study between June 15 and November 12,2000.

431 Molecular Weight (gm mole ') 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 quantitative standards used to quantify them. For this reason, and because the related calculations involve only ratios of the compound concentrations (see Appendix B, Equations 88 and B36), the resulting rate and half life estimates are largely independent of the material purity levels.

317 Table 3. Characterizations of Test and Reference Substances I PFOA (Ammonium Salt) I PFBS (Ammonium salt) I P I I Source I 3M ICPlPCP Division I 3M Specialty Chemicals]

perfluorobutanesulfonate A 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 containing the internal standard perfluorobutanesulfonate (PFBS) and frozen. The resulting PFBS concentration in all these samples was 158 ng/ ml; the resulting PFOA concentration in the spiked samples was 143 ng/ ml above the original sample concentratian. After the appropriate incubation times, subsets of the sample vials were removed from the incubator and then spiked (as required), diluted, and frozen as Page 11 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. 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/ methanol solvent gradient) and an ALS Model G I 322A degassing module. An ALS Model G1316A column heater maintained the column temperature at 40° C, 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 41 3, respectively. We processed the resulting data using the computer program Target@ NT Genie Integrator. Further analytical details, including the gradient elution program, instrument and detector parameters, and performance specifications, are presented in Appendix A.

Deviations No deviations from the procedures defined in the analytical method (Appendix A) were noted during the study. All calibration and sample results that failed to meet the data quality objectives of the method (and were excluded from further analysis) are noted in the following sections.

Page 12 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 Results and Discussion Data Qualii Objectives (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 to charge (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 = 1 1 .O failed to meet this data quality objective. No least squares determinations of a slope are possible in this case, so we have excluded all the pH = 11 .O data from further consideration. Finally, the "Day 14" samples at pH = 1.5 (061500 PFOA 075 through 061500 PFOA 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@ Excel@ ' 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 50° C were extrapolated to 25° C by dividing by a factor of 10; this approximation is valid for reactions with Arrhenius heats of activation near 18 Kcal/ mole. 2 Data Summary and Discussion The LOQ is defined as the concentration of the lowest (accepted) standard in the calibration set for which the known concentration exceeds 400% of the indicated solvent blank level (see Appendix A). During this study, the LOQ for PFOA was 25 ng/ mL. Results for the internal standard (PFBS) were very consistent throughout the study. The percent relative standard deviations of the measured values, calculated for each of the four pH levels discussed here (1.5, 5.0, 7.0, and 9.0), ranged from 1 to 2%.

Figure 2 illustrates the concentration ratios for the four pH levels versus time. Table 4 presents the results of the 50° C rate determinations based on these data.

Figure 2. Observed PFOA Degradation for Various pH levels.

" I 0.04 1 * . I .

._ : .. .

1 __ 4 f. . 0.12 0.14 0.16 1 1 a I I 1 0 20 40 60 80 100 120 Time (days)

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 5.0 7.0 9.0 1.7 x 1.5 x 1 .8 ~ 1.1 x 597 76 664 244 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.

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 I Observed Rate Constant at 50" C 8.1 x IO" Percent (20) Rate Constant Uncertainty at 50" C (day ') Calculated Rate Constant at 25" C (day1) 8.1 x Calculated Half Life at 25° C 235 (years) Calculated (20) Half Life Minimum at 25" C (years) 92 Page 15 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 Figure :3. Pooled (pH = 5.0, 7.0, and 9.0) PFOA Data and Slope Regression.

0.05 CI 0 P  0.00 B C  0 Solid Line: y = 8.08E 05~ + 1.06E 03 R2 = 7.49E 02 0 Dashed Lines: 20 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 A t (days) 109 In both Equations 3 and 4, the mean PFOS concentration (p,) and standard deviation ( op) can be either molar or mass quantities. Table 6 presents the results of the calculation.

