Document 85vLZzww4bYer4gbxoMKyO54Z

AR22-W* 0 STABILITY IN WATER (HYDROLYSIS) TEST SUBSTANCE Identity: N2-(N-methylperfluorooctanesulfonamido)-ethyl acrylate; may also be referred to as N-MeFOSEA, or MeFOSEA. (2-Propenoic acid, 2[[(heptadecafluorooctyl)sulfonyl]methylamino]ethyl ester, CAS # 25268-77-3) Remarks: Material is an amber, waxy solid, coded THAR3F2. Sample purity was not characterized. METHOD Method: OPPTS 835.2110 GLP (Y/N): No Year completed: 1999 Type: Abiotic Stock solution and test sample preparation: A 10,730 mg/L stock solution of MeFOSEA in acetone was prepared. Test solutions were then prepared by adding 10 uL of the stock solution to 1.0 mL of five solutions individually buffered to pH values of 1.5, 5.0, 7.0, 9.0, and 11.0. This calculates to a 107.3 mg/L concentration of MeFOSEA in each buffered solution. Remarks: Modification of the test method included using a wider range of pH and longer time periods for a more complete understanding of the behavior of the test substance. RESULTS pH impact on Hydro ysis Half-lives at 50C pH Half-life (days) 1.5 9.4 5.0 17.8 7.0 9.9 9.0 9.3 11.0 7.9 pH impact on Hydrolysis Half-lives at 25C** pH Half-life (days) 1.5 94 5.0 178 7.0 99 9.0 93 11.0 79 ** Extrapolated from values for 50C. 000026 Remarks: The analysis showed that concentration of MeFOSEA declined in all aqueous pH buffered solutions with time. The degradation rates fit second order kinetics better than first order kinetics. Nevertheless, the report authors assumed first order kinetics and calculated the half-life after six time periods. Generally, the calculated half-life increased with time. The half-lives reported above are averages of the half-lives calculated after each of the six time periods. The report does not explain how the extrapolation was made from the half-lives at 50C to 25C. Author states assumed AG = 15-18 kcal/mole which would give one order of magnitude increase in T 1/2 per 25C. CONCLUSIONS This study indicates that MeFOSEA is hydrolytically unstable under environmentally relevant conditions. Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 DATA QUALITY Reliability: Klimisch ranking 1 REFERENCES Study conducted by the 3M Company, Environmental Laboratory, St. Paul, MN. OTHER Last changed: 5/17/00 000027 3M Environmental Laboratory Report No. W 1868 Study of the Stability of MeFOSEA in Aqueous Buffers Using Gas Chromatography with Atomic Emission Detection 3M Environmental Laboratory Contact Thomas L. Hatfield, Ph.D. Building 2-3E-09 935 Bush Ave. St. Paul, MN 55144 Phone: (651) 778-7863 FAX: (651) 778-6176 Requester 3M Company Report Date: June 14,1999 Report Summary A study was conducted on 2-(N-methylperfluorooctanesulfonamido)-ethyl acrylate (MeFOSEA) to determine its half-life under environmentally relevant hydrolysis conditions. Its behavior was examined in aqueous solutions buffered at five pHs: 1.5, 5.0, 7.0, 9.0, and 11.0. The analysis was performed according to 3M Environmental Laboratory Method ETS-8-90.0, with modifications that followed the U.S. Environmental Protection Agency's Fate, Transport and Transformation Test Guidelines document OPPTS 835.2110, "Hydrolysis as a Function of pH*. Modifications included using a wider range of pH and longer time periods for a more complete understanding of the behavior of MeFOSEA. Data were collected at the start of the study (Time 0) and after 0.94, 1.92, 6.72, 13.90, 20.71, and 27.77 days of sample agitation and incubation at 50C. After incubation, isopropyl alcohol (IPA) was added and the aqueous samples were extracted with hexane. The hexane extracts were dried with anhydrous sodium sulfate and injected into a gas chromatograph with an atomic emission detector (GC/AED). The analysis showed that concentrations of MeFOSEA declined in all aqueous pH buffers with time. Half-lives increased with time within each pH data set at 50 C, averaging 9.4 days at pH 1.5,17.8 days at pH 5.0, 9.9 days at pH 7.0, 9.3 days at pH 9.0, and 7.9 days at pH 11.0. Extrapolation of the 50 C data to room temperature (25 C) resulted in a half-lives averaging 94 days at pH 1.5, 178 days at pH 5.0, 99 days at pH 7.0, 93 days at pH 9.0, and 79 days at pH 11.0. These results indicate that MeFOSEA is hydrolytically unstable under environmentally relevant conditions. Attorney Ciient/W ork Product Privileged Do N ot Diacloae Do N ot Copy Page 1 o f 13 000028 3M Environmental Laboratory Report No. W 186S 1 INTRODUCTION..................................................................................................................... 3 Figure 1. Generic Hydrolysis Reaction.................................................................................. 3 Figure 2. MeFOSEA and Possible DegradationProducts...................................................... 5 2 SAMPLE RECEIPT................................................................................................................ 5 3 HOLDING TIMES.................................................................................................................... 5 4 METHODS- ANALYTICAL AND PREPARATORY.............................................................. 6 4.1 Standards:......................................................................................................................... 6 4.2 Sample Preparation and Analysis Dates:........................................................................ 6 5 ANALYSIS.............................................................................................................................. 7 5.1 Calibration......................................................................................................................... 7 5.2 Blanks............................................................................................................................... 8 5.3 Surrogates......................................................................................................................... 8 5.4 Matrix Spikes................................................ - .................................................................. 8 5.5 Laboratory Control Samples.............................................................................................8 5.6 Sample Related Comments..............................................................................................8 6 DATA SUMMARY................................................................................................................... 8 Figure 3. Representative GC/AED Chromatograms.............................................................. 9 Figure 4. MeFOSEA Concentration Versus Time................................................................ 10 Table 1. Fit of Second-Order and Linear Equations to MeFOSEA Degradation D ata...... 10 7 CONCLUSION...................................................................................................................... 11 Table 2. Half-Lives of MeFOSEA Versus Tim e................................................................... 11 8 DATA/SAMPLE RETENTION..............................................................................................11 9 SIGNATURES....................................................................................................................... 12 10 APPENDICES....................................................................................................................... 13 Appendix A: EPA Guidelines Appendix B: MeFOSEA Preparation and Analysis Method Appendix C: Sample Preparation Logsheets Appendix D. GC/AED Chromatograms (see separate bound volumes) Appendix E: Spreadsheets: GC/AED Results Appendix F: Spreadsheets: Calculation of Kinetic Parameters Attorney Client/W ortr Product Privileged Do N ot Dlaeloee 000029 Do N ot Copy Page 2 o f 13 3M Environmental Laboratory Report No, W 18B8 1 In tro d u ctio n ' Hydrolysis is one o f the main mechanisms by which organic compounds, both natural and synthetic, decompose in the environment. Testing for hydrolysis of compounds is relevant to determining the persistence and environmental fate of many pesticides and polymers such as polyesters, poiyethers, and polyamides, and for determining shelf life of products containing such compounds (Appendix A, EPA Guidelines). Hydrolysis is a reaction between some species (in this case o f the type R-CO-X), with water that results in the substitution of X with OH: F ig u ra i. Generic Hydrolysis Reaction OO Il , II R -- C --X H- H20 -- - R -- C -- OH 4- HX R = some hydrocarbon or fluorocarbon material X halogen, OR, or NR In dilute solutions the rate law for chemical loss by a hydrolysis reaction is shown with the following equations, where "ester" signifies the starting material. It is important to note that the equation must be modified in solutions that are not dilute. d [ester] dt % d'esteri or kt ln The rate constant k is the negative slope of the line fit to a plot of the natural log of the fraction of compound remaining at time t, versus time. The half-life of the compound at a specific pH is related to the rate of hydrolysis by: Attorney ClientAMxk Product Privileged DoNotO teetoem 000030 Do N ot Copy Page 3 o f 13 . ! 1/2 _ -- 0.6k 93 3M Environmental Laboratory Report No. W 1868 With the above equations and considerations as guides, the study monitored the loss of MeFOSEA over an extended period of time to determine the overall rate of reaction. A predicted product of hydrolysis of MeFOSEA was N-MeFOSE alcohol. Analytical difficulties were encountered in attempting to monitor the appearance of this reaction product in an effort to confirm the degradation route. The primary goal o f the study was to determine, to a first approximation, the hydrolytic stability of the MeFOSEA. Since levels of MeFOSEA steadily declined over time, data collection stopped after 28 days. Samples of MeFOSEA were prepared in buffer solutions of pH 1.5, 5.0, 7.0, 9.0, and 11.0 according to published guidelines (Appendix A and references therein). A solution of MeFOSEA in 1.0 mL of each buffer was prepared by adding 10 pL of a 10,730 ppm solution of MeFOSEA in acetone. This corresponds to 107.3 ppm MeFOSEA in each buffer. Significant environmental pHs were chosen (e.g. pH 1.5 is physiologically relevant as stomach pH in case of ingestion). The addition of a pH 11.0 buffer in the present study was made to better understand the behavior of MeFOSEA in basic solutions. The solvent chosen for quenching was hexane, used to extract remaining MeFOSEA from the aqueous matrix. This allowed injection o f material onto the gas chromatograph. Previous studies have shown that analysis of diluted aqueous buffers by gas chromatography results in chromatographic anomalies and column degradation. In this study, biodegradation of MeFOSEA is ruled out for two reasons. First, the 50C temperature used will impede degradation due to microbial growth in the buffered media. This temperature is hostile to the growth of most mesophillic microorganisms, the type usually inhabiting laboratories. Thermophlllic microorganisms, which do thrive at 50C and above, typically inhabit environments such as hot springs and hydrothermal vents at the bottom of tectonically active ocean basins, but not laboratories. Also, one can hypothesize that the maximum loss rate of MeFOSEA would occur at a different pH if accomplished by hydrolysis versus biodegradation. Since acids or bases typically catalyze hydrolysis, hydrolysis rates are usually maximum under acidic or basic conditions and minimal at or near neutral conditions. This contrasts with the activity of microbes, which typically demonstrate maximum growth rate at or near neutral pH. Maximum rates of hydrolysis were not observed at pH 7.0 in this study. A proposed mechanism for hydrolytic degradation of MeFOSEA is shown in Figure 2. Attorney Client/W ork Product Privileged Do N o t D iacloae 000031. Do N ot Copy P a g a 4 o f1 3 3M Environmental Laboratory Report No. W 1888 Figure 2 MeFOSEA and Possible Degradation Product MeFOSEA A sample of MeFOSEA (coded THAR3F2) was obtained from C. Elsbernd, 3M Chemicals, on October 13,1998. The sample was placed into the hydrolysis storage cabinet in the 3M Environmental Laboratory. The sample receiving date, an electronic MSDS, the sample production methodology and predictive chemistries were entered into the 3M proprietary database "Hydrolysis Tracking." 3 H o m im m The samples were prepared and analyzed within the applicable holding time criteria. Attorney C lientM ork Product Privileged Do N o t D iadose 0q0032 Do Not Copy PageB o f 13 3M Environm ental Laboratory Report No. W 1868 3M Environmental Laboratory Method ETS-8-90.0 ` Determination o f the Stability of MeFOSEA in Aqueous Buffers Using Gas Chromatography with Atomic Emission Detection' was followed except where noted below. This method is presented in Appendix B. The GC/AED system used was a Hewlett-Packard (HP) 5890 Series II GC equipped with an HP 5921A AED, and an HP 7673 auto-sampler. The column used was a J&W DB5-MS, 30 mm x 0.25 mm x 0.25 pm film thickness. The oven program had an initial temperature of 50C, initial hold time of 1.0 min., final temperature of 300C, and a temperature ramp-rate of 15C per minute. 4.1 Standards: Test Analyte: 10,730 ppm MeFOSEA in acetone (ID 98086-3-16) Internal Standard: 9.324 ppm N-EtFOSE alcohol in hexane-1 % IPA (ID 98086-3-19, and ID -98060-15-16) Spiking Standard: 473.4 ppm N-MeFOSE alcohol in methanol (ID W398-1117) (This is an order of magnitude lower than the amount intended due to a calculation error.) 4.2 Sample Preparation and Analysis Dates: Time 0: 0.94 Days Samples 112398-MeFOSEA-001 to 112398-MeFOSEA-015 Prepared and immediately quenched on 11/24/98. Analysis by GC/AED was begun on 11/25/99. Samples 112398-MeFOSEA-016 to 112398-MeFOSEA-030 Incubation started at 3:30 PM on 11/23/98 Quenched at 2:30 PM on 11/24/98 Analysis by GC/AED was begun on 11/25/98 (pH 1.5,5,7) and on 11/30/98 (pH 9,11) 1.92 Days 6.72 Days 13.90 Days Samples 112398-MeFOSEA-031 to 112398-MeFOSEA-045 Incubation started at 3:30 PM on 11/23/98 Incubation stopped at 2:10 PM on 11/25/98 Analysis by GC/AED was begun on 11/26/98 (pH 1.5,5,7) and on 12/1/98 (pH 9,11) Samples 112398-MeFOSEA-046 to 112398-MeFOSEA-060 Incubation started at 3:30 PM on 11/23/98 Incubation stopped at 8:54 AM on 11/30/98 Analysis by GC/AED was begun on 12/22-23/98 (pH 1.5,5,7), and 12/1/98 (pH 9,11) Samples 112398-MeFOSEA-061 to 112398-MeFOSEA-075 Incubation started at 3:30 PM on 11/23/98 Incubation stopped at 1:02 PM on 12/7/98 Attorney C iientM tork Product Privileged Do N o t D lacloae Do n o t Copy P a g e * o f 13 000033 3M Environmental Laboratory Report No. W 1868 Analysis by GC/AED was begun on 12/23/98 (pH 1.5,5,7) and on 12/89/98 (pH 9,11) 20.71 Days Samples 112398-MeFOSEA-076 to 112398-MeFOSEA-090 Incubation started at 3:30 PM on 11/23/98 Incubation stopped at 8:38 AM on 12/14/98 Analysis by GC/AED was begun on 12/28/98 (pH 1.5,5,7) and on 12/1516/98 (pH 9,11) 27.77 Days Samples 112398-MeFOSEA-091 to 112398-MeFOSEA-105 Incubation started at 3:30 PM on 11/23/98 Incubation stopped at 9:55 AM on 12/21/98 Analysis by GC/AED was begun on 12/29/98 (pH 1.5,5,7, 9) and on 12/30/98 (pH 11) Sample quenching was completed approximately 1 hour after incubation was stopped. Sample preparation logsheets are presented in Appendix C. 5.1 Calibration Standard calibration curves were prepared using a mix of test analyte (MeFOSEA) and degradation product (N-MeFOSE alcohol). Examination o f the chromatograms revealed that the intended internal standard (N-EtFOSE alcohol) was in a region of chromatographic overlap of residual components in MeFOSEA. Thus, N-EtFOSE alcohol could not be used as an internal standard with GC/AED testing. Solvent/Standard Name Hexane solvent used IPA solvent used MeFOSEA standard N-MeFOSE alcohol standard N-EtFOSE alcohol standard Solvent/Standard Number TN-A-2009 TN-A-2102 98086-3-16 S398-331 S398-332 The calibration standard set consisted of the following: Reference # 98086-46A 98086-46B 98086-46C 98086-46D 98086-46E 98086-46F 98086-46G 98086-46H MeFOSEA (p p m ) 64.38 48.28 32.19 16.09 6.438 4.828 3.219 1.609 N-MeFOSE alcohol (ppm) 63.12 47.34 31.56 15.78 6.312 4.734 3.156 1.578 N-EtFOSE alcohol (ppm) 9.324 9.324 9.324 9.324 9.324 9.324 9.324 9.324 Attorney C lhntflM ork Product Privileged Do N ot D lte lo a e 000034 Do Not Copy Page 7 o f 13 3M Environmental Laboratory Report No. to' 1868 The standard curves were linear, with the coefficients o f determination (r2) greater than 0.990. Calibration standards were analyzed in duplicate at the beginning of every sample run. At regular intervals (e.g. after 6 - 8 sample injections) blanks consisting of hexane with 1% IPA and 9.324 ppm N-EtFOSE alcohol were analyzed. A mid-range calibration standard was periodically tested throughout each sequence. When the percent difference of amount of measured analyte was greater than + 25% from the true value, relative to the initial standard curve, the run was discarded. Only samples analyzed before the last acceptable calibration check-standard were considered as valid results. 5.2 Blanks The internal standard was a solution of 9.32 ppm N-EtFOSE alcohol in hexane/1% IPA. Approximately 1 mL aliquots were transferred to autovials and used as solvent blanks in the analysis. These blanks served as an instrumental check for analyte carryover. Acceptable values for the blanks were less than half the practical Quantitation Limit of the method {the concentration of the lowest standard used in the curve). 5.3 Surrogates No surrogate analyte was used in this analysis. 5.4 Matrix Spikes Matrix spike samples were prepared by introducing a known concentration o f the target analyte into a sample. - These matrix spike samples were carried through the entire sample preparation process. Comparison of the amount quantified from the matrix spike with that of the unspiked sample provided information on contribution of the sample matrix to the analytical results. One of the spiking solutions used was a 473.4 ppm N-MeFOSE alcohol standard. This concentration was one-tenth of that which would have been optimal. As such, the amount o f N-MeFOSE alcohol added was lower than the lowest calibration standard, precluding quantitation. Spike samples on Day 21 and Day 28 also contained 10 pL of a 10,730 ppm solution of MeFOSEA in acetone. For all the pHs extracted on Days 21 and 28, acceptable MeFOSEA recoveries of 80 to 123% were noted. The average recovery of MeFOSEA was 95%. 5.5 Laboratory Control Samples Laboratory control samples were not prepared for this analysis. 5.6 Sample Related Comments The MeFOSEA results for the Day 2, pH 7 samples were rejected, as the mid-range calibration standard that followed these samples did not pass quality control criteria specified in the analytical method (Appendix B). The 3M Environmental Laboratory developed a method for the quantitative determination of MeFOSEA using GC with atomic emission detection. This method was successful using five pH buffer matrices. Sample chromatograms are presented in Appendix D as separate bound Attorney Cllent/W ork Product Privileged Do N ot Dteetoee 000035 Do N ot Copy P a g e t o f 13 3M Environmental Laboratory Report No. W 1868 volumes. A representative QC/AED chromatogram o f a standard mixture and a sample are presented in Figure 3a and 3b, respectively. Figure 3 ______________________Representative GC/AED Chromatograms___________________ Peak retention tim es are 9 .5 4 minutes (N -M eFO S E alcohol), 10.0 minutes (internal standard), and 10.82 minutes (M eFO SEA ) a. Standard (6.438 ppm MeFOSEA, 12/22/98,7:33:14 PM) b. Sample (MeFOSEA-1.5-1-7,12/22/98,9:31:59 PM. Quantified as 5.47 ppm MeFOSEA) Attorney Client/W ork Product Privileged Do N o t D isclose 000036 Do N ot Copy P a g e 9 o f1 3 3M Environmental Laboratory Report No. W 1868 The calculated concentrations of analyte in sample, duplicate, and matrix spike samples are presented in spreadsheet format in Appendix E. These data, plotted as MeFOSEA concentration versus time in Figure 4, show that degradation of MeFOSEA is in general non linear and a function of pH. Samples from the pH 5.0 and 7.0 series can be fit equally well with either a linear or second-order equation (see Table 1). A second-order equation provides a better fit than a linear equation for the data at pH 1.5, 9.0, and 11.0. Figure 4 MeFOSEA Concentration Versus Time MeFOSEA Extract Concentration (PPM) PH = 1.5 PH = 5.0 A pH = 7.0 9.0 pH = 11.0 li So. Hour* Table 1 Fit of Second-Order and Linear Equations to MeFOSEA Degradation Data tM 2nd-0nJefS aition 1.5 v= 2 e1 flV -0.0191x +8.9477 0.9263 5.0 v - 5e1 o V -0.0097X +9.698 0.9289 7.0 v 1 e1 0 V -0.0186X +9.6171 0.9449 ____ 1_1_.0____I v= 2e10'ix2-0.0277X +9.956 V 3e10V -0.0283X +9.832 0.9719 _____0-9859 U n ter fHM tfal v= -0.0086X +8.3400 V" -0.0067X +9.5239 v= -0.0112x+9.1490 v= -0.0121X +9.0474 ___ Vs -0.0118x +8.8757 U M a rfK li 0.835 0.9153 0.9119 0.8645 ____ 0.8625 Attorney Client/W ork Product Privileged Do Not D iecloae 000037 Do Not Copy Page 10 o f 13 3M Environmental Laboratory Report No. W 1968 At the conclusion of the experiment (27.77 days), approximately 20 - 30% of the original MeFOSEA remained for samples hydrolyzing at pH 1.5, 7.0, 9.0, and 11.0. At pH 5, approximately half of the original MeFOSEA was present at the end of the experiment. Calculations of kinetic parameters are presented in Appendix F. A general trend is that the half-life of MeFOSEA increased with increasing time, especially at pH 1.5, 5.0, 9.0, and 11.0 (Table 2). This behavior doesn't match the mathematical model for a first order reaction. However, the first order approximation for a hydrolysis reaction assumes a single compound degrades to form only two distinct product species. The results shown in Table 1 indicate this assumption may not be realistic for MeFOSEA. As implied in Figure 2, the degradation of MeFOSEA may involve multiple reaction pathways. MeFOSEA is a 3M control compound, whose behavior is used to predict that of other synthetic chemistries. Overall, the results of this study are sufficient for that purpose. Table 2 Half-Lives of MeFOSEA Versus Time 0.94 1.92 6.72 13.90 20.71 27.77 2.58 ' 3.99 6.87 11.44 15.85 15.91 3 j0 4.79 5.98 16.94 27.93 22.64 28.45 3.09 .... 8.05 12.23 14.61 11.53 iliiillll 11.99 4.51 6.96 9.67 9.62 12.80 lL O 3.34 5.72 6.97 8.51 9.97 12.81 7: C onclusion The 3M Environmental Laboratory developed a method for hydrolysis and analysis of MeFOSEA. The hydrolysis study showed pH dependent half-lives which increased with time within each pH data set at 50 C, averaging 9.4 days at pH 1.5,17.8 days at pH 5.0, 9.9 days at pH 7.0, 9.3 days at pH 9.0, and 7.9 days at pH 11.0. Extrapolation of the 50 C data to room temperature (25 C) resulted in a half-lives averaging 94 days at pH 1.5,178 days at pH 5.0, 99 days at pH 7.0, 93 days at pH 9.0, and 79 days at pH 11.0. It is the conclusion of this study that MeFOSEA is unstable against hydrolysis under environmentally relevant conditions. *0 Reserve samples and all original paper data will be retained in the archives of 3M ET&SS for a period often years following the signing of the final report. Attorney CUentM/ork Product Privileged Do N ot D tadoae 000038 Do Not Copy Page 11 o f 13 c . . Thomas L. Hatfield, Ph.D., Tearfvleader 3M Environmental Laboratory Report No. W 1868 Gregory Maisel, Analyst William K. Reagen, Ph. D., Technical Reviewer Date Note: Jeanette Wink, Analyst, did the majority of the laboratory work for this project. She reviewed the original data, but has since left 3M Environmental Laboratory. Her assistance during the course of the study is appreciated. Attorney CHent/Work Product Privileged Do N ot DlecJoae 000039 Do N ot Copy Page 12 o f 13 3M Environmental Laboratory Report No. W 1868 Appendix A: EPA Guidelines Appendix B: MeFOSEA Preparation and Analysis Method Appendix C: Sample Preparation Logsheets Appendix 0 . GC/AED Chromatograms (see separate bound volumes) Appendix E: Spreadsheets: GC/AED Results Appendix F: Spreadsheets: Calculation of Kinetic Parameters S^Sif'rff58ii9S& Attorney Client/W orir Product Privileged Do N ot D ladoae 000040 Do Not Copy Page 13 o f 13 712-C-98-057, January 1998 3M Environmental Laboratory Raport No. W 1868 Attorney CHent/Work Product Privileged Do N o t D isclose 000041 Do Not Copy EPA UEnnvitierdonSmtaetnetsal Protection Agency Prevention. Pesticides and Toxic Substances (7101) EPA 7 1 2 -C -98-057 January 1998 Fate, Transport and Transformation Test Guidelines OPPTS 835.2110 Hydrolysis as a Function of pH / 000042 Introduction dpUeensvitetielcTodidpheieSssdtaagtbnueysdidEtteholniexnviiecOrosfinfusimbcoesetnnaoetnfacolePfsPr,earavonetsendecrtittioiheonsen, doPAefvegsteeetlnisoctcpiydmgeuesfiondratenoludifnseeTtesoisntxthidctahatteSahuttabehvssatettiannmbgceueeossntf, be submitted to the Agency for review under Federal regulations. Nl(CObohiOsalfhafehsEftanPieipCcodddoTteneDelehdalrbovu)el.yeftItliTh,OPooteenpheSfcsfeeuthitdePbcinOscerctiiheirtcdnovhagaeegfipalsnnPtPIegtirginrrzuooeuafignovRdtirdireaoamneannomltnacifindsoetfitneoo(harT,OnentoPPEhdxCSerPciseorooc)truednsivwqcgeoiihuhc(dmOioeierciafesPck(mPFNapCaeTneHrpnddo)opteoScseTrape)aanetsorlhsrdxaeaaRnditctoadieiofpegnSnxptuuhhieplsbaaeaautsntrrebitgemddoalduinnociDiscndnaieenite(zsivltCoaiheTnn(tFleOieosioRtspPnOlo)emP,pfffTtue4tthihhnbcS0aeeet),t