Maximum Maximum Calculated Observed Rate at Calculated Half Life 50" C Rate at 25" C at 25" C PP 0,

653 7.0 2.0 x IO' 2.0 x I O + 2 97 (ng/ ml) (nglml) (day ') (day I) (years)

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 50° C and extrapolated the results to 25° C. We included six different pH levels in the study, though data from two of these pH levels (3.0 and 11) failed to meet the data quality objective for matrix spike recovery. We also rejected the data obtained for pH = 1.5 because ion pairing led to artificially low concentrations for all the incubation periods. Our results for the remaining pH levels (5.0, 7.0, and 9.0) indicate no clear dependence of the degradation rate of PFOA on pH. From the data pooled over these three pH levels, we estimate that the hydrolytic half life of PFOA at 25° C 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: 835.21 I O : Hydrolysis as a Function of pH," U. S. EPA Office of Prevention, Pesticides and Toxic Substances, publication number 71 2 C 98 057, January 1998.

p. 131, 1962. Experimental Physical Chemistry", F. Daniels, et al., McGraw Hill Book Co. (New York),

Page 19 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 Signatures 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 Perfluorooctanoic Acid (PFOA) Hydrolysis Samples in Buffered Solutions and Analysis by High Performance Liquid Chromatography with Mass Spectrometry Detection."

This Appendix presents the analytical method employed in this study.

Page 21 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 I ! I "

~MENVIRONM ENTAL LABORATORY METHOD PREPARATION OF PERnUOROOCTANOIC ACID (PFOA) HYDROLYSIS SAMPLES IN BUFFERED SOLUTIONS AND hJAL, YSIS BY HIGH PERFORMANCE LIQUID ~OMATOGRAPHY WITH MASS SPECTROlMETRY DETECTION 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 mdAnalysis by WLC/ MS Page 1 of 16 Page 22 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 I k 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. Compatible analytes. PFOA and PFBS samples may be prepared and analyzed by this method. Acceptable matrices. Aqueous buffered solutions ranging from pH 1.5 to 1 1 .O are accqtable. Method Performance. This method is defined as performancebased (see Section 14). 1.2 1.3 1.4 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 kperature requirement o f f 0.1 "C has been relaxed (it is impossible to hold this tight of temperature and open the incubator to take out samples.) Oxygen is to be excluded (according to the OPPTS methodology) to minimize bacterial growth. However, the 50° C temperature used in the present study is forbidding to most mesophillic organisms and the pH dependence for bacterial growth is different than that observed for most chemical reactions that occur in water. Aliquots of PFOA solution are added to sample vials that contain 5 mL of buffered solution of pH 1.5,3.0,5.0,7.0,9.0, or 11.0, Appropriate quality control samples are prepared. Sample vials are tightly capped and placed into an orbital incubator/ shaker at 50 f 3 "C and 100 f 50 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 15 minutes. 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 3M Environmental Laboratory Report No. E00 1851 I t . . r.__ .  ,  ,

3.0 DEFINITIONS 3.1 Method blank. The method blank determines if there is contamination of the matrix. It 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 is prepared identically to other samples, but it does not contain analyte (see Section 12.1.1). It is used alone and in conjunction with a method spike to detect accidental contamination (see Section 14.3). Method spike. A method spike is a spiked method blank (see Section 12.1.1) used to establish that the sample preparation method and analytical method would quantitatively detect target analyte in the method blank. (see Section 14.6). Solvent (methanol) blank. To isolate instrument contamination, pure methanol is analyzed. If the instrument is contaminated, analyte will be detected in the solvent blank. (see section 14.4). Sample triplicates. Samples are prepared in triplicate for each time point and pH, and are analyzed identically (see Section 12.1.1). The averaged result represents the PFOA concentration for that time point and pH. Sample spike. A sample spike confim 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 concentration in all samples and standards through the entire measurement process. Precision. Precision is the degree of agreement between individual sample results. It is usually expressed as a standard deviation. Bias. Measurements are biased if they are consistently high or low (a systematic error), as compared to a known value. Calibration standard. A calibration standard is a solution containing a known concentration of analyte. A series of calibration standards is used to calibrate analytical instrument response, producing a calibration curve to determine analyte concentrations in samples. Continuing calibration verification (CCV) or Check standard. 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 compared to the calibration curve to ensure that the calibration curve is valid for all samples over time, that the instrum ent has not drifted out of calibration. Dilution. A miscible solvent is added to all samples to 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 concentration predicted by the calibration curve, 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 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 I / ." ~