OPPTTShegupiudreplionsees oisf tohamrminoinmizizinegvatrhieasteiongsuiadmeloinnegsthinettoesatinsginpgrloecesdeut roesf mtheant tmalusPtrboetepcetirofnormAegdentcoymuenetdethretdhaetaTroexqiucirSeumbesntatsnocefsthCeoUn.trSo.l EAncvtir(o1n5 U(7.SU.C.S..C2.60113)6,aentdsetqh.e).Federal Insecticide, Fyungicide and Rodenticide Act t GletoivneFrniBnmaoelanrGtdP.uridinBetliyinnge OmRfoefdilceeeam,seW: adTsihhaiilns ggt2ou0nid2,e-Dl5iCn1e22-i10s34a08v27a,oilnabtTelelhneefrtFomedaentrhdael UBu.Sl. ftp: fedbbs.access.gpo.gov (IP 162.140.64.19), or call 202-512-0132 for disks or paper copies. This guideline is also available electronically in ASCII and PDF (portable document format) from EPA's World Wide Web site (http://www.epa.gov/epahome/research.htm) under the heading " Research ers and Scientists/Test Methods and Guidelines/OPPTS Harmonized Test Guidelines." l 000043 CROinooPgndPterT(nroaSetl)iqcA8Suid3iccreo5tep.m(A2Te1ec--Sn1tCt0((sAFlI))FHoA(Rf1yp5Adpbr)Ulooi(cl.t7Syhas.bUCiis..ltSih2ta.eyC6s.0.aT1F1)hfe.3udi6sne,rcgeatutliiosdneeIqlnoi.ns)feeacpntiHisdc.iidtnhetee. nTdFoexudinctgoiScmuidbeese,ttantaecnsetds omtifoonpnHio(z.2ef)dpHOPaPtTB2Sa5ctkeCsgtr,goauunindddelO.inETeChaeDresgo4uu0irdCceeFliRnmea7t91e61ri1.a3l5H0uy0sdeHrdoylidynrsiosdlyeavssieslaoapsFianungFcuttinhocins har suitab(ble) aGnuailydtaicnacleminetfhoordm;avtaiopno--r p(r1e)ssPurree-rceuqruvies.ites. Water solubility data; chcoimhanignalphynubg(rtte2eioet)miitenewsQpsraetoueertnaedaarctlutitwfhisroyieoentilhnurrmgebetsehlsuesucelthltatcsmastonesmehmtitsohopmeuoonedlucndtnosvd.dubierslePsod.cuncrToromicebhnceeesunadrirdnte.aedhlrielseyrcdeou.,rmneTbcmluehevtreisatrtanchtiietneastltytpeggomirtuneapinddeetreexialatitslrnuuaerebpefsafosteplaacpanttslicinoeeagssf ganivceen(f3oin)r PpSarteramangdarnaauprfdhac(dtfu)orcoeufNmthoeitsniftgiscu.aidTtieohlniisnEetPeasAntd, gAounuidgteuhlseitnPe1r8ei,sli1mb9ia7ns8ae.rdy oDnramfteGthuoidds r(Hinia)ydtdahTrte(ihooceel)nynsMtvaeiisnsretdotiinnshimgosodneot--nheftes.ro(u1efbf)ostPhrtaeeunromcpneoosessfteoo,fcrrotehhmlyeemdvmraoonanliycnresie,dsaaecipgstirporalnediclsaeatvctiaooionnnnttpr,toaoaltnlhtihdnsegloiirmfapbsieuitorsbtssioictsfatedntneecscgetes.. mica(nporadHemlilccpy1a(roiu-tfiui2o)cnn)uigaAdnflo.dorwprHihprnoyoehndtctyhhersiedeotirousleylrnhoseoviygstidihrtcobroeaonerldlhmypeatseutveiensrsirotptmpiron(rpsigonneHdese.ues4dchh-tsyos9ud.)tlroIdoat bnliysdebseitueshnxecradaadmertreerignsmireeadoidsdraeaoitmtuaioctppniHodoprictnrvaoacndolatuunceadptslissatoinrtoheoninarnstt lbsiuunlletkbin(saioisdile)uidftfiSeuournperonfhnatycdredae-rctgoeorslnayidtsnriasoth,lilooeenmsdproeargcteeeiaansclelttoyhiouanisnnsswotchloaueuntlisdoosnioblsme.epnetrvieimrdoiecnstmedpernfetrd.oomTmhitinhsaismtegauyoivdreeer GlSiouowboisdnt(ag2Ln)daceebfsoinrCaitotDionorentyrfsoinPlairlAtsaioccottnaic(pseTpaSlSynCtdatAonu)dtanhariinstddsst.etaTshptehpgedluyeiddfetieonfliiinttnihioetii.nsosntesinstin4g0useiCdcFteilRoinneP.3arTtohf7e9th2foe--lToxic the Hydrolysis net exchange roeffetrhse tgoroaupreXacwtioitnh OofHaatchtheemriecaacltiRonXcewnittehr: water, with 1 00004:4 RX + HOH > ROH + HX in thiHs ysidmropllyifsiiesdrpatreo,cethsse irsagteivaetnwbhyi:ch the concentration of RX decreases second order reaction rate = k [H2O] [RX] or first order reaction rate = k [RX] bdeaxsyepcateehpsnessdercieunoldgamotoip-ofnanirrsteshhtdieoptr:rodaetthererdeceahtceetrmimoinicnaiinln, gwthhsitisecpthy. ptBheeeocoafbursseeearcvwteidaotneraristeisucspounraeslstlaeynndtt eiissncgrgiirvbeeeandt kobs --k [H2O] and can be determined from the expression Kobs = 2.303/t logxo(Co/Ct) where t = time, and Co and Ct = concentrati/o/ ns of RX at times 0 and t Tlifheeoufnthites roefactthioisn c(otinmsteafnotrh5a0vpeerthceen'dtiomfeRnXsiotno roefac(tt)imiseg)i-v1eannbdythe half- ti/2 = 0.693/kobs coetftioihrfgoleaanltnonhtciwcoe(ne3efigsO)n.ttagEohTeCnTchoeDamewmsb/EeelpRtesEhasuseuCorbf1ebde-s.Lstrtatamheaannnebnacdocycerere2e.abss.T:suteounhltrebpesyeseswdetrIafnhdonntearoecntmrteacseaboa,dnemr(oefiept)rhpmaoerArmproissvlpmooitnidyiremeeitTdndheeopaistdnrotniidinmastgilDamlarapiceiarlapeyzasliieinnsensoddoc.nwlttuhTohdaaherteoenedfcfaruieielnnsrisbevutdrtelhhasteesas ref Table 1.--Values of Rate Constants and Half-Lives for Aspirin1,2 pH K [10* se c-'] tin (h) 3 .5 .......!..................................................................... 5 .0 ............................................................................. 7 .4 ............................................................................. 9.5 ............................................................................. 11.3 ........................................................................... 0.065 0.15 0.13 0.37 16 300 130 150 52 1.2 1 Data taken at 17 C 2 Aspirin (CAS no. 5 0-78 -2 ) (2-acetylsaficyiic acid) data from L.J. Edwards, Transactions o f tha Fara day S ociety 723-735 (1950). 2 0 0 0 0 ^5 Table 2.--Values of Rate Constants and Half-Lives for Oiazinon1 10 C 20 0C 40 C 60 C pH K (10J U n K [103 t(/2 K [10s 11/2 K [103 tl/2 sec-'] (h) s e c -1] (h) sec-1] (h) sec-1] (h) 10.43 ............................................. 0.061 310 0.13 150 0.41 9.0 ................................................. -- -- 0.0059 3300 -- 7.4 ................................................. -- -- 0.00043 4400 -- 5.0 ................................................. -- 0.026 740 -- 3.1 ................................................. 0.75 260 1.6 120 6.6 48 -- -- 29 15 12 .. -- -- . -- 25 7.8 1 Oiazinon (CAS no. 333-41-5) (O,Odielhyl-i>(2-isopropyl-4-m ethyl]-6-pyrim idinyl phosphorothioate) data from H.M. Gomma et al. Residue Reviews 29:171 (1969). EmemasfoyvEoalesvlCdtyraoe,irwmf(pIiaiianeiass)bidtrneitFtalrhiiincuncTteudyroyattlmhahbwthreheplelahreaylsviirrcgeiieb3nhhss.eobftulenetulotxhtehesfTncrneoteoehcueosrfeedtbgeisOhtsnsoeaugEfiwr1lntCePo2hes.xorDdauoyfItl-gtungEsitress.hEaisnneomCc.gmamuTlLtelsheheea,deecbsaPooTefsarfoeerarrsdsttetoinsitfrnuGhf.yeleutrtTishenirhdneetaeeetsrltrueigebcnlsutoupetsmifsrdfgpeepeiusrrnlaeeiisrndnstieetehisennloeidhtnneatOehd,ts.eEehbshTCotetaihewenDvsingest/ (A) Substance: Aspirin Table 3.--Reaction Rate Constant in KPaec-1 pH 1 .2 ......................................................... 3 .0 ......................................................... 7 .0 ......................................................... 9 .0 ...................................................... ... tem pera ture, C 35-40 20 40 20 40 20 40 V mean value stand ard devi ation coeffi cient of vari ation, % range 1.013 0.080 0.556 0.205 1.339 1.278 0.056 0.112 0.033 0.004 126.2 70.3 20.1 15.9 0.3 0.109-1.916 0.040-0.119 0.477-0.635 0.182-0.228 1.335-1.341 0.309 0.160 51.7 0.196-0.442 0.953 0.006 0.6 0.949-0.957 n* of results 2 2 2 2 2 2 2 1 3 000046 Table 4.-- Half-life in hours pH tem pera ture, C mean value stand ard devi ation coefficient of variation, % range n* of results 1 .2 .......................................... !. 35-40 93.71 118.3 3 .0 ............................................. 20 40 319.7 35.4 7 .0 ............................................. 20 40 95.1 14.4 9 .0 ............................................ 20 40 72.1 20.2 (B) Substance: Diazinon 222.5 7.1 15.1 0.0 37.3 Q.1 126 10.05177.36 70' 162.3-477.0 20 30.3-40.4 20 84.4-105.6 - 14.4-14.4 50 45.7-98.5 0.0 20.1-20.3 2 2 2 (1 lab) 2 2 (1 lab) 2 2 (1 tab) Table S.--Reaction Rate Constant in 103seer1 pH 1 .2 ..................................................... 3 .0 ..................................................... 7 .0 ..................................................... 9 .0 ..................................... ............... tem pera ture, C 35-40 20 40 50 60 20 40 50 60 20 40 50 60 mean value stand ard de viation coeffi cient of vari ation, % range n* of results 30.36 2.866 9.038 5.77 36:085 0.933 0.231 0.200 1.638 1.103 2.568 0.292 2.801 8.10 0.825 '2.447 4.27 11.088 1.796 0.294 0.023 3.154 2.113 6.900 0.034 4.125 27.0 28.8 27.1 74.0 30.7 192.4 127.3 11.3 192.6 191.6 268.7 11.6 147.3 21.40-38.46 1.675-3.841 5 .7 0 8 14.165 0.85-8.58 25.53551.449 0.005-3.626 0.042-0.895 0.184-0.216 0.303-9.413 0.007-4.271 0 .0 6 4 20.955 0.268-0.316 0 .2 4 1 12.604 4 7 11 (10 labs) 3 (2 labs) 6 4 8 2 8 (7 labs) 4 9 2 8 (7 labs) t 4 000047 Table 6.--Half-life in hours PH tem pera ture, 8C mean value standard deviation coefficient of variation, % range n ' of results 1 .2 .................................. 3 .0 .................................. 7 .0 ................. ................. 35-40 20 40 50 60 20 40 50 0.672 7.27 2.25 9.00 0.57 1707.75 215.16 97.07 9.0 ................................... 60 20 40 50 60 38.68 1150.75 124.38 66.40 25.13 (C) Substance: Atrazine 0.187 2.40 0.57 11.53 0.17 1875.18 166.12 10.97 * 20.98 1395.58 102.45 7.74 25.67 27.9 0.501-0.900 33 5.0-11.5 25 1.4-3.3 128 2.24-22.31 29 0.37-0.75 110 5.3-3660.9 77 21.5-460.7 11 89.31- 104.83 54 2.0-63.5 116 4.5-2840.5 82 0.9-298.7 12 60.92-71.87 102 1.5-79.8 4 7 11 (10 labs) 3 (2 labs) 6 4 8 2 8 (7 labs) 4 9 2 8 (7 labs) Table 7.--Reaction Rata Constant in 10*sec-> pH tem pera ture, C mean value stand ard d e v i-. ation ' , Coefficient of variation, % range n* of results 1 .2 ............................................... 3 .0 ............................................... 7.0 9 .0 ............................................... 35-40 20 40 60 40 20 40 0.546 0.014 0.140 0.808 0.009 0.013 0.008 0.416 0.008 0.082 0.397 0.011 0.016 0.010 76.3 56.8 58.4 49.1 124.8 130.1 123.7 0.76-0.948 0.005-0.020 0.028-0.222 0.282-1.283 0.001-0.016 0.001-0.024 0.001-0.015 4 3 6 5 2 _ 2 Table 8.-- H alf-life in hours pH 1 .2 .................................... 3 .0 .................................... 1 7 .0 .................................... 9 .0 .................................... tern- ,, perature, C mean value standard deviation coefficient of variation, % range n* of results 35-40 20 40 60 40 20 40 54.76 1867.88 240.50 31.42 9000.15 44.36 1446.58 239.61 21.51 11033.77 1792105 24188.21 8005.35 9539.51 81.0 77.0 99.6 69.0 123.0 135.0 119.0 20.3-115.35 9 8 0 .7 3537.14 111.71696.79 15.0-68.3 1198.116802.2 8 1 7 .4 35024.7 1259.914750.8 4 3 6 5 2 2 2 5 000048 (D) Substance: Di(2-ethylhexl) phthalate (DOP) Table 9.--Reaction Rate Constant in 103sec-' PH tem pera ture, C mean value stand ard devi ation coefficient of variation, % range n* of results 3 .0 ..................... 9 .0 ..................... 7 .0 ..................... 20 20 40 60 20 40 60 40 0.048 0.040 0.166 0.084 0.073 (1.627) (0.092) 0.126 0.051 0.047 0.202 0.022 0.064 -- -- 107.8 116.7 121.8 26.3 88.8 --r -- -- 0.009-0.106 0.007-0.073 0.023-0.309 0.068-0.099 0.027-0.118 -- -- -- 3 2 2 2 2 1 1 1 Table 10.-- H alf-life in hours pH tem pera ture, C mean. value standard coefficient devi of variation, ation % range 3 .0 ............... 20 40 60 990.20 452.56 239.33 996.32 551.98 63.75 7 .0 ............... 20 40 60 40 440.30 (11.83) (208.19) (152.53) 391.35 -- -- (E) Substance: Ethyl acetate 101 / 122 V 89 -- * / 182.4-2103.5 62.25-842.86 194.25-284.41 163.57-717.02 -- -- -- Table 11.--Reaction Rate Constant in KPsec-1 pH tem pera ture, C mean value standard coefficient devi of variation, ation % range 3 .0 ................. ................... 7 .0 .................................... 9 .0 .................................... 1 20 (0.0012) 40 , (0.012) 60 (0.355) 20 (0.003) 40 (0.008) 60 (0.137) 20 (0.063) 40 (0.153) 60 (1.547) -- - -- -- - -- -- -- -- - -- -- -- -- -- -- -- - -- -- - -- -- -- n* o f results 3 2 2 2 1 1 1 n* of results 1 1 1 1 1 1 1 1 1 6 000049 Table 12.-- Half-life in hours pH 3.0 ...:.............................. 7 .0 .................................. 