..  * __

100. Residuals for linear calibration curves can be determined using Excel. For non linear calibration curves, the following equation should be used to determine a residual.

4.0 WARNINGS AND CAUTIONS 4.1 Health and safely warnings 4.1.1 4.1.2 4.1.3 Wear the proper lab attire for all parts of this procedure. Wear appropriate gloves and proper eyewear at all times. For sample preparation and whenever possible, use solvents in the hood. 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 42.2 4.2.3 4.2.4 Rinse all glassware for standards preparation with MeOH and acetone and dry, to reduce the possibility of contamination. Prepare enough fresh HPLC mobile phase to analyze all samples. Do not allow the HPLC pump to run dry. Ensure that there is ample memory on the computer hard drive to save all run data. 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). 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). 5.2 6.0 EQUIPMENT 6.1 6.2 6.3 Analytical balance sensitive to 0.0001 g Sh; dcer/ incubator capable of maintaining a temperature of 50 k 3 OC 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 G13 16A or equivalent Dionex IonPac@ NG 1 column, 35 mm x 4.0 mm, 10 pn dime& packing, or equivalent 6.4 ETS 8 212.0 PFOA Hydroiysis and Analysis by HPLUM Page 4 of 16 Page 25 of 99 BACK TO MAIN 6.5 6.6 6.7 6.8 6.9 6.10 7.0 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 7.10 3M Environmental Laboratory Report No. E00 1851 ~. I. " I a .

Mass spectrometer. Hewlett Packard LCMSD, or equivalent, capable of operating in the selected ion monitoring mode 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. Corning Model 308 pH/ Temperature Meter with 3 in 1 gel filled combination electrode (pH/ reference/ temperature), or equivalent. The pH meter must be calibrated with suitable buffer standards (e. g. pH 4.0,7.0 and 9.0  Mallinckrodt or equivalent) as recommended by the manufacturer for this broad of a pH range. Refrigerator, capable of maintaining 4 f 3 "C, or a freezer capable of maintaining 20 f 10 OC Data system. A PC computer capable of simultaneously controlling the HPLC system and recording and processing signals from the detector Data analysis sohare. Hewlett Packard ChemStation@, Version A 6.03 or higher, or Target Software.

SUPPLIES AND MATERIALS  Vials, 40 mL VOA (I CHEM or equivalent) Crimpcap autovials, 1 .5 d Labels Graduated pipets, glass, disposable, 1 mL to 10 mL Pasteur pipets, glass, disposable Hamilton Gastight@ syringes (precision f 1% of total volume), lo@ to 1000 pL Volumetric flasks, lo, 2 5 , loo, 1 000, and 4000 mL. Beakers, glass, various sizes Automatic pipettor, capable of dispensing 10 to 5000 pL Miscellaneous equipment as needed 8.0 RE. 4GENTS AND 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 dihydrogen phosphate (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 Perfluorooctanoic acid (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 BACK TO MAIN 8.3 8.4 8.5 8.6 8.7 8.8 8.2.1 8.2.2 8.2 3 8.2.4 8.2.5 8.2.6 82.7 8.2.8 3M Environmental Laboratory Report No. E00 1851 I ,. . ~