9 .0 .................................. tem* perature, C 20 40 60 20 40 60 20 40 60 mean value (1656) (1612.85) (54.30) (7553.1) 2511.81) (140.38) (305.55) (125.71) (12.44) standard coefficient devi of variation, ation % - - * -- - -- _/ _ - -- -- - -- -- -- range IL. -- - -- -- - -- -- -- n* of results 1 1 1 1 1 1 1 1 1 cepuoxssneucuesatdsla(lso4yn,-)tfoaidrcnscudtur, roitnrhiPgdneerrhridenyfiadlocutrritfpeoei,llxeysetsohdoilasuf.pttHtHitohheneaen,nctcdweoeshn,ttecitmchemhnepteemrktrahiaenttoaieuodntrnis,ec.st(ohif)oafwtInhwaytatedhtreerroreleiynsmsvpiaisrrinoeassnreemensgtesenienntn,etlricaaahrllgellyyem icals coiresspH(eici3)iOfiT+ch,be(aHhsey+d)c,raotaalnyldysissOisr.He-a,ctiinonwmhiacyh bcaesienfilt/uiesn' rceefderbryedactoidaics osrpebcaisfiicc sapcied fitasiinroudsntsteo(hodifrei)id:t)siemlrToephb.eeeThochaofevntihcoloeerng)raterrgsaiiuttvhiloetmisnnsgothofsefttrtharheaiegthtecetosctlnoincnseuesntb(atsarntasatstniufocmrneosiminsagrdtefheirpetseltrof-mototrreimdndeeurdalgaoaarsi(npiafsstefluoutidgnmoicoe- kob* = - slope x 2.303 rttahiabctruseoolualc(ugroitvhnet)setttmhaemneptepsureasarWetatuthrooueetfrhnedethir(irKteeti)ce's.Amtlnyrpr,oehtrietapntiriusuarscuetssircueiaslaablptllyieloontptotsoehsddispeiatbegilrneamintwionshteeitcsahthiemratrhateeteceicplotorhngoesactraacilonthnotmsfftoatrhonefta par t rputossshhiieanfospiorslnerautr,hosmala(sdidton5seefuu)dttbeccngeeriontuubshndis,iedwslueiintettnaiayetllnihrtpnchtmcaseilQearre)inctno.sudiusnceaeTbmudttlelhh1aiasit3aeintryliansmcpndrcl2pHaocuarterifpspetsosaleetievn(rhccrseedcaoied.aetnsgoone--e.sfxbttwayaoyc(sngnriiit)rtagaeathcnsalnnRuydn.atmefaiiiocpmcrdsradretsplaovtodrrnddionaeuciuvvetfceicefitsoiaudicpnbtrsuHiiehcoollsoitonftinuacyel(tnasl.esrd)ndseoMseplbboretpeoeneahafvsaeorruenetafnrhptg2eteheormm.iaar5gstcppeheehphnedniretp.es(sarirfvctTt)eouiie(ncvhf2nrigeee)thydroly- 7 000050 reacti(oiin) Sraetnessitaivnidt,y.thMeroesftorhey,dhroallyf-sliisverseaacrteioninsdfeoplelonwdenatppoafrecnotncfiernsttroartidoenr tj/2 = 0.693/kobs T(1f0h)(-i22s--) u1o0sfu~t3ahlilMsy gputeiodrmeeliintnsvei.rtohnemaepnptlailcactioonndiotifonlasbo(r<at1o0r-y6 rMes)ultusnddeerterpmariangerdapaht pcohafrehamgy(irdicairaip)olhslSy(sppfi)res(oc2vmi)fiideocaiifntstyguh.ribesSdogetvuhineidrpaebHllointehaexn)a.pdmurpteelmeaspneodrfantguaortouedrahlaagvwreaetebemreseennftomrbeeaatwsvuearerenidetry(asteoeesf the su(db)stance Diseslecsrsiptthioann 2ofxth1e0-t2esMt p, raocheadlfu-sraet.u(r1a)teIdf stohleutwioanterinsowluabteirlity of iuissn'spptrareebpplaearreaeddre. aIttefsltetehsdse atshtoalauntb1illeCiatHyst iMtsw.gorSetuaebmtesrptaentrhacaetunsrek2snoxbwet1nw0e-to2e,nbteh0e-h4yt0edsrtoCls.yotlOiucttahiloelnyr eb2aosuxrr5lee,tbrsaastuCpsuanonbdailmcasepertpisetgrdtrateoherdptaeeortsieptepaorurtetoctt,dohethnsuaatrndctioeniutag1iktgohnayaletetspaa2rasr5aett)rl.ieCltmeTh.acirhnsoeotaensrsteyeiwdlteneoevrosaettttidenesmdtghap.byetSedrluemarbtoapusltertyaret5asnic0tcaubelrseleCytsfwo, seuftoaenanrnbddloe0tnot-he4(bet0eiw/d2seateCataka,t pdisocrrlroooiblbgyle(isec2dimas)blstleeydlsoutimweshpPtoooorrurebtlpauadanfpbfrteH)ear;-tpscipoteaHarnttfaso4lm--yr.m0sai;(ysei.)dpbHMeatua7ftso.e0eurd;ri.aadUlnisfds--feepr(oHeAnf)ta9Bp.p0HuH. f'E-fsse:itrtaahttseopralHvubotuii1dfo.fs2nersp(s.iof(ta1pesn)htdyTieashle hy pared(2u)siFnogrrethaigsenptugrrpaodsee,c0h.e0m5 icMalsstaenrdiledibstuiflfleedr,ssotleurtiiloenwsastehro.uTldhebbe upffreer upaprsstie5hyatshHst.esoat:ettfuehteuoedleomdlf.fhrsbeabIehautseaqycfrusbfhdeeheiemrrrobeboeupnadlusyllsyfdosreftsiyeeedtsbcmreeoemduapmsp.neosnodrmTlounaahtettrweueintedohhrdnueepeetsrrhdaetmeeaonsutouaetnahfsnltytdhitbspteeebiordrcireeabspaciluntacioesfrhrfbieatoeeosqhgrcnreuerkrasiaoevrfpycdoeefshedmlttalewa(oetmfatwni)entl(thei2sunbaa)susgfaleottofedfrTcf0reanar.ttm1lhshbaibetilaispeernycsaHgshbttuiee1uenudima3fdfnfd.le,eiupicltreHoisa1nn.f4lsecy.mSbp.,esoehTteaimetotnnhhemsdgeere Table 13.--Buffer Mixtures of Clark and Lubs1,3 Composition 0.2 N HCI and 0.2 N KCI 47.5 ml HC1 + 25 ml KC1 diluted to 100 ml 32.25 ml HC1 + 25 ml KC1 diluted to 100 ml pH 1.0 1.2 8 000051 Table 13.--Buffer Mixtures of Clark and Luba*,2--Continued Composition PH 20.75 ml HC1 + 25 ml KC1 dlluted to 100 ml .......... 13.15 ml HC1 + 25 ml KC1 diluted to 100 ml .......... 8.3 ml HC1 + 25 ml KC1 diluted to 100 ml .............. 5.3 ml HC1 + 25 ml KC1 diluted to 100 ml .............. 3.35 ml HC1 + 25 ml KC1 diluted to 100 ml ............ 0.1 M potassium biphthalate + 0.1 N HCl 46.70 ml 0.1 N HC1 + 50 ml biphthalate to 100 ml .. 39.60 ml 0.1 N HC1 + 50 ml biphthalate to 100 ml ... 32.95 ml 0.1 N HC1 + 50 ml biphthalate to 100 ml ... 26.42 ml 0.1 N HC1 + 50 ml biphthalate to 100 ml ... 20.32 ml 0.1 N HC1 + 50 ml biphthalate to 100 m l... 14.70 ml 0.1 N HC1 + 50 ml biphthalate to 100 m l... 9.90 ml 0.1 N HC1 + 50 ml biphthalate to 100 m l.... 5.97 ml 0.1 N HC1 + 50 ml biphthalate to 100 m l.... 2.63 ml 0.1 N HC1 + 50 ml biphthalate to 100 m l..... 0.1 M potassium biphthalate + 0.1 N NaOH 0.40 ml 0.1 N NaOH + 50 ml biphthalate to 100 m l.. 3.70 ml 0.1 N NaOH + 50 ml piphthalate to 100 ml .. 7.50 ml 0.1 N NaOH + 50 ml biphthalate to 100 ml .. 12.15 ml 0.1 N NaOH + 50 ml biphthalate to 100 ml 17.70 ml 0.1 N NaOH + 50 ml biphthalate to 100 ml 0.1 M potassium biphthalate + 0.1 NaOH 23.85 ml 0.1 N NaOH + 50 ml biphthalate to 100 ml 29.95 ml 0.1 N NaOH + 50 ml biphthalate to 100 ml 35.45 ml 0.1 N NaOH + 50 ml biphthalate to 100 ml 39.85 ml 0.1 N NaOH + 50 ml biphthalate to 100 ml 43.00 ml 0.1 N NaOH + 50 ml biphthalate to 100 ml 45.45 ml 0.1 N NaOH + 50 ml biphthalate to 100 ml 0.1 M monopotassium phosphate + 0.1 N NaOH ' 5.70 ml 0.1 N NaOH + 50 ml phosphate to 100 m l... 8.60 ml 0.1 N NaOH + 50 ml phosphate to 100 ml ... 12.60 ml 0.1 N NaOH + 50 ml phosphate to 100 ml . 17.80 ml 0.1 N NaOH + 50 ml phosphate to 100 ml . 23.45 ml 0.1 N NaOH + 50 ml phosphate to 100 m l. 29.63 ml 0.1 N NaOH + 50 ml phosphate to 100 m l. 35.00 ml 0.1 N NaOH + 50 ml phosphate to 100 m l. 39.50 ml 0.1 N NaOH + 50 ml phosphate to 100 m l. 42.80 ml 0.1 N NaOH + 50 ml phosphate to 100 m l. 45.20 ml 0.1 N-NaOH + 50 ml phosphate to 100 m l. 46.80 ml 0.1 N NaOH + 50 ml phosphate to 100 ml . 0.1 M H2B02 in 0.1 M KC1 + 0.1 N NaOH 2.61 ml 0.1 N NaOH+50 mlboric acid to 100 ml .... 3.97 ml 0.1 N NaOH+50 mlboric acid to 100 ml .... 5.90 ml 0.1 N NaOH+50 mlboric acid to 100 ml .... 8.50 ml 0.1 N NaOH+50 mlboric acid to 100 ml .... 12.00 ml 0.1 N NaOH + 50 ml boric acid to 100 ml .. 16.30 ml 0.1 N NaOH + 50 ml boric acid to 100 ml .. 21.30 ml 0.1 N NaOH + 50 ml boric acid to 100 ml .. 26.70 ml 0.1 N NaOH 50 ml boric acid to 100 ml .. 32.00 ml 0.1 N NaOH + 50 ml boric acid to 100 ml .. 36.85 ml 0.1 N NaOH + 50 ml boric acid to 100 ml .. 40.80 ml 0.1 N NaOH + 50 ml boric acid to 100 ml .. 43.90 mi 0.1 N NaOH + 50 ml boric acid to 100 ml . 1.4 1.6 21..08 2.2 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.2 5.4 5.6 5.8 6.0 6.0 6.2 6.4 6.6 6.8 7.0 7.2 7.4 7.6 7.8 8.0 7.8 8.0 8.2 8.4 8.6 8.8 9.0 9.2 9.4 9.6 9.8 10.0 1 Data taken at 20 C. 2 The- pH values reported in these tables have been calculated from the potential measurements using Sorensen's standard equations (1909). The corresponding pH values are 0.04 unit higher than the tabulated values. 9 000052 Table 14.--Citrate Buffers of Kolthoff and Vleeschouwer12 Composition PH 0.1 M monopotassium citrate and 0.1 N HCl 49.7 ml 0.1 N HC1 + 5 0 ml citrate to 100 ml .. 43.4 ml 0.1 N HC1+ 50 ml citrate to 100 ml .. 36.8 ml 0.1 N HC1+ 50 ml citrate to 100 ml .. 30.2 ml 0.1 N HC1+ 50 ml citrate to 100 ml .. 23.6 ml 0.1 N HC1+ 50 ml citrate to 100 ml .. 17.2 ml 0.1 N HC1+ 50 ml citrate to 100 ml .. 10.7 ml 0.1 N HC1+ 50 ml citrate to 100 ml ... 4.2 ml 0.1 N HC1 + 50 ml citrate to 100 ml .... 0.1 M monopotassium citrate and 0.1 N NaOH 2.0 ml 0.1 N NaOH + 50 ml citrate to 100 m l...... 9.0 ml 0.1 N NaOH + 50 ml citrate to 100 m l...... 16.3 ml 0.1 NNaOH + 50 ml citrate to 100 m l.... 23.7 ml 0.1 NNaOH + 50 ml citrate to 100 ml.... 31.5 ml 0.1 NNaOH + 50 ml citrate to 100 m l.... 39.2 ml 0.1 NNaOH + 50 ml citrate to 100 ml.... 46.7 ml O .i NNaOH + 50 ml citrate to 100 m l. . 54.2 ml 0.1 NNaOH + 50 ml citrate to 100 m l.... 61.0 mi 0.1 NNaOH + 50 mi citrate to 100 ml.... 68.0 ml 0.1 NNaOH + 50 ml citrate to 100 ml.... 74.4 ml 0.1 NNaOH + 50 ml citrate to 100 ml.... 81.2 ml 0.1 NNaOH + 50 ml citrate to 100 m l.... 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4 5.6 65..08 1 Data taken at 18 C. 2 Add tiny crystal of thymol or a few milligrams of mercury .or mercuric iodide to prevent growth of molds. Table 15.--Borate Buffer Mixtures of Sorensen Composition 0.05 M borax 0.01 N HCI (ml) (ml) 5 .2 5 ..... ........... 5 .5 0 ................. 5 .7 5 ................. 6 .0 0 ................. 6 .5 0 ................. 7 .0 0 ................. 7 .5 0 ............... . 8 .0 0 ................. 8 .5 0 ................. 9 .0 0 ................. 9 .5 0 ................. 1 0.0 0 ............... 1 0 .0 ................. 9 .0 ................... 8 .0 ................... 7 .0 ................... 6 .0 ...... ............ 4.75 4.50 4.25 4.00 3.50 3.00 2.50 2.00 1.50 1.00 0.50 0.00 0.00 0.00 0.00 0.00 0.00 0.01 N NaOH (ml) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.0 1.0 2.0 3.0 4.0 Sorensen (18 C) 7.62 7.94 8.14 8.29 8.51 8.08 8.80 8.91 9.01 9.09 9.17 9.24 9.24 9.36 9.50 9.68 9.97 Walbum, pH at 10 C 40 C 7.64 7.98 8.17 8.32 8.54 8.72 8.84 8.96 9.06 9.14 9.22 9.30 9.30 9.42 9.57 9.76 10.06 7.55 7.86 8.06 8.19 8.40 8.56 8.67 8.77 8.86 8.94 9.01 9.08 9.08 9.18 9.30 9.44 9.67 70 C 7.47 7.76 7.95 8.08 8.28 8.40 8.50 8.59 8.67 8.74 8.80 8.86 8.86 8.94 9.02 9.12 9.28 ccodeodinsn)t,tcirlelaa(neBntdtid)ro,anttsshitoeesnrhipol(euTusrelewedessattnOteosaProtvPlaweuTixltiSaticohbenl8eedss3t.0efto.rTh7rihle8mee4l0eboc,suhfsfWeeftrmehareoitcefmsarul0ebs.d0sosiu1tluuabmnbsMtcialeiantodycsrd,eheohsdsuhahlaldotfkouetblhidteef.labesTsaemkhtupdermlioascestyoitoeonhldnv ed in 10 000053 otsinhhneolmyuhlaydinkdirbncoeaglyslesueipssssuptbhrthsoetacanesnsocsl1e.ustpioewnricsteh. nTtl,ohweanudwsaettheoerf ssoomlluvixebenidltitysso.hloTvuehlnedtsanmoistourinnetcteoromffemrseoelnvwdeienthdt otssethrumodbupiulee(dfCrdfae,)btruesrsheuyosssu,etledsGdmealfaolbeisresdswcvsoaoatrrelrrarseytie.liiinlpzeAgte,udlolom.urg-tSclialfttosohsstpehwepdeaherrytteeedud,srbtoewlsivyshosailcibrusheemirnpmeegrtauercfisctcetoironbrnfedelsdau.sicnkIatefnserddtth(hnaienteocaethdhlgeeervmsepapaiatcHseceade)lrange should be avoided. dhtttahrineioogerdndhivnesc(saapo3,ttpenu)iUrvccrAeieeefVs(ninssco-tu)avr,frtlaioeaysttnithiaboidecllnlliaeodqsslwueusatmbpineddserdetcematttmhncreinhoorcamaeprdytoh.iibmwnooTenataeihotntlbimeloogygncearottanaroenaypssfsltu,hyietsiyhtdctti,aeo.cobnadIflldteeixfsummfaotcerenmutratiaesvhcenlttioytitcdbtoyoisne,cpmwageslbiauclamilsifnnefbedasictcethhaiieorodtfnondoetmtht.rloemeyarftmatopsetegiHsinonrteanssedipotlheilbvuocyyef, htpuiIaetfteir0mgriet5.shamh1p0teeieu(emrr4nrhaCC)pettyteso.udTamriirrtsAnteepoasstrnenltwteyrhdtqtaoaeicitutfpcooufritpernarebmrremendeoidsgnaihpp..teigarineFIoivr0tnafonaair-tortiose4anur--mt0nrceoteyosh(esftniCeas)etsicvhnttbhTaeaeeermnnetoeyshttmptuo,ihsesntbopeertdsuhrmeartgeartabptuhnanhyerdtgtcire.useeaeatTrtotpeouiehlrfsrrre.meeteauylhbF'isinemnyotbmkaradi1entnat0eixheoyaottxwernrbtsCryasrnhemp.a,ossopoituahnaloblaoagdltptuateairitoliobedindnonleeainsmdbtfearetipmboonfuymdoaparorrltmpoyntotlhyeeeesteraameeedassssett.,t omrtiiroeendaa)sr.ou(giuorit)ensuLtshsiighrnohoguut galadhnnytbdhseeuoitxstaaoykblgevleneennm.ttoAefotelhlrxoco5dlfumttdoheienauvohtoxyeiydsdgrbepoenlhfyoos(rtiesoe.lgryp.etraibeccpyteaiofrbfnaeutscibotsbsnh.lioonAugfllldtnhsbieuteristoaocgblaeurlne abrt45toeen.l0seqdddt,uaeanis7tyr(thoe5.es0cod)eat,un.{dPtalavTd\dnienrrihdrteobeifdon>eo9unamr.canp0m1tel.eainroaltyIytfennfaeotsiaclrtolcliermeyanf)sl,ges1ordm0ftietshlhpeoeteartvhenhneraecqocnthud1ehtteni0eermmttseeptsdiium--neuc.srabptItcl(shefeibtre)ntaieashtnitPenucsocriuersotfeeuifnalfastbiisl,htmcsiecditt5eoiahenn0rnnereatcecalredepy0cnyrt.itpei1shroltryainkemedtnsciCrioitiosnsonweala.AoyrntbatyinstecpeodaatrreclebvlsshlyteeeimdnouisssitnfniaatsfanipbttvreoaHleyert Tathsheedse(befiiluine)fcefHtederdyebddytreottmehlsyeptseiprssraoetlouluifrmtieuoisnnn. assTrtayoobftlteeteshstste,utbfshousertbastfnetiasrctsnetcs-peo.rroIdscfheerotdhuubelrdeeshuabibsvesittooatrhnebcereeamcaiohssstufraoentltaslectodatwibosalne:t 11 0000^4 dotasohoteffrltoueehsnertiyixmeod(n4oirsn,opfasla7tythhci,sooeeiun9sdm)sldo)d.