.,

Ammonium acetate stock solution. Dissolve approximately 3.9 g CH3C02; NH, in MeOH to a total volume of 100 mL to give approximately 500 mM CH, C02 NH4. 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. 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. Hydrochloric acid (HCI) stock solution. Add approximately 8.6 mL. of concentrated HC1 to approximately 600 mL LW, dilute to a total volume of 1 L to give approximately 0.1 M HC1. Sodium hydroxide (NaOH) stock solution. Dissolve approximately 4.0 g of solid NaOH in LW to a total volume of 1 L to give approximately 0.1 M NaOH. 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). Borax stock solution. Dissolve approximately 9.54 g of N~ B40,~ 10H20 in LW to a total volume of 1 L to give approximately 0.025 M N5t2B40,. 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,. PFOA test analyte solution. Dilute 2 mL of PFOA stock solution (Section 8.2.2) with MeOH to a total volume of 10 mL to give approximately 2,000 pg/ mL, PFOA. PFOA spike solution. Dilute 0.5 mL of PFOA stock solution (Section 8.2.2) with MeOH to a total volume of 10 mL to give approximately 500 p g /d PFOA. PFBS diluting solution. Dilute 400 pL of PFBS stock solution (Section 8.2.3) with MeOH to a total volume of 4 L to give approximately 200 ng/ mL PFBS. Chromatographic solvents 8.6.1 Chromatographic solvent A. Dilute 10 mL of ammonium acetate stock solution (Section 8.2.1) LW to a total volume of 1 L to give approximately 5 mM CH, CO,* NH,. Chromatographic solvent B. Dilute 10 mL 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,. 8.6.2 Calibration buffers for pH meter. Use commercially available pH meter calibration buffers of pH 4.0,7.0, and 10.0 (Mallinckrodt or equivalent) as recommended by the manufacturer for this broad of a pH range. 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 a) Dissolve approximately 10.2 g of potassium acid phthalate (KHP) with approximately 600 mL of LW water in a 1 L volumetric flask. b) Add approximately 223 mL of HC1 stock solution (Section 8.2.4). 8.8.2 Hydrolysis buffer pH 3.0 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 I I c) Adjust the pH to 3.0 with either HC1 stock solution (Section 8.2.4) or NaOH d) Bring to a find volume of 1 L with LW.

a) Dissolve approximately 10.2 g of potassium acid phthalate (KHP) with 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 d) Bring to a final volume of 1 L with LW.

a) Add approximately 500 mL of potassium &hydrogen phosphate stock 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 d) Bring to a final volume of 1 L with LW.

a) Add approximately 500 mL of borax stock solution (Section 8.2.7) to a 1 L b) Add approximately 46 mL of HCl stock solution (Section 8.2.4). c) Add LW to a total volume of approximately 950 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.

a) Add approximately 500 mL of sodium bicarbonate stock solution 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 (Section 8.2.5). e) Bring to a final volume of 1 L with LW. stock solution (Section 8.2.5).

8.83 Hydrolysis buffer pH 5.0 approximately 600 mL of LW in a 1 L volumetric flask.

stock solution (Section 8.2.5).

8.8.4 Hydrolysis buffer pH 7.0 solution (Section 8.2.6) to a 1 L volumetric flask.

stock solution (Section 8.2.5).

8.8.5 Hydrolysis buffer pH 9.0 volumetric flask.

8.8.6 Hydrolysis buffer pH 11.0 (Section 8.2.8) to a 1 L volumetric flask.

9.0 SAMPm HANDLING 9.1 Retard the times that samples were initially prepared, removed fiom the incubator, placed in the fkeezer (when applicable), removed from the hezer (when applicable) and subsequently diluted, using the fluorochemical degradation (hydrolysis) analysis sample preparation sheet (Attachment B). All samples for the same pH group should be analyzed together. RefXgerate or freeze them if necessary, and dilute them immediately preceding the analysis.

10.0 QUALITY CONTROL 10.1 Sa: Section 12 for directions on preparing quality control samples.

ETS 8 2 12.0 PFOA Hydrolysis and Andysis by HPLC/ MS Page 7 of 16 Page 28 of 99 BACK TO MAIN 102 10.3 10.4 10.5 10.6 10.7 10.8 11.0 3M Environmental Laboratory Report No. E00 1851 Calibration standards. Analyze a complete series of calibration standards before and after each analytical run for use as calibration curve. At the discretion of the analyst, t h i s complete series may be run more often in the d y t i c a l run. Continuing calibration venfiation (CCV). A CCV sample should be analyzed after no more than 20 sample injections. A single calibration standard or a complete series of such standards (for use as a calibration curve) will satisfy this requirement. Method blank. Analyze a minimum of one method blank per time point per pH (e. g., Day 42, pH 7.0). Solvent blank. Analyze one solvent blank before and after every calibration curve as well as before and after every CCV. Sample triplicates. Prepare and analyze all hydrolysis samples in triplicate to determine analysis precision. Sample spikes. Prepare a sample spike for each pH and time point used in the study. Final (diluted) spike concentrations should approximate a mid range calibration standard. The sample spike sample should be analyzed immediately following the sample triplicates to which it corresponds. Internal standards. Aliquots of PFBS stock solution (Section 8.2.3) are added to calibration standards to give a final internal standard concentration of approximately 158 ng/ mL PFBS. Samples should also contain approximately the same concentration of PFRS. CALIBRATION AND STANDARDIZATION 11.1 11.2 Standard preparation. Prepare at least five calibration standards of approximately 25 to 1000 ng/ mL PFOA, containing approximately 158 ng/ mL PFBS internal standard. Standard curve. Relate the ratio of the analyte peak area of the calibration standards to the internal standard peak area, using linear regression software. If calibration ratios are inconsistent, external standard calibration may be used. Consult the Team Leader or designated supervisor for recommendations before using external calibration.

12.0 PROCEDURES ETS8 2 12.0 PFOA Hycirolysis and Analysis by HPLUUY Page 8 of 16 Page 29 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 . 1 .. .. ~, ... ..... ... ._ .._....._..._. .. ...,_.._I ..... . ,. ._

Analyte X Calibration standards 12.1 Sample preparation and hydrolysis 12.1.1 The following table summarizes sample preparation.

Diluting solution Buffer containing Spike internal standard X X  Methanol only Incubate /shake Methodblanka I  I X I X I  Continued Calibration verification (CCV) X X X

Triplicate I X I X 1 X I .  Solvent blank Sample Duplicate   _  X X X  X X X Sample spikeb Method spikeC  I x X X X X  X X X  I x   I x X 12.1.2 Determine the number of time points and corresponding samples to be analyzed. Each time point should have six vials per pH: sample, duplicate, triplicate, sample spike, method spik, and method blank. 12.1.3 Obtain the appropriate number of 40 mL VOA vials with caps, and the partitioned cardboard box they were shipped in. It will be helpll to use a separate box to hold the vials for each time point. 12.1.4 Prepare sample preparation worksheets (Attachment B), 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. 12.1.5 Add 5 mL of the appropriate buffer solution to all of the labeled vials. Always recap each vial immediately to minimize solvent evaporation. 12. l. 6 Using a 10 pL Gastight' syringe, add 15 pL of PFOA 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 12.2 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 separate box to hold the vials for each time point. 12.1.8 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 samples h 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 spik vials (see Section 12.1 A). Recap the vials tightly, and invert them several times to mix.