(pftabHhtteeah'samaptnaoitadtienldesytaltzsec,echdthnemeooimnrfpmiettchraiamaelllt.yuesreTbeilnheeitcetnetwrertvedheaeaenltcsectmia2wos0pnheeiprcosaehhftrouecpurleerlendvostavwbtiadeenidetdhetaxe7ram0emmppilipeninrceieaamrdtctuiueornmanett bplheysci(ooimilio)pgoHicuyandldlyrosslhiygosnuisilfdiactaalnpstoHtebm1e.2pc.earTrarhtiueerdeabo(3ou7vt eaCtte)ps.tHfo1r.2a, heymdprololyytiincgallay suinngstlae, tlsoiioognnioa(oenC)fatlfyviserirssstuoDsroafrtrtdoaaemnradntkhtdheinerselertoepipcaoescr:.ttioiTnnhg--erat(de1a)ctaoT"nrostebaatnattminkeeodnbts sochafolucrueldslautbleteds--bpy(lio)trteCegdroensaftir m a kobs = 2.303 x slope olidnse,b(teihyi)eonrIendatctehtrieponsrceiotsapnteioootnffitrohsfitsroteredsstuerpl,trsai.nncIdifptlthehe.eddaatatamduost-nboet afnaalllyoznedabystrmaeigthht (2) Test report (i) The test report should include information on: (A) Sample purity. stanc(eBs.) Any results appropriate to thp procedure employing reference sub for ea(Cch) sDeettoafileexdpteersimt pernotcse. dure including the temperature, pH and, buffer iins gusde(edDta)tiolDesdeetpmaaierletahdteodatnhoaeflcyehtxiectmraaliccmtaiolentfhraoonmddutrhseeecdoavqfeourreyotuhdeastpatehisaftseaedn. seuxbtrsatactnicoen, minectlhuodd serve(dEt)oAorlligcinonacteenatrnaotniplinn-etaimr elogdactoanpceonintrtsatfioonr-triemacetipolnost. which were ob (F) Possibility of acid or base catalysis. plicat(eidi), Ais psuregsgeenstteedd: format for sample reporting form, which can be du 12 0 0 0 0 55 ostinhhneolmyuhlaydinkdirbncoeaglyslesueipssssuptbhrthsoetacanesnsocsl1.eustpioewnricste.hnTtl,ohweanudwsaettheoerfssomolluvixebenidltityssoh. loTvuehlndetsanmoistourinnetcteoromffemrseoelnvwdeienthdt ostssehthrumoodbuupiullee(ddfrCdfae,b)btreueGsrshaeuylvosassou,setilesddsdwmeeafdaolb.reiresed.cvsoaAotrrelrlarlsytieliiginlpzelgtae,udsooms.uwr-tSacilftrtoohestp,ehepdewhehrytteediucdsrbhtoelsivmysosaulibrusseemtirnpeebgrtaeercficticeionronernfredlstdau.sicnkaItfnesdtdthh(ehnaeteopcaeHhdlgeermvsrepaaainatcsecgeadee)l dhatttrihneioogerdndhivnesc(asapo3,ttpen)iuvrcUcrAeieeefVs(ninssc-otu)avr,frtlaioeaysttnitihaboidecllnlliaeodqsslweuusatmbipenddsredetemcatttmhnecrinrhoocamapedrytoh.iibmwonoTenataeihotnltbimeloogygncearottanaroenaypssfsltu,hyietsihytdcttia,eo.cobnadIlfldteeixfsummfaotcernemturatiaesvhcelntityotitcbtdoyoisn,ecpmwageslbiaculamilisfnnefebdasictcethhaiioreodtfonndoetmt.htrolemeyarftmatopsetgeiHsinonrtaenssedpiotlheilbvuocyyef, htapuiIteftier0mgiret5.shamh1p0eteieu(emrr4nrhaCC)pettyteso.udaTmirirtsrAnteepoasstrnenltwteyrhdtqatoaeicitutfpcooufritpernarebmrreemndeoidsngahipp..teigarienFIoivr0tnfaonaair-tortioes4anur--mt0nrceoteyosh(esftniCeas)etsicvhnttbhaTeaeeermnnteoeyhsttmptou,ishestnbopeertdushmraertgaertabptuhnanhyerdtgticr.euseeaaetTrtotpeouiehlrfrsrre.meeteauylhbF'isinmenytobmkaradi1entnat0eixheoyaottxwrenrbtsCyrasrnhemp.a,sosopotiuhanalboalogadltptuaetairitoliobedindnonleeainsmdbtfearetipmboonfumydoaparorrlmtpoyntotlyheeeesteramaeeedasssset.tt, rmotiiroeendaa)sr.ou(giuorit)ensuLtshsiighrnohoguutgaladhnnytbdhseeuoitxstaaoykblgevleneennm.ttoAefotelhlrxoco5dlfumttdohieenauovhtoxyeiydsdgrbeopenlhyfoos(ritesoe.lgryp.etraibeccpyteaiofrbfnaeutscbiotsbsnh.lioonAugfllldtnhsibeuteristoaocgbaleurlne btar4t5oeen.l0seqdddt,uaeains7tyr(theo5.es0cod)eat,un.(dtPalavTddinie/rri2hdrteobeifdon>eo9unamr.can0pm1tel.aeinoraltyIytfennfaeotsicalrtolcliermeyanf)sl,ges1ordm0tfeitshlhpeoeteartvhenhneraecqocnthude1htteni0eermmttseeptsdiium--neuc.srabptItcl(shefeibtre)natieashtnitPenucscoriuersotfeueifnalfastbiisl,htmcsiecditt5eoaihenn0rnnreeatceclareedyp0cnyrt.itpie1shroltryainkeemdtnsciCrioiitosnsonweala.AoyrntbatyinsetcpeodaatrreclebvlsshlyteeeimdnouisssitnfniaatsfanipbttvraeoHleyert Tathsheedse(befiiluine)fceftHederdyebddytreottmehlsyeptseiprssaroetlouulifrtmieuosinnn. assTtrayoobftlteeteshstste,utbfshousertbastfnetiarsctsnetcs-poe.rroIdscfheerotdhuubelrdeeshuabibsvesittootarhnebcereeamcaihossstufraoentltaslectodatwibosalne:t 11 0 0 0 0 5 6 sooflustixionspsahcoeudlddabtea apnoainlytsz,ednoinrmtaimllye binettewrveaenls 2w0hipcehrcpernotviadned a70mipneimrcuenmt daothtefrtoeehneryemd(4oirn,ofal7tythi,soei9nsm)so).(pftHhteh'samtaittdedesaltecchthemeomfpeitcrhaaelt.usreTelheicentertdheaetcectmiaospneerosahftoueulreledvsawbteeidthetxeramempplieinrceaadttuioranet pbhleysci(ooimilio)pgoHicuyandldlyrosslhiygosnuisilfdiactaalnpstoHtebm1e.2pc.earTrarhtiueerdeabo(3ou7vt eaCtte)ps.tHfo1r.2a, heymdprololyytinicgallay suinngstlae, lstoiioognnioa(oenC)fatlDyfvisearirtsssatuosraonfrtrddoaemnrrdetpkhthoeinerstelritoneipcagesc--:.tio(T1nh)erTatrdeeaactaot*mn'soetbantntationkefodbr*esschuaolltucsul--dlat(bei)ed Cbpoylontrfteiergdmreasat kobi = 2.303 x slope loidnse,b(teihyi)eonrIendatctehtrieopnsrceiotsapnteioootnffitrohsfitsrotreedsstuerpl,trsai.nncIdifptlthehe.eddaatatamduostrnboet afnaalllyoznedabystmraeigthht (2) Test report, (i) The test report should include information on: (A) Sample purity. / (B) Any results appropriate to the procedure employing reference sub stances. for ea(cCh) sDeettoafileexdpteersimt pernotcs.edure including the temperature, pH and, buffer iins gusde(edDta)tiolDesdeeptmaaierleathdteodathnoeaflcyehtxiectmraaliccmtaiolentfhraoonmddutrhseeecdoavqfeourreyotuhdseatpatehisaftseaedn. seuxbtrsatactnicoen, minectlhuodd serve(dEt)oAorlligcionnacteenatrnaotniolinn-etaimr elogdactoanpceonintrtsatfioonr-rtiemacetipolnost. which were ob (F) Possibility of acid or base catalysis. plicat(eidi), Ais psuregsgeenstteedd: format for sample reporting form, which can be du 000057 12 DATA SHEET FOR HYDROLYSIS STUDIES L a b o ra to ry :_______ D a te:______________ Test Substance:____ Formula:______ Name (IUPAC):. Test protocol A. Preliminary test yes_______ no_______ buffer systems used: pH 4.0_________ pH 7.0_________ pH 9.0_________ Approximate saturation concentration mola/L Co: Initial concentration............................................................ C: Final concentration after relays; tn u 5 ......................... t ................................................................................................. (Co - C)/Co x 100 at 50 0.1 C ........................................... 4.0 pH 7.0 9.0 13 O O O O iib B. Determination dweitthermSreeippnalairtcaiaottneioranut naeslteavotantpeeHdo tf4emt.0h,pese7er.a0t(,uthraeen).dmTi9dh.0de lesaatmtetmhe epfoecrrhamotuasert newihtneomuthlpdeerbcaeatusureese(osd)f for each pH. Buffer solution used___________________________ Temperature_______ :_________________ Approximate saturation concentration,________________________ t [ 10 C. fm nlft/Ll ..... Ion C. ............. . Hydrolysis at pH 1-2 Buffer solution used_______________ pH-----------------------------------------, Temperature_______________________ Approximate saturation concentration t[ 10 C, [mola/L] Ion C. ........... Final data l pH temperature C initial concentration, Co [mole/L] reaction rate con stant, koba (1/S X 10] half-life, ti coefficient of correla tion, r2 14 000059 C. Report on test method tPtharieonvtineidsgtessdtoeelrutiatliiitolyend;, tedotecsa.cv(rPoipildetiaopsnheouotsfoeltyhsdeecpeaexrfpafeetercitsmsh;eetneottaoelxfccpolaunpddeeirti.o)oxnysg, een.g;. toforprmepaainre Analytical combinations used h pH electrodes ........... h UV-visible spectrophotometry Conductivity.............. Gas chromatography High pressure liquid chromatography.... - Extraction and forma tion of derivative(s) / / Details of the analytical performance: Type of apparatus Test conditions Was the accuracy of this result determined in any additional way ? Particular incidents: Comments: 15 0 0 0 0 6 0 dition(af)l backgrRoeufnedremnacteesr.iaTlhoen ftohlilsowteisntgguriedfeerliennec.es should be consulted for ad Ed., W(1)ileKy,olptpho3f4f,-3I.6M(.1a9n4d1)L. aitinen, H.A. pH and Electro-Titrations, 2nd Cicoaml Cp(2ho)uemnMdiasstbrieynyR,WeWfae.treaernndUcenMDdeialrlt,aET7n.,:v3Cir8or3int-im4c1ae5lnRt(a1el9vC7ie8ow)n.doiftiHonysd. rJoolyusrinsaolfoOfrPghanysic Revie(w3)s G29o:m17a1a,(1H9.6M9.).et al. Kinetics of Hydrolysis of Diazoxon. Residue (4) OECD Document A80.30, Summary of OECD-EEC Laboratory Intercomparison Testing Programme, Part 2, Umweltbundesamt, Berlin, Ma%y 1980. / l 16 qOOOGI 3M Environmental Laboratory Report No. W 1868 Appendix B: 3M Environmental Laboratoiy Method ETS-8-90.0 "Determination o f the Stability ofMeFOSEA in Aqueous Buffers Using Gas Chromatography with Atomic Emission Detection" Attorney CHenVWork Product Privileged Do N o t Dlactoae 0000G2 Do N ot Copy 3M Environmental Laboratory Method Determination of the Stability of MeFOSEA in Aqueous Buffers Using Gas Chromatography with Atomic Emission Detection Method Number: ETS-8-90.0 Adoption date: Revision Date: NA Author: Thomas Hatfield, Ph.D./Cleston Lange, Ph.D./Gregoiy Maisel/Jeanette Wink Approved by: Laboratory Manager ------------- C / " 7 / ? f Date 1.0 S c o p e a nd A p p l ic a t io n 1.1 This procedure defines the steps for preparation and analysis of 2-{N- methylperfluorooctanesulfonamido)-ethyl acrylate (MeFOSEA) from aqueous hydrolysis by gas chromatography with atomic emission detection (GC/AED). 1.2 Acceptable Matrices: Aqueous solutions at various buffered pHs. Word 6.0/95 StabilityMoeftMhoedFEOTSSE*A8-b9y0.G0 C/AED Page 1of 13 O0 0 S 3 2.0 S u m m a r y o f t h e M eth o d 2.1 One milliliter of buffered aqueous sample from the hydrolysis of MeFOSEA is quenched with 0.5 mL isopropyl alcohol (IPA) and extracted with 10 mL hexane. A portion (1-2 mL) of the separated hexane phase is dried through an anhydrous sodium sulfate column and then analyzed on a gas chromatograph with an atomic emission detector. 3.0 D e f in it io n s ___________________________________________________________________________________ 3.1 Duplicate analyses. Analyses or measurements of the analyte of interest performed identically on the same sample. The results from duplicate analyses are used to evaluate analytical or measurement precision but not precision of sampling, preservation or storage internal to the laboratory. 3.2 Sample duplicates. Two samples taken from and representative of the same sample source and carried through all steps of the sampling and analytical procedures in an identical manner. Duplicate samples are used to assess variance of the total method, including sampling and analysis. 3.3 M atrix spike. Prepared by adding a known mass of target analyte to specified amount of a sample matrix for which an independent estimate of target analyte concentration is available. Matrix spikes are used to determine the effect of the matrix on the method'srecovery efficiency. 3.4 Solvent blank. A sample of analyte-free medium to which all reagents are added in the same volumes or proportions as used in sample processing but is not carried through the complete sample preparation and analytical procedure. 3.5 Continuing Calibration Verification (CCV). A standard analyzed periodically during an analytical run to verify the continued accuracy of the calibration curve. This solution may be prepared from a different source of lot number than the calibration curve standards. 3.6 Lim it of Quantitation (LOQ). The lowest concentration that can be reliably achieved within specified limits of precision and accuracy during routine laboratory operating conditions. It may be nominally chosenwithin these guidelines to simplify data reporting. For many analytes, the LOQ analyte concentration is selected as the lowest non-zero standard in the calibration curve. Sample LOQs are highly matrix dependent. StabilityMoeftMhoedFEOTSSE-A8-b9y0.G0 C/AED Page 2 of 13 0000G4 4.0 W a r n in g s a n d C a u tio n s 4.1 Health and Safety Warnings: 4.1.1 Wear the proper lab attire for all parts of these procedures. Wear gloves at all times. 4.1.2 Handle all solvent in a hood for all parts of the described sample preparation procedure. 4.1.3 For potential hazards of each chemical used, refer to material safety data sheets, packing materials and 3M Environmental Laboratory's Chemical Hazard Review. 4.1.4 Use care when working with GC/AED because high temperatures and ultraviolet light are present. 4.2 Cautions: 4.2.1 Rinse with solvents all glassware used to prepare standards to reduce the possibility of contamination. 5.0 I n t e r f e r e n c e s ___________________________________________________________________________ 5.1 Contaminants in solvents, reagents, glassware, and other sample processing or analysis hardware may cause interferences. Routinely analyze laboratory solvent blanks to demonstrate that no interferences are present during the analysis. 6.0 E q u ip m e n t _________________________________________________________________________ _ 6.1 Balance, capable of measuring to 0.1 mg. 6.2 Shaker, incubating, capable of holding at 50C 3C. 6.3 pH meter, Coming Model 308 pH/Temperature Meter with 3-in-l gel filled combination electrode (pH/reference/temperature) or equivalent. 6.4 Gas Chromatograph, HP 5890 Series II, with HP 5921A Atomic Emission Detector (AED) or equivalent. 6.5 Column, J & W Scientific Incorporated, DB-5MS, 30 m x .25 mm x .25 pm or equivalent. StabilityMoeftMhoedFEOTSSE-A8-b9y0.G0 C/AED Page 3 of 13 0000S5 6.6 Data Recording System, HP ChemStation Rev. A.05.04 with Windows NT software. 6.7 Autosampler, HP 7673 or equivalent. 6.8 Clock. 7 .0 S u p p l ie s a n d M a t e r ia l s ________________________________________________________________ 7.1 Autovials, crimp top, 1.5 mL. 7.2 Vials, glass screw top, 40 mL, I-CHEM or equivalent. 7.3 Labels, Avery 5160 or equivalent. 7.4 Graduated pipettes, glass, disposable, various sizes. 7.5 Pasteur pipettes, glass, disposable. 7.6 Volumetric flasks, various sizes. 7.7 Beakers, glass, various sizes. 8 .0 R e a g e n t s a n d S t a n d a r d s _______________________________________________________________ 8 .1 Buffer solutions Prepare the buffer solutions in 1000 mL quantities. Adjust pH with NaOH or HC1. Use a portable pH meter to calibrate all buffer solutions. Record final pH measurements of buffers. Store the buffer solutions in sealed 1000 mL flasks. Prepare buffers as follows: 8.1.1 p H 1.5 0 .3 a) 250 mL of 0.1 M HC1, b) 125 mL of 0.2 M KC1, c) Bring to a final volume of 1L with ASTM Type IH 20. StabilityMoeftMhoedFEOTSSE-A8-b9y0.G0 C/AED Page 4 of 13 0000G6 8.1.2 pH 5.0 0.3 a) Dissolve 3.57 g ammonium acetate in 200 mL ASTM Type IH 20. b) Add 230 mL of 0.052 M acetic acid (3 mL glacial acetic acid into 1 L ASTM Type IH 20) c) Bring to a final volume of 1 L with ASTM Type IH 20 . 8.1.3 pH 7.0 0.3 a) Dissolve 7.9 g Trizma-HCl in 200 mL ASTM Type IH 20 . b) Adjust pH to 7.0 with 0.IN NaOH. c) Bring to a final volume of 1 L with ASTM Type IH 20. 8.1.4 pH 9.0 0.3 a) 46 mL of 0.1 N HC1. b) 125 mL of 0.1 M borax (sodium borate, 10 hydrate). c) Adjust pH to 9.0. d ) Bring to a final volume of 1 L with ASTM Type IH 20 . 8.1.5 pH 11.0 0.3 a) 250 m LofO .lN NaOH. b) 250 mL of 0.1 M borax. c) Adjust pH to 11.0. d) Bring to a final volume of 1 L with ASTM Type IH20. 8.2 Acetone, spectroscopy grade or equivalent. 8.3 IP A, spectroscopy grade or equivalent. 8.4 Hexane, 85% n-Hexane, spectroscopy grade or equivalent. Use hexane in post injection solvent washes for the GC/AED. Prepare a one L hexane solution containing 10 mL of IPA (hexane-1% IPA) to use for extraction and for solvent blanks. StabilityMoeftMhoedFEOTSSE-A8-b9y0.G0 C/AED Page 5 of 13 0000G7 8.5 MeFOSEA, prepared in acetone, approximately 10,000 ppm. Weigh 0.1 g of MeFOSEA and dissolve in 10 mL acetone. Use this solution for calibration standards, test analyte samples and spikes. 8.6 Sodium sulfate, anhydrous, 60 mesh, reagent grade. 9.0 S a m p l e H a n d l in g __________________________________________________________________ 9.1 Handle all samples and standards in a well-ventilated area. Wear gloves when handling solutions. 9.2 Prepare hydrolysis sample prep worksheets for each sample set. (Attachment A.) Prepare a tracking schedule for sample extraction. 9.3 Analyze all samples as soon as possible after extraction. I f samples cannot be analyzed immediately, store in refrigerator at approximately 4C. 10.0 Q u a l it y C o n t r o l ___________________________________________________________________ 10.1 Solvent blank. Prepare solvent blanks (hexane-1% IPA). This serves as an instrumental check for any analyte carryover. 10.2 Duplicates. Prepare a sample and a duplicate. Perform two injections of each. 10.3 M atrix spikes. Prepare a post-hydrolysis matrix spike for each of the pHs used in the study. Perform two injections of each spike. 10.4 CCV. Run a CCV every 15 or fewer injections. 11.0 C a l i b r a t i o n a n d S t a n d a r d i z a t io n 11.1 Standard preparation. Prepare six calibration standards of MeFOSEA. Standards from approximately 1.6 to 32 ppm are suggested. 11.2 Calibration standards. Analyze calibration standards at the beginning of the run. 11.3 Coefficient of Determination. The acceptable coefficient of determination (r2) is 0.990 or greater. Curves should be examined closely for linearity and intercept, particularly for accuracy of quantitation at the high and low ends of the curve. StabilityMoeftMhoedFEOTSSE-A8-b9y0.G0 C/AED Page 6 of 13 0000S8 12.0 PROCEDURE 12.1 Sample preparation. 12.1.1 Establish time points for sample analysis. Typical time points are at days 0 ,1 ,2 , 7,14,21 and 28. 12.1.2 For each pH to be tested, set up the 40 mL I-Chem vials to allow for a sample, a duplicate and a spike for the duration of the experiment. Each time point has 3 samples per pH and five pHs for a total of 13 vials per time point. 12.1.3 Create labels and affix to vials. Label information should include date, a sample number; the pH; whether the vial contains sample, duplicate or spike; the time point; and the initials of the analyst. An example using June 15, 1999 is: 61599-MeFOSEA-002 pH 1.5 Duplicate Day 0 CCL 12.1.4 Remove vial cap. With a pipette, add 1 mL of buffer to the bottom of each vial, taking care to avoid the walls of the vial. Always replace cap immediately after any addition to minimize evaporation. 12.1.5 Using a 25 pL gas-tight syringe, add lOpL of MeFOSEA test analyte solution to each vial with buffer, except for those marked Day 0. Tilt the vial so the buffer runs to one side of the bottom of the vial. Add the test analyte solution on the opposite side of the vial, away from the buffer. 12.1.6 Prepare time zero samples when adequate time is available to immediately quench the samples. Set up each sample individually. Extract each one with hexane-1% IPA before starting another to get a true time zero. 12.1.7 Fill out hydrolysis sample prep worksheets (Attachment A) for each sample set. 12.1.8 Place the samples in the 50C incubator. Set for 100 rpm shaking. Note time, date, and temperature on worksheets. 12.1.9 At the specified time point, remove samples from the incubator. Let cool to room temperature for 15 minutes. 12.1.10 Add 10 jtL of the MeFOSEA spike solution to the bottom of each spike vial so it mixes with buffer. StabilityMoeftMhoedFEOTSSE-A8-b9y0.G0 C/AED Page 7 of 13 000069 12.1.11 Add 0.5 mL oflPA to all vials. Swirl to mix. 12.1.12 Add 10 mL of the hexane-1% IPA to vials. Recap vials and shake vigorously for 10-15 seconds. Let settle for 1 minute. The water phase is on the bottom; the hexane phase is on the top. 12.1.13 With a pipette, pull off a portion (1-2 mL) of the top phase. Dispense the hexane onto a column consisting of approximately 1 inch height of NajSC^, in a Pasteur pipette. Allow the hexane extract to flow through the column into a prelabeled autovial. Use two autovials per sample. Cap the vials. Store one set of vials in the freezer at approximately -20C. Place the other set of vials in the autosampler for analysis. If samples cannot be immediately analyzed, store in refrigerator at approximately 4C. 12.2 Solvent blanks. 12.2.1 To 40 mL I-Chem vials, add 10 mL of hexane-1% IPA. Analyze in the same manner as the samples. 12.3 Sample analysis. 12.3.1 Install the analytical column and establish instrument conditions. Allow the system to equilibrate for 30 minutes before starting the analysis. T a ble 1. Su ggested G C C o n d itio n s fo r Sa m ple a n a ly sis P a ram eter Inlet temperature: Inlet liner: Detect temperature: Carrier gas: Oven Program: Initial temperature: Initial time: Rate: Final temperature: Final time: Suggested Value 180C 4 mm ID, single gooseneck, glass 280 Helium 50C 1.00 min. 15.0C/min. 300C 0.00 min. StabilityMoeftMhoedFEOTSSE-A8-b9y0.G0 C/AED Page 8 of 13 000070 12.3.2 Set head pressure for a linear velocity through column between 28-32 cm/sec. T a ble 2. Su g g ested A ED C o nd itio ns fo r Sa m ple a n a ly sis P a ram eter Transfer line: Cavity: Min. peak width: Data rate: Solvent ventprogram: On time: O ff time: Elements: Spectra: Suggested Value 280C 280C 0.054 min. 5.0 hz 0.00 3.50 minutes Carbon 193, Sulfur 181, Nitrogen 174 Save 12.3.3 T a b l e 3. S u g g e s t e d A u t o s a m p l e r C o n d i t i o n s fo r Sa m pl e A n a ly sis P aram eter Autosampler injector: Sample washes: Sample pumps: Injection volume: Syringe size: On column: Nanoliter adapter: Post Injection Solv A washes: Post Injection Solv B washes: Viscosity delay: Plunger speed: Suggested value 7673 1 3 1.0 pL 5.0 pL O ff O ff 4 (hexane) 4 (hexane) 0 sec Fast 12.3.4 Enter the standard and sample information into the sequence table. Analyze calibration standards first, then a sample set of 15 or fewer injections, followed by either the continuing calibration verification standard or by the full set of calibration standards. Run a solvent blank after the highest calibration standard and after a set of 15 or fewer injections to check for any analyte carryover. StabilityMoeftMhoedFOETSSE-A8-b9y0.G0 C/AED Page 9 of 13 000071 12.3.5 Place the standards, samples and QC (duplicates, matrix spikes, and blanks) into the autosampler tray according to the order they are listed in the sequence table of the HP ChemStation. 12.3.6 Start the sequence. 13.0 D a t a A n a l y s is ________________________________________________________ 13.1 M atrix spike recoveries. Calculate spike recoveries using the formula below: %recovery - ---(-s-p-i-k-e-d--sa-ma--cp-tul-ea-l-re-ss-pu-ikl-te---d--a-m-s-ao-mu-np--tle--r-e-su--lt-)-- x 100 13.2 MeFOSEA concentrations. Calculate the concentration of MeFOSEA in the hexane extract by external method using the calibration curve. 13.3 Data plot. Obtain a plot of MeFOSEA concentration in the hexane extract as a function of time for each pH. Use these data for degradation rate determinations. 14.0 M e t h o d P e r f o r m a n c e ____________________________________________________________________ 14.1 Solvent blanks. The measured value for the solvent blank should be less than half the LOQ of the method. 14.2 Sample duplicates. The warning limits are the average twice the relative percent difference. The control limits are the average _three times the relative percent difference. I f the lower value of the warning or control limit calculates to be less than zero, use zero as the low limit. 14.3 M atrix spikes. The recovery warning limits are the average spike recovery twice the standard deviation. The recovery control limits are the average spike recovery three times the standard deviation. 14.4 CCV. Analyze a mid-range calibration standard and a solvent blank after 15 or fewer sample injections and at the end of the run. If the percent difference for the amount of measured analyte exceeds + 25% of the true value, relative to the initial standard curve, stop the run. Use only those samples analyzed before the last acceptable calibration check standard. Reanalyze the remaining samples with a new calibration curve. StabilityMoeftMhoedFEOTSSE-A8-b9y0.G0 C/AED 000072 Page 10 of 13 14.5 Coefficient of Determination. The coefficient ofdetermination (r2) should be 0.990 or greater. The curves should be examined closely for linearity and intercept, particularly for accuracy of quantitation at the low and high ends of the curve. 14.6 LOQ. The LOQ is equal to the lowest standard in the calibration curve. 15.0 P o l l u t i o n P r e v e n t io n a n d W a s t e m a n a g e m e n t __________________________________ 15.1 Dispose of sample waste according to acceptable laboratory practice. Refer to the 3M Waste Stream procedure for further information. 16.0 R e c o r d s ______________________________________________________________________________ ________ 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 instrument ID. 16.3 Record sample weights and extraction information on the hydrolysis sample prep worksheets (Attachment A). 16.4 Print out the sample sequence table, reduce the size with photocopying and tape the photocopy into the instrument log. Keep all the original copies in the raw data files package. 16.5 Print chromatograms and internal standard reports for all analyses. 16.6 Print calibration tables and curve information and store in raw data file. 16.7 Store hydrolysis sample prep worksheets in the raw data file. 16.8 Enter all standard preparation information in the standards preparation logbook. 16.9 Backup all electronic data to appropriate media. 17.0 T a b l e s . D ia g r a m s . F l o w c h a r t s , a n d V a l id a t i o n D a t a _________________________ 17.1 Method validation has not been performed for this method. StabilityMoeftMhoedFEOTSSE-A8-b9y0.G0 C/AED Page 11 of 13 0000^3 18.0 R e f e r e n c e s 18.1 Fate, Transport and Transformation Test Guidelines, Office of Prevention, Pesticides and Toxic Substances. (OPPTS). 835.2110. Hydrolysis as a Function of pH and Temperature. EPA. 712-C-98-057. January 1998. 18.2 Fate, Transport and Transformation Test Guidelines, Office of Prevention, Pesticides and Toxic Substances. (OPPTS). 835.2130. Hydrolysis as a Function of pH and Temperature. EPA. 712-C-96-059. April 1996. 18.3 H andbook o f Chemical Property Estimation Methods. Rate of Hydrolysis, pp. 7-1 through 7-48. 18.4 CRC H andbook o f Chemistry and Physics, 1st Student Edition. "Buffer Solutions Operational Definitions ofpH." Robert C. Weast, Ph.D. 1988, p. D-87. 