autovial. Cap the vials. 12.1.14 Aliquot approximately 1 mL of each sample into the appropriately labeled 12.1.15 Transfer the vials to the HPLC autosampler. HPLC set up 123.1 Review instrument method 1 101 PF0A. M. Note that the following instrumentation set up procedures apply to Hewlett PacbdAgilent HPll 00 equipment only. 12.2.2 For each analysis, ensure the appropriate HPLC column is in the instrument (Dionex IonPacdPNG l, 35 mm x 4.0 mm, 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 complete the analytical sequence. 12.2.4 Place the samples in the autosampler tray and construct a sequence table with calibration standards, calibration check standards, and solvent blanks. 12.2.5 Verify that all samples and standards are positioned correctly. Enter sequence information: sample or standard ID, method name, and one injection per sample. 12.2.6 Save sequence as analysis date (e. g., on September 14,2000 save sequence as 091400. s). Save data to a subdirectory labeled with analysis date (e. g., 091400). 12.2.7 Set the post sequence command macro to shut the system down (" STANDBY" on HP systems). 12.2.8 Use the following solvents (see Section 8.6), gradient, and instrument settings (or equivalent  note that the following instrumentation set up procedures apply to Hewlett PackardAgilent Hpl 100 MSD equipment only). <IP_ADDRESS> Chromatographic solvent A (Section 8.6.1). <IP_ADDRESS> Chromatographic solvent B (Section 8.6.2). <IP_ADDRESS> 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 ,

<IP_ADDRESS> 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 1 100 MSD equipment only.)

* M I I+ is the molecular ion with a loss of proton. For example, the molecular weight of PFBS is 300, when it loses a proton, it assumes a negative charge and has a mass 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 BACK TO MAIN ~

3M Environmental Laboratory Report No. E00 1851 I * . . , . ~

_ ~

.._

12.5 Sample analysis 12.5.1 After setting up the HPLC, the mass spectrometer, and the autosampler, analyze a CCV after every 20 sample injections, and the calibration standards at the end of the sequence. To check for analyte carry over, run solvent blanks after the highest calibration standard as well as before and after the ,CCV (see Section 10.0). 12.52 Identify the electronic acquisition files with an appropriate prefix. Do not exceed five characters if the sequence contains more than 99 lines.

13.0 DATA ANALYSIS AND CALCULATIONS 13.1 Peak evaluation. Anal@ and internal standard peaks must be symmetrical  if peak tailing is observed, consult team leader or designee for direction. They must be identified by measuring their retention times and by the 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 calibration methodology. 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. Percent recovery. Calculate the percent of PFOA recovered from each of the sample spikes using the following equation. 13.2 133 x 100% [ PFOA] dcrecred in mpie spike  [ PFOA] detected in comspondig ~mnpl.

[ PFOA] in SompIe spike, added via s p ~e % Recovery =

13.4 Sample triplicates. Use the following equation to calculate the relative standard deviation (RSD) for the triplicate samples.

x 100% Standard Deviation Mean Concentration RSD =

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 determined by plotting ETS 8 212.0 PFOA Hydolysis and Analysis by HPLUM Page 12 of 16 Page 33 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 .I. .. .; .... . . .I . .. ._. , .. . . .. , .. . . , , . ,. . , . . . .

I Ln (E;) versus negative elapsed time ( 0,

where the subscripts t and 0 refer to analyte concentrations at time t and at r = 0, respectively. The slope of the resulting line is k.

14.0 METHOD PERFORMANCE 14.1 Calibration curves. An acceptable coefficient of determination (R') for linear curves is 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 0.9!? 0 or greater. Accuracy should be verified, particularly at upper and lower calibration limits by calculating the residuals residuals generated in curve fitting must be between 0 and 25%. Alternative methods 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 parameters are not met, consult team leader or designee for direction. Continuing calibration verification (CCV). Analyte concentration must not differ by more than 25% of its expected value, relative to the initial calibration curve. Accept only those samples analyzed before the last accepted calibration verification. Reanalyze remaining samples with a new calibration curve. Method blank. If the contamination levels are greater than 5% for any particular target, consult the Team Leader or designated supervisor for recommendations. For example, if PFOA were targeted at 500 ppb, contamination should be less than 25 ppb. In those instances where the 5% level would be below the lowest point 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). 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 af3Fecting the LOQ (see Section 14.8), the run should be stopped. This indicates that the instrument is contaminated and should be thoroughly cleaned. Pay particular attention to the electrospray source. The column and tubing may need to be replaced. When the solvent blanks are improved, reanalyze the sequence beginning at the last acceptable CCV or calibration curve, starting with a new calibration curve. Sample triplicates. If RSD precision values are 25% or greater, consult the Team Leader or designated supervisor for recommendations. Sample spikes. If sample spike recoveries are less than 70% or greater than 130%, conlsult the Team Leader or designated supervisor for recommendations. Residuals. The acceptance criterion for the residuals is less than or equal to f 25%. If the residuals are higher than this, consult team leader or designee for direction. No calibration curve will be accepted with residuals outside this range. Limit of Quantitation. The limit of quantitation (LOQ) is equal to the lowest standard in the calibration curve that gives a response of more than four times that of the test anadyte in the solvent blanks. Method Spike. If method spike recoveries are less than 70% or greater than 130%, corlsult the Team Leader or designated supervisor for recommendations.