19.0 A f f e c t e d D o c u m e n t s 19.1 None 2 0 .0 R e v is io n s ___________________________________________________________________________ Rev number Revision reason Rev date StabilityMoeftMhoedFEOTSSE-A8-b9y0.0GC/AED Page 12 of 13 000074 TEST ANALYTE: HOURS: Sample No. . - Fluorochem ical Degradation (H ydrolysis) A nalysis Description Sample Duplicate Spike f. 1 Tim e o f Initial PrBP Buffer pH 1.5 1.5 1.5 Buffer Volume Test Analyte (mL) Solution (pL) 1.0 1.0 1.0 ISTD Solution (pL) Spike Solution (pL) Time of Quenching Quenching Solvent (mL) . Sample - Duplicate - Spike I__J 5 1.0 5 1.0 5 1.0 . . Sample - Duplicate - Spike 1 1 . . Sample - Duplicate - Spike 1 1 7 1.0 7 1.0 7 1.0 9 1.0 9 1.0 9 1.0 -- m Sample - Duplicate - Spike 1 1 D ate o f Initial Prep: 11 1.0 11 1.0 11 1.0 Date o f Q uenching: Test Analyte Solution Standardflraceability No. Component Concentration (pg/mL) ISTD Solution Spike Solution Quenching solution NA Temperature of Incubator (C): Incubation Start (Date and Time): Incubation Stop (Date and Time): Total Incubation Time: 0000*75 Buffer Addition by: ISTD Addition by: Test Analyte Addition by: Quenching by: Spire Addition by: AttachmentAutovial Aliquoting by: a Centrifugation Yes / No Centrifuge: RPM: Time: min - By: StabilityoMfMetheFoOdSEETAS-b8y-9G0.C0/AED Filtration: Yes / No By: Pore Size: um, Brand: Reviewed by: Page 13of 13 Page 13of 13 3M Environmental Laboratory Report No. W 1868 Appendix C: MeFOSEA Sample Preparation Logsheets Attorney Ciient/W ork Product Privileged Do N o t D ladoae 000076 Do Not Copy o o o -o. TESTANAYLTE: HOURS: Sample No. /101 998 -MeFOSEA-001 101 998 -MeFOSEA-002 101998 -MeFOSEA-003 Fluorochemical Degradation (Hydrolysis) Analysis Methyl FOSEA C T M C jf l') Date 11/23/98 day 0 Description Time of Initial Buffer Volume Test Analyte Prep Buffer pH (mL) Solution (pL) ISTD Solution (pL) Spike Solution (pL) Sample Duplicate Spike n 0 //-2Y-9S 2 t>b#eV 2 ` CO/^/hZ^ 2 .ox f f - z i ,,e 1.5 1.5 1.5 1.0 1.0 1.0 10 in quench Q 10 in quench Q 10 in quench lfl Time of Quenching Quenching Solvent (mL) acj z ' OZj 2: 0 2 lfl lfl lfl 10- 998 -MeFOSEA-004 10 998 -MeFOSEA-005 10 998 -MeFOSEA-006 Sample Duplicate Spike Z '. b-L uo 7 2 5 5 5 1.0 1.0 1.0 10 in quench fl 10 in quench A 10 in quench Ifi ? 2 '><9 lfl lfl lfl 10 998 -MeFOSEA-007 Sample 7, :oO 7 1.0 10 998 -MeFOSEA-008 Duplicate. U ' Ol* 7 1.0 10 998 -MeFOSEA-009 Spike |_ tl U. 7 1.0 10 in quench fl 10 in quench Q 10 in quench lfl 2-C ' (a 7*. Df i JA lfl lfl 10- 998 -MeFOSEA-010 Sample 2 '. o r 9 1.0 101 398 -MeFOSEA-011 Duplicate 2*7 o 9 1.0 101 398 -MeFOSEA-012 Spike I A I 7.' I O 9 1.0 10 in quench fl 10 in quench Q 10 -in quench JA 2-'. *?* t o i to lfl lfl lfl 101 398 -MeFOSEA-013 101 398 -MeFOSEA-014 101 998 -MeFOSEA-015 Sample Duplicate _ Z. ' 1*7 Spike [ L -rt. Date o f Initial Prep: //-2 11 11 11 1.0 1.0 1.0 10 10 10 Standard/Traceability No. Component Concentration (ng/mL) Test Analyte Solution ISTD Solution n w fc y -** /*< F o ie # tfA t o n t o n , __ l&ipnj r M f Quenching Solution ? *8 6 -V /*f ile** t t ir />//*-< Buffer Addition by: ~3 3 Test Analyte Addition by: QC L , ^O W H iihtngbyi T25U ^^--.AddMonfay;t C L^ G C /L - rW r - z L . Yes C No \ Centrifiige: Roujan RPM: Time: mm By: 3M Environmental Laboratory Request No: U2744 in quench Q lfl in quench Q Z */2 lfl in quench Ifl Z /Z . lfl Date o f Quenching: / / - 9 - 7 Temperature of Incubator (C): Incubation Start (Date and Time): Incubation Stop (Date and Time): Total Incubation Time: 50 / / t / `/S- ^ / / Y `i J ' - ' ^ <?) j m w u * Yes(KNo ) By: Pore Size: urn, Reviewed by: Brand: BESTCOPYAVAILABLE TEST ANAYLTE: HOURS: s VF Sample No. m 8#-MeFOSEA-016 1015 38 -MeFOSEA-017 1019 38 -MeFOSEA-018 Fluorochemical Degradation (Hydrolysis) Analysis Methyl FOSEA Date 11/23/98 day 1 Description Time of Initial Buffer Volume Test Analyte Prep Buffer pH (mL) Solution (pL) ISTD Solution (PL) Spike Solution (PD Sample Duplicate Spike D Z Z 50 S '* & : SO S * 1.5 1.5 1.5 1.0 1.0 1.0 10 in quench Q 10 in quench 10 in quench m Time of Quenching Quenching Solvent (mL) Z :?o m IQ lfl 1019 )8 -MeFOSEA-019 1019 )8 -MeFOSEA-020 1019 38 -MeFOSEA-021 Sample Duplicate ,, Spike ] &S ? :o Z 5 1.0 5 1.0 5 1.0 10 in quench 10 in quench 10 in quench m I IQ lfl 1019 38 -MeFOSEA-022 1019 38 -MeFOSEA-023 1019 38 -MeFOSEA-024 Sample Duplicate. , Spike 1/ 1 $ *S lo S 7 1.0 7 1.0 7 1.0 10 in quench 10 in quench 10 in quench jfl lfl lfl nr 1015 98 -MeFOSEA-025 1015 38 -MeFOSEA-026 1015 98 -MeFOSEA-027 Sample Duplicate Spike 1 Jr 3-2l> ^ o ?' lO 9 1.0 9 1.0 9 1.0 10 in quench 10 in quench Q 10 - in quench J fl IQ I lfl 1015 98 -MeFOSEA-028 Sample 11 1015 98 -MeFOSEA-029 101! 98 -MeFOSEA-030 Duplicate Spike u 3 :</0 11 11 \ / Date of Initial Prep: l / ' Z ? `f f r ' 1.0 1.0 1.0 10 10 10 'N i 00 Test Analyte s e n Quenching Solution ISTD Solution Solution Solution Standard/Traceability No. q jfo fb -s -n to y tf-D n im b - i vf Component 6 r/v4 x U A Concentration (pg/mL) ------------ fr ^ -- W* rrr-T o li C cT fli i afc >MAiiquottoo-by e c u Ye(^No^ Centrifuge: Roujan RPM: Time: min By: in quench in quench Q Q 1> i in quench m Date of Quenching: I JL I ' Temperature of Incubator (C): 50 andTima): 3 :3^ H / i Z h g ^(IlS^fipnSlpirfM M ntfJim ak 2 'O W a>|)9 HiMna Yes /' By: Pore Size: urn, Brand: Reviewedby: s S 'n 7 K -A ^ ~ 37^3/91 3M Environmental Laboratoiy Request No: U2744 TEST ANAYLTE: HOURS: Sample No. jZ T i8<MeFOSEA-031 A ' 101 (98 -MeFOSEA-032 P 10 98 -MeFOSEA-033 101 98 -MeFOSEA-034 101! 98 -MeFOSEA-035 Ts98 -MeFOSEA-036 101S )8 -MeFOSEA-037 101S )8 -MeFOSEA-038 1019 )8 -MeFOSEA-039 Fluorochemical Degradation (Hydrolysis) Analysis Methyl FOSEA Date 11/23/98 day 2 ISTD Spike Time of Initial Buffer Volume Test Analyte Solution Solution Time of Quenching Description Prep Buffer pH (mL) Solution (pL) (pL) (PD Quenching Solvent (mL) S am ple Duplicate ^Spike I 2 2 1.5 1.0 1.5 1.0 1.5 1.0 10 in quench 0 l3tei 10 in quench Q 'J'fd2.L> ID 10 in quench IQ -------- J"-- S am ple Duplicate Spike I n/ I 3 *7 net 5 5 5 1.0 1.0 1.0 10 in quench Q 2 `03 10 in quench Q 2\cn 10 in quench ID a - t o ID ID ID S am ple ?:e? 7 1.0 ,Duplicate f.o ? 7 1.0 Spike I v | 39 7 1.0 10 in quench D 2 ' i 10 in quench D a : Bf 10 in quench 3D 2T77 ID ID ID & 000079 1019 )8 -MeFOSEA-040 101S 98 -MeFOSEA-041 1019 98 -MeFOSEA-042 S am ple Duplicate Spike I \ / i I'.io ?!l.V> 9 9 9 1.0 1.0 1.0 10 10 10 10198 -MeFOSEA-043 101S 98 -MeFOSEA-044 101SI98 -MeFOSEA-045 I/r Sam ple ,Duplicate 3 r/0 3 10 Spike I V/l 3' Date o f Initial Prep: 11 11 11 - Z5 -YA 1.0 1.0 1.0; 10 10 10 Test Analyte Solution ISTD Solution (L Solution Quenching Solution Standard/Traceability No. Component Concentration (pg/mL) /'U-f't'HV) Buffer Addition by: i ') n eoC r (IFS) __ 7 t o if-? n * r A iM a- / -AT Y >-7^ ir* v, i r Centrifugation Yes \N o v ISTD Addition by: _ Test Analyte Addition by: c--c----u--r<r;rwV^lA--h Centrifuge: R oujan RPM: Quenching by: Spike Addition by: TM6? Time: By: min Autovial Aliquoting by: h b A d d x d 0 >^L i J 'f t ~b A &.U \A rf- r( tva*- /) / ' p ru r b a dd t fifr1 c d i 3M Environmental Laboratory Request No: U2744 in quench Q 2 '0 4 in quench D 2'OT- . in quench ID a ID ID ID in quench D Xoi in quench D 2-.0X in quench ID Date ofQuenching: ID ID ID // L-T -i r Tem perature o f Incubator (C): 50 Inpubation Start (D ate and Time): v^gg*eeonStop (Dateend Time) -- .Total Incubation Time: -- -r '- . V1 yFiltration: Yes { No By: Pore Size: urn, to : Brand: Reviewed by: i $ 4 ' V I >0 & TESTANAYLTE: HOURS: Sample No. i m $ 8 iMeFOSEA-046 101 398 -MeFOSEA-047 101 398 -MeFOSEA-048 101 398 -MeFOSEA-049 101 998 -MeFOSEA-050 101998 -MeFOSEA-051 101 198 -MeFOSEA-052 101 198 -MeFOSEA-053 101 198 -MeFOSEA-054 101 198 -MeFOSEA-055 101 198 -MeFOSEA-056 101 198 -MeFOSEA-057 101 398 -MeFOSEA-058 101 398 -MeFOSEA-059 100 398 -MeFOSEA-060 Fluorochemical Degradation (Hydrolysis) Analysis Methyl FOSEA day 7 D a te Time of Initial Buffer Volume Test Analyte Description Prep Buffer pH (mL) Solution (pL) 11/23/98 ISTD Solution (pL) Spike Solution (pL) Sample Duplicate Spike 1*S\ IS V t'S 'f 1.5 1.5 1.5 1.0 1.0 1.0 10 in quench Q 10 in quench Q 10 in quench Jfl Sample Duplicate Spike 1\A T r f 5 5 5 i.o 1.0 1.0 10 in quench Q 10 in quench 10 in quench Ifl Time of Quenching Quenching Solvent (mL) r 35" Jfl Jfl Jfl 4--5 *T 4 T ~ Jfl Jfl Jfl Sample Duplicate / Spike [ Z lu i ? 7 7 7 1.0 1.0 1.0 10 in quench Q 10 in quench 10 in quench Jfl -& IQ Jfl Jfl Sample Duplicate Spike 1 \ Y 3 :1 'I'LO ? io 9 9 9 1.0 1.0 1.0 10 in quench Q 10 in quench 10 in quench Jfl i& i lfl Jfl Jfl Sample Duplicate Spike \~%jj 7 `VO 11 11 11 1.0 1.0 1.0 Test Analyte Solution set. ISTD Solution Solution Quenching Solution 10 in quench Q ts f Jfl 10 in quench 10 in quench JA 7F 4 c ~ Jfl Jfl Date of Quenching: / / . S c ' 9 Temperature of Incubator (C): 50 g $^ n ft^ Start(Dataeed Time):- y s p u jzg f r f Incubation Stop (Date and Time): j ^ n , 'hofaS 3^Jncu b g fe n Timet 000080 tafttWdWonbyitffH?*Additon by? m ^ 5C--------------J ^TW tAnaiyteAddrtionby^ m e. Quenching by: Spike Addition by: Autovial Aliquoting by: 1m 6> fld ik d 0- 5 m L Pfl -fd > . tJ i a^ O n t r H> a iiih c ^ x o f /t Wa / 7 J Centrifuge: Roujan RPM: Time: min By: i 3M Environmental Laboratory Request No: U2744 1. JM 6 Httfaflona Yes W Pore Size: urn. _____________ Brand: Reviewedby: s/tsf a TEST ANAYLTE: HOURS: \ ^ i t * Sample No. m !98vMeFOSEA-061 101 98 -MeFOSEA-062 101 98 -MeFOSEA-063 Fluorochemical Degradation (Hydrolysis) Analysis Methyl FOSEA Date 11/23/98 day 14 Description Time of Initial Buffer Volume Test Analyte Prep Buffer pH (mL) Solution (pL) ISTD Solution (pL) Spike Solution (pL) Sample Duplicate Spike I ts U DSC, Zb 1.5 1.5 1.5 1.0 1.0 1.0 10 in quench Q 10 in quench 10 in quench ifl Time of Quenching Quenching Solvent (mL) M t e* hSf I 5 Ifl 1 Ifl 101 I98 -MeFOSEA-064 Sample 3 " 5 1.0 i 101 98 -MeFOSEA-065 Duplicate V /> 5 1.0 101 8 -MeFOSEA-066 Spike I \A V tf 5 1.0 10 in quench Q a u n 10 in quench Q 3l\ v% 10 in quench a IQ Ifl Ifl 101 398 -MeFOSEA-067 101 398 -MeFOSEA-068 101 398 -MeFOSEA-069 Sample Duplicate Spike ?// 7 1.0 y .v / 7 1.0 ? 7 1.0 101 98 -MeFOSEA-070 Sample Z'. t o 9 1.0 101 98-MeFOSEA-071 Duplicate / ZVO 9 1.0 101 98 -MeFOSEA-072 Spike I \A T 'to 9 1.0 10 in quench q J i o f 10 in quench Q '.CO- 10 in quench i f l 2 ' o % 10 in quench Q 2'0$ 10 in quench Q Zhb*> 10 in quench ifl Ifl Ifl Ifl ifl ifl ifl 101 98 -MeFOSEA-073 Sample & i/O 101198 -MeFOSEA-074 101498 -MeFOSEA-075 Duplicate x Spike YZX 3 'M o t'VD G 11 11 11 1.0 1.0 1.0 10 10 10 H Standard/Traceability No. Component Concentration (pg/mL) Test Analyte Solution V o tl-u l tA tf& C A ISTD Solution yw r in S fC Qiuenching SoHluUftion Solution ^tofoiS'iL i ) J $ i l 'i i i m McvJ f a fltcthoi * js fm u in quench fl S i'M . in quench 0 '.o s in quench , I f l '-Q S y^D ate o f Quenching: ifl ifl ifl L' g i n z ' Temperature of Incubator (C): 50 iocubabo^tart (Date idTime)! /i]l3>fa Incubation Stop pate and Time): te-hnftk /U2qw iM ferAddition by; 'T 3 T ( * l , 4 A * io n b * A 0 N \^ M ^ M y te .Addition byr & L_ Quenching by: - f tJ[ fa Spike Addition by: b Autovial Aliquoting by: _________ ridOJ 0 fa i l / 9A jn/(A tf/J . o n e r io f r & L ih 'n o r 1 rfv J t* . 0J Centrifuge: Roujan RPM: Time: min By: 3M Environmental Laboratory Request No: U2744 ct Yes ^ N o )_____________ By: Pore Size: urn, Brand: Reviewed by: TESTANAYLTE: HOURS: ,1 ^ 1 Sample No. vfGft I98 -MeFOSEA-076 101 98 -MeFOSEA-077 1019 98 -MeFOSEA-078 1019 18-MeFOSEA-079 1019 18-MeFOSEA-080 1019 18-MeFOSEA-081 1019 38 -MeFOSEA-082 1019 98 -MeFOSEA-083 101S 98 -MeFOSEA-084 101 98 -MeFOSEA-085 101! 98 -MeFOSEA-086 101! 98 -MeFOSEA-087 101! 98 -MeFOSEA-088 101198 -MeFOSEA-089 101J98 -MeFOSEA-090 V i/ Standard/Traceability No. Component Concentration (pg/mL) Fluorochemical Degradation (Hydrolysis) Analysis Methyl FOSEA D a te 11/23/98 day 21 Time of Initial Description Prep Sample t.C f Duplicate Spike I y I QJ 1 t i-.SSSJ Buffer Volume Buffer pH (mL) 1.5 1.0 1.5 1.0 1.5 1.0 Test Analyte Solution (pL) 10 10 10 ISTD Solution (PL) in quench in quench in quench Spike Solution (pL) IQ Sample 3 # 5 1.0 Duplicate 5 1.0 Spike Q 7] (0 5 1.0 10 in quench Q 10 in quench Q 10 in quench IQ Time of Quenching Quenching Solvent (mL) m 4:41 H'42. Ifi I1fQi IQ IQ IQ Sample Duplicate Spike I \A (0 Sample Duplicate Spike IT717T VU 3 i* 3-13 S3- 333V0v 7 7 7 9 9 9 1.0 1.0 1.0 1.0 1.0 1.0 10 in quench Q 10 10 in quench in quench QQ 10 10 in quench in quench Q Q 10 . in quench IQ f 444 V<K IQ IQ m IQQ 1Q Sample Duplicate , ^ Spike U/3 (U 3iSO 33-:sf do Date of Initial Prep: /7 - 7- ? 