ETS 8 212.0 PFOA Hydrolysis anddnalysis by HPLUM Page 13 of 16 Page 34 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 .

15.0 POILUTION PREVENTION AND WASTE MANAGEMENT 15.1 Dispose of sample waste by placing it in high or low BTU containers as appropriate. Use broken glass containers to dispose of glass pipettes. 15.2 Collect HPLC solvent waste in the satellite accumulation can. When the satellite can is full, empty it into the flammable storage drum in the hazardous 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 16.3 16.4 16.5 16.6 16.7 16.8 17.0 Sign and date all graphics, and label with the instrument ID. Immediately fill out the hydrolysis sample preparation worksheet completely, including all initials and dates. Print chromatograms and internal standard reports for all analyses. Print calibration tables and curve information, and store them in the raw data file. Store hydrolysis sample preparation worksheets in the raw data file. Enter all standard preparation information in the standards prepmation logbook. Make a photocopy of the logbook page and include the copy in the raw data file. Archive electronic data to appropriate media when necessary.

ATTACHMENTS 17.1 17.2 Attachment A. Representative Chemical Structures Attachment B. Hydrolysis Sample Log sheet 18.0 REFERENCES 18.1 Fate, Transport and Transformation Test Guidelines OPPTS 83. i. 21 IO: Hydrolysis as a Function ofpH; EPA 712 C 98 057; U. S. Environmental Protection Agency, Office of Prevention, Pesticides and Toxic Substances, U. S. Government Printhg Office: Washington, DC, 1998. CRC Handbook of Chemistry and Physics, 1 st Student Edition; We&, R. C., Ed., CRC Press: Cleveland, OH, 1988; p. D 87. 18.2 19.0 AFWECTED DOCUMENTS None.

20.0 REVISIONS &ision Number Reason for Revision ETS 8 212.01 PFOA Hydolysis andAnalysis by HPLUMS Page 14 of 16 Page 35 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 I .

Attachment A. Representative Chemical Structures R' = NH, ' in this study, but may also be Li', Na', K+, H'.

1. PFOA (Perlluorooctanoic Acid) h4W (anion) = 413 2. PFBS (? erlluorobutanesulfonate) MW (anion) = 299 ETS 8 212.0 PFOA Hydrotysis anddnalysis by HPLC/ US Page 15 of 16 Page 36 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 I /

Attachment B. Sample Preparation Sheet Fluorochemlcal Degradation (Hydmiysls) Aniilysb ETS 8 2 12.0 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 mathematical description of the kinetics m'odel employed 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).

(81) k, @ n, A, + Yd P + H 2 0 (m = 1 toN)

(82) k h A, +H, O Ym2 (m= 1 toN)

where the general symbols Y,, and Ym2 represent 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 dp=($ P nm kpm] dt Equation 84 may be directly integrated to 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 Environmental Laboratory Report No. E00 1851 N k, nm k,, .

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 Po and later values P measured at later times t , one can calculate and plot the (linear) quantity [ In (P/ Po 11 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, first order differential changes in the product concentrations 4, (using Equations 82 and B6) are dA, = ( n, kpmP  kAmAm) dt = ( nmkPmPO e kp  kAmA,) dt (B11)

and the (first order, non separable) differential equation governing the product concentrations is %+ k, Am = nmkPmPO e 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) = nmkPmPO e kpt .

The general solution A, to Equation 61 2 is contained in where and IS( t) dt  IS( t') dt'  k h l d t  e k b t e e e

Q( t) dS( t') dt' dt + C = n, kprnPo~ ekht e kptdt + C I There are two cases of Equation B18 to consider. In the circumstance that k,, = k, , 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,)

A, ekpt = nmkPmPO t + C and, using the initial condition A,( t = 0) = A, , the specific solution to Equation18 is (for k, = k,)

A, =( nmkPmPO t+ A, o) e kpt .

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 kp and 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 hydrolytically stable products)

A, =AmO + nrnkF'mPO (~~k ~t )

k P B4. Relationships Between the Parent and Compound Concentrations Equations 87 and 824 can be combined to obtain (for hydrolytically stable products)

Page 42 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 so that (for hydrolytically stable products)

or (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 I 1 )

h (l +X )=X  x2 1 + 1 x3 x4+ 1 ..... 4 L 3 and Equation B23 becomes (for hydrolytically stable products and I m Page 43 of 99 BACK TO MAIN 3M Environmental Laboratory Report No. E00 1851 or (for hydrolytically stable products and lzflrn << Po I m I k t g P 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, = AfQ. 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 concentrations of 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/:) min . 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 measured for the mth product have the mean value p,,, and standard deviation om, 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 standard deviation 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)

r 1 1  A t Po In( 2) A r Q + Z2orn] . (B35)

Below LOQ Cons tan t Tv2 2 = P (k, 1

The reader Should note that Equations B34 and B35 are valid only when both 1) the products are hydrolytically stable and 2) the concentrations of all the potential products are measured.

B7. Parent Half Life Estimates Based on the Experimental Precision of Parent  Concentrations In certain experiments, the hydrolytic parent remains at an essentially constant 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 kp . If the set of concentrations measured for the parent have the mean value pp and 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 increased from the initial value pp  op to the value pp + op at time t = A t . This reasoning suggests that the following estimate of the maximum parent hydrolysis rate is appropriate:

(for esseritially constant parent concentrations with mean value pp and standard deviation (5,, )

2%

CLp A t kp I (kp),, = .

Under these circumstances and assumptions, the experimental data indicate that the parent half life TI'; is greater than the value (T v i ) . as follows: rnm (for essentially constant parent concentrations with mean value pp and 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 50° C = 323 K. Of greater interest are the corresponding results for the environmentally important temperature 25° C = 298 K.

When the Arrhenius activation energy for a reaction is AHa, Equation B38 B' provides the following relationship between the hydrolysis rates (kl and k2) for that reaction at two different absolute temperatures (T, and T2):

where R = 'I .99 x AH,= 18 KcaVmole, the rate ratio k,/ k, at the corresponding temperatures TI =298 K and T2= 323 K is Kcal mole ' K ' is the ideal gas constant. Using the valueB2 = exp{ 18 [ 1 L]} = exp( 2.35) = 0.095 :k 1.99~ 10" 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 25° C than at the chosen experimental temperature of 50° C. Accordingly, the rate reactions reported here for the temperature 25° C are ten times lower than those measured at 50" C, and the hydrolysis half life estimates reported here for 25° C sarnples are ten times longer than those calculated from the 50° C experimental data.

References to Appendix B:

B1 I. N Levine, "Physical Chemistry," McGraw Hill (New York), pp. 498 501 (1978).

F. Daniels, et al., "Experimental Physical Chemistry", McGraw Hill (New York), p. 131 (1962). 82 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.

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