11 11 ' ctf1T1 1.0 1.0 1.0 10 in quench Q u l, 10 in quench Q 10 in quench 1Q rr S IQ IQQ fiate of Quenching:#^ Test Analyte ^ S o lu tio ri_ _ ISTD Solution `fv K -S -rt Quenching Solution 4 V U 0 -t$ 'l> Temperature of Incubator (C): t gpubaBon Start (Dale and Tima): Incubation Stop (Date and Time): 50 ! 000082 BOffer-Ackftion by. * & C ?v C U - ISTD Addition by: rT l TWtvAnriyte Addition byt Quenching by: Spike Addition by: .Tll/I G\ Autovial Aliquoting by: _______ CP Hlso spikd wi^1 IM of a/ ' . w r t a i , ?^ fppPp'-v^' iiVv cnU'*trr~L/ ! { Mhv* H I d fot 1m i Centrifuge: Roujan RPM: T im e: min By: ' .^i - 3 S E L Yes By: Pore Size: urn, Reviewed by: J/A bead v\d prier k rironmental Laboratify Request Ne/U2744 Q ) A _ & / opi^M U . *-.> "t ( I k?f 1 V i / I f c r * .. . -I r -I /- " Brand: " TESTANAYLTE: HOURS: 9 Sample No. m \ gaJheFOSEA-091 TOI 98-MeFOSEA-092 101! 98 -MeFOSEA-093 Fluorochemical Degradation (Hydrolysis) Analysis Methyl FOSEA Date 11/23/98 day 28 Description Time of Initial Suffer Volume Test Analyte Prep Buffer pH (mL) Solution (pL) ISTD Solution (pL) Spike Solution (HL) Sample Duplicate Spike ITTlrffl J;.' 0 ?: iu V oe. 1.5 1.5 1.5 1.0 1.0 1.0 10 in quench Q 10 in quench Q 10 in quench 10 Time of Quenching Quenching Solvent (mL) i} l'.M } & 10 10 10 101! 98 -MeFOSEA-094 Sample ? v r 5 1.0 1015 98 -MeFOSEA-095 Duplicate r - t s 5 1.0 101S 98 -MeFOSEA-096 Spike CZl 1\) 5 1.0 10 in quench Q io-3} 10 in quench to-. Z? 10 in quench IQ l -il 10 10 10 1015 98 -MeFOSEA-097 Sample 7 1.0 101SB8 -MeFOSEA-098 Duplicate ^ 71 i 7 1.0 101E 38 -MeFOSEA-099 Spike QZl (0 7'tZ 7 1.0 10 in quench I0-.& 10 10 in quench io .35 10 10 in quench 1 l ; & 10 101 38 -MeFOSEA-100 101 38 -MeFOSEA-101 101 38 -MeFOSEA-102 1015 98 -MeFOSEA-103 101 98 -MeFOSEA-104 101 S)8 -MeFOSEA-105 NJ Standard/Traceability No. Component Concentration (pg/mL) Sample 3 - t o 9 1.0 Duplicate / f'Zv 9 1.0 Spike H71/D 3 - f & 9 1.0 Sample 3'-S& 11 Duplicate ? -d 11 Spike I i/l/D 11 Date o f Initial Prep: / / - IT T W 1.0 1.0 1.0 Test Analyte Solution ISTD Solution w ' 5 P K 0 Quenching Solution Solution 1m cim s m 4M?f;. 10 in quench ...\o ;S i 10 in quench Q l ^ 10 in quench 10 10 10 10 10 in quench Q W-9 10 10 in quench Q lo-y 10 10 in quench 1 w s t 10 Date o f Quenching: S-fo.\ ? Tem perature o f Incubator (C): 50 Migiibation Sg*t(pate and Time): 3 '3o / * l gc^ . Incubation Stop (D ate and Tim e): 7 '5 5 /jt., hi h i7 .-? 7 o U ^ 0000S3 Duner nuuiuun uy. ISTD Addition by: B C A n ^ te A d d ltio n b y t Quenching by: Spike Addition by: A utovial A liquoting by: JhA&i___________ M>\\U6t totlh. IiaJ? <rf tJ'ivuftiyl rl)JJ)CiCAA. /o, 7 ? r 3 v\Ur^~' ( T'/i 0' - / / 'i 1 7 h i t W - l u h Yes Centrifuge: Roujan R P M :_____________ Tim e: minni______ B>/>y: _________________ M c U d 0 - 5 m l t p f t -h jumA * * 2 , * Yes By: Pore Size: urn, ^ A?7\Reviewed by: n b w Jtys*- f y t f K h Brand: : ~ h -T z- Appendix D: GC/AED Chromatograms See separate bound volumes. 3M Environmental Laboratory Report No. W 186B Attorney CllentAAtork Product Privileged Do N ot D ieciose 000084 Do Not Copy 3M Environmental Laboratory Report No. W 1868 Appendix E: Spreadsheets: GC/AED Results Attorney Client/Work Product Privileged Do Not Disclose 000085 Do Not Copy MeFOSEA GC/AED results Note that each extract was injected in duplicate. pH 1.5 DATA day Sample number 0 112398-MeFOSEA-OG1 112398-MeFOSEA-001 0 112398-MeFOSEA-002 1 12398-M eFO SEA-002 0 112398-MeFOSEA-003 112398-MeFOSEA-003 0.94 0.94 0.94 112398-MeFOSEA-016 112398-MeFOSEA-016 112396-MeFOSEA-017 112398-MeFOSEA-017 112398-MeFOSEA-018 112398-MeFOSEA-018 1.92 1.92 1.92 112398-MeFOSEA-031 112398-MeFOSEA-031 112398-MeFOSEA-032 1123 9 8-M e F O S E A -0 3 2 112 3 9 8-M e F O S E A -0 3 3 112 3 9 8-M e F O S E A -0 3 3 6.72 6.72 6.72 112 3 9 8-M e F O S E A -0 4 6 112 3 9 8-M e F O S E A -0 4 6 112398-MeFOSEA-047 1123 9 8-M e F O S E A -0 4 7 112 3 9 8-M e F O S E A -0 4 8 112398-MeFOSEA-048 13.90 13.90 13.90 112398-MeFOSEA-061 112398-MeFOSEA-061 112398-MeFOSEA-062 112398-MeFOSEA-062 112398-MeFOSEA-063 112398-MeFOSEA-063 20.71 20.71 20.71 112398-MeFOSEA-076 112398-MeFOSEA-076 112398-MeFOSEA-077 112398-MeFOSEA-077 112398-MeFOSEA-078 112398-MeFOSEA-078 27.77 27.77 27.77 112396-MeFOSEA-091 1 12398-M eFO SE A -091 112398-MeFOSEA-092 112398-MeFOSEA-092 112398-MeFOSEA-093 112398-MeFOSEA-093 MeFOSEA (ppm) 9.896 9.891 9.872 9.858 9.722 10.132 7.590 8.021 8.079 8.385 8.919 8.994 7.502 7.605 7.612 7.666 7.987 7.735 5.537 5.467 4.752 5.830 5.561 5.540 4.211 4.246 4.365 4.420 5.320 5.168 3.644 3.650 5.058 5.003 12.952 12.795 2.764 2.826 3.543 3.666 13.411 13.154 average ppm 9.894 % spike recovery for MeFOSEA %RPD calculations 0.3 9.865 9.927 n/a 7.806 5.3 8.232 8.957 n/a 7.554 1.1 7.639 7.861 n/a 5.502 3.9 5.291 5.551 n/a 4.229 3.8 4.393 5.244 n/a 3.647 5.031 12.874 79.5 31.9 2.795 3.605 13.283 94.0 25.3 000086 MeFOSEA GC/AED results Note that each extract was injected in duplicate. pH 5 DATA day Sample number 0 112398-MeFOSEA-004 112398-M eF O S E A -004 0 112398-MeFOSEA-005 112 3 9 8 -M e F O S E A -0 0 5 0 112398-MeFOSEA-006 112398-MeFOSEA-006 0.94 0.94 0.94 112398-MeFOSEA-019 112398-M e F O S E A -0 1 9 112398-M eF O S E A -020 112 3 9 8 -M e F O S E A -0 2 0 112398-MeFOSEA-021 112398-MeFOSEA-021 1.92 1.92 1.92 112 3 9 8-M e F O S E A -0 3 4 112 3 9 8-M e F O S E A -0 3 4 112 3 9 8-M e F O S E A -0 3 5 112398-MeFOSEA-035 . 112398-MeFOSEA-036 112398-MeFOSEA-036 6.72 6.72 6.72 112398-MeFOSEA-049 112398-MeFOSEA-049 112398-MeFOSEA-050 112398-MeFOSEA-050 112398-MeFOSEA-051 112398-MeFOSEA-051 13.90 13.90 13.90 112398-M eF O S E A -064 112398-MeFOSEA-064 112398-M eF O S E A -065 112398-MeFOSEA-065 112398-MeFOSEA-066 112398-MeFOSEA-066 20.71 20.71 20.71 112398-MeFOSEA-079 112398-MeFOSEA-079 112398-M eF O S E A -080 112398-MeFOSEA-080 112398-MeFOSEA-081 112398-MeFOSEA-081 27.77 27.77 27.77 112398-MeFOSEA-094 112398-MeFOSEA-094 112398-M eF O S E A -095 112398-MeFOSEA-095 1123 9 8-M e F O S E A -0 9 6 112398-MeFOSEA-096 MeFOSEA (ppm) 10.323 10.208 10.368 10.493 10.416 10.236 9.465 9.408 9.285 9.402 9.431 9.198 ' 8.491 8.660 8.467 8.823 8.496 8.592 7.910 8.592 7.702 7.718 8.518 8.457 7.131 7.431 7.864 7.744 7.710 bad injection bad injection 5.789 5.639 5.546 18.636 19.054 5.448 5.215 5.636 5.518 15.199 15.132 average ppm 10.266 % spike recovery for MeFOSEA %RPD calcu1l.a6tions 10.431 10.326 n/a 9.437 1.0 9.344 9.315 n/a 8.576 0.8 8.645 8.544 n/a 8.251 6.8 7.710 8.488 n/a 7.281 6.9 7.804 7.710 n/a 5.789 5.593 18.845 122.9 3.5 5.332 5.577 15.166 90.5 4.5 000087 MeFOSEA GC/AED results Note that each extract was injected in duplicate. pH 7 DATA day Sample number 0 112398-MeFOSEA-007 112398-MeFOSEA-007 0 112398-MeFOSEA-008 112 3 9 8-M e F O S E A -0 0 8 0 112398-MeFOSEA-009 112398-MeFOSEA-0;)9 0.94 0.94 0.94 112398-MeFOSEA-022 112398-MeFOSEA-022 112398-MeFOSEA-023 112398-MeFOSEA-023 112398-MeFOSEA-024 112398-MeFOSEA-024 MeFOSEA (ppm) 10.598 10.573 10.440 10.356 10.453 10.785 8.535 8.503 8.627 8.547 9.023 8.882 average ppm 10.586 % spike recovery for MeFOSEA %RPD calculations 1.8 10.398 10.619 n/a 8.519 0.8 8.587 8.953 n/a 1.92 1.92 1.92 1123 9 8-M e F O S E A -0 3 7 112398-MeFOSEA-037 112398-MeFOSEA-038 112398-MeFOSEA-038 112398-MeFOSEA-039 112398-MeFOSEA-039 6.72 6.72 6.72 1123 9 8-M e F O S E A -0 5 2 112398-M eF O S E A -052 112398-MeFOSEA-053 112398-MeFOSEA-053 112398-MeFOSEA-054 112398-MeFOSEA-054 8.660 8 .^ 6 8.762 *H ^ - 8.746 -tr tS T S 1 -K S S 8 78ft 8 754 ^ '' . 6.534 6.871 5.410 5.542 5.947 5.801 6.703 5.476 5.874 n/a n/a 20.1 13.90 13.90 13.90 112398-MeFOSEA-067 112398-MeFOSEA-067 112398-MeFOSEA-Ot58 112398-MeFOSEA-068 112398-MeFOSEA-069 112398-MeFOSEA-069 4.793 4.940 4.278 4.180 5.507 5.585 4.867 4.229 5.546 14.0 n/a 20.71 20.71 20.71 112398-MeFOSEA-082 112398-MeFOSEA-082 112 3 9 8-M e F O S E A -0 8 3 112398-MeFOSEA-083 112398-MeFOSEA-084 112398-MeFOSEA-084 4.506 4.684 3.512 3.360 14.152 13.941 4.595 3.436 14.047 93.5 28.9 27.77 27.77 27.77 112 3 9 8-M e F O S E A -0 9 7 112398-MeFOSEA-097 112398-MeFOSEA-098 112 3 9 8-M e F O S E A -0 9 8 112398-MeFOSEA-099 112 3 9 8-M e F O S E A -0 9 9 1.958 2.041 2.021 2.060 14.490 14.089 2.000 2.041 14.290 114.3 Results for Day 1.92 were not included in the graph, due to failed QC criteria. 000088 MeFOSEA GC/AED results Note that each extract was injected in duplicate. pH 9 DATA day Sample number 0 112398-WeFOSEA-010 112398-MeFOSEA-010 0 112398-MeFOSEA-011 112398-MeFOSEA-011 0 112398-MeFOSEA-012 112398-MeFOSEA-012 0.94 0.94 0.94 112398-MeFOSEA-025 112398-MeFOSEA-025 112398-M eF O S E A -026 112398-M eF O S E A -026 112398-MeFOSEA-027 112398-MeFOSEA-027 1.92 1.92 1.92 112398-M eF O S E A -040 112398-MeFOSEA-040 112398-MeFOSEA-041 112398-MeFOSEA-O.M 112398-MeFOSEA-042 112398-MeFOSEA-042 6.72 6.72 6.72 112398-MeFOSEA-055 112398-MeFOSEA-055 112398-MeFOSEA-056 112398-MeFOSEA-056 112398-MeFOSEA-057 112398-MeFOSEA-057 13.90 13.90 13.90 112398-M eF O S E A -070 112398-M eF O S E A -070 112398-MeFOSEA-071 112398-MeFOSEA-071 112398-MeFOSEA-072 112398-MeFOSEA-072 20.71 20.71 20.71 112398-MeFOSEA-085 112398-MeFOSEA-085 112398-MeFOSEA-086 112398-M eF O S E A -086 112398-M eF O S E A -087 112398-MeFOSEA-087 27.77 27.77 27.77 112398-MeFOSEA-1i)0 112 3 9 8-M eF O S E A -100 112398-M eFOSEA-101 112398-MeFOSEA-101 112 3 9 8-M eF O S E A -102 112 3 9 8-M eF O S E A -102 MeFOSEA (ppm) 9.998 9.469 10.312 10.533 10.313 9.881 10.996 11.293 11.386 10.059 8.713 8.517 9.897 8.800 7.263 7.326 7.457 7.189 5.036 4.992 6.114 5.082 6.263 5.481 4.436 4.394 4.365 4.624 2.980 2.960 2.601 2.475 2.312 2.269 11.365 11.252 2.392 2.371 2.415 2.361 11.798 11.972 average ppm 9.734 % spike recovery for MeFOSEA calcVu.RlaPtDions 6.8 10.423 10.097 n/a 11.145 10.723 8.615 n/a 3.9 9.349 7.295 7.323 5.014 5.598 5.872 24.7 n/a 11.0 n/a 4.415 1.8 4.495 2.970 n/a 2.538 2.291 11.309 82.9 10.3 2.382 2.388 11.885 88.5 0.3 000089 MeFOSEA GC/AED results Note that each extract was injected in duplicate. pH 11 DATA day Sample number 0 11239B-MeFOSEA-013 112398-MeFOSEA-013 0 11239B-MeFOSEA-014 112 3 9 8 -M e F O S E A -0 1 4 0 112398-MeFOSEA-015 112398-MeFOSEA-O' 5 0.94 0.94 0.94 112398-M eF O S E A -028 112398-MOFOSEA-028 112398-MeFOSEA-029 112398-MeFOSEA-029 112398-MeFOSEA-030 112398-MeFOSEA-030 1.92 1.92 1.92 112398-MeFOSEA-043 112398-MeFOSEA-043 112398-MeFOSEA-044 112398-MeFOSEA-044 112398-MeFOSEA-045 112398-MeFOSEA-045 6.72 6.72 6.72 112398-MeFOSEA-058 112398-MeFOSEA-058 112398-MeFOSEA-059 112398-MeFOSEA-059 112398-M eF O S E A -060 112398-MeFOSEA-060 13.90 13.90 13.90 112398-MeFOSEA-073 112398-M eF O S E A -073 112398-MeFOSEA-0"'4 112398-M eF O S E A -074 112398-M eF O S E A -075 112398-M eF O S E A -075 20.71 20.71 20.71 112398-MeFOSEA-088 112 3 9 8-M eF O S E A -088 112398-M eF O S E A -089 112398-MeFOSEA-089 112398-MeFOSEA-090 112398-MeFOSEA-090 27.77 27.77 27.77 112398-MeFOSEA-103 112 398-M eF O S E A -103 112 3 9 8-M e F O S E A -1 04 112 3 9 8-M e F O S E A -1 04 112398-MeFOSEA-105 112398-MeFOSEA-105 MeFOSEA (ppm) 12.496 10.362 9.650 10.302 10.306 9.674 8.971 8.648 9.218 8.988 8.596 8.527 7.315 8.749 9.143 8.833 8.525 8.434 5.947 5.630 5.966 5.103 5.315 5.035 3.360 3.260 3.471 3.325 3.545 3.802 2.144 2.354 2.885 2.795 12.385 12.647 2.268 2.300 2.497 2.488 12.028 12.442 average ppm 11.429 % spike recovery for MeFOSEA %RPD calculations 13.6 9.976 9.990 n/a 8.810 3.3 9.103 8.562 n/a 8.032 11.2 8.988 8.480 n/a 5.789 4.5 5.535 5.175 n/a 3.310 2.6 3.398 3.674 n/a 2.249 2.840 12.516 92.9 23.2 2.284 2.493 12.235 91.8 8.7 000090 QA/QC calculations Matrix spika racovary calculations e u Sample 1.5 112398-MeFOSEA-078 1.5 112398-MeFOSEA-093 5 112398-MeFOSEA-081 5 112398-MeFOSEA-096 7 112398-MeFOSEA-084 7 112398-MeFOSEA-099 9 112398-MeFOSEA-087 9 112398-MeFOSEA-102 . 11 112398-MeFOSEA-090 11 112398-M eFOSEA-105 Average recovery Standard deviation %Relative standard deviation Lower warning limit Upper warning limit Lower control limit Upper control limit "/.Recovery 79.5 94.0 122.9 90.5 93.5 114.3 82.9 88.5 92.9 91.8 95.1 12.7 13.4% 69.6 120.5 56.9 133.3 Sample precision calculations, using the sample and duplicate to calculate the RPD Average RPD Standard deviation Lower warning limit Upper warning limit Lower control limit Upper control limit 8.5 9.0 0.0 26.6 0.0 35.6 o00091 3 M Environmental Laboratory Report No. W 1868 Appendix F: Spreadsheets: Calculation o f Kinetic Parameters Attorney ClientAMork Product Privileged Do N o t Dlacloae Do Not Copy 000032 K in etics Equations used: The hydrolysis rate constant, k=[ ln(RX> - ln(RX). ] /1 where RX is Molar concentration U-. = 0.693/ k, MeFOSEA was tested by the addition of 10 microliters of 10,730ppm MeFOSEA in acetone to 1 0ml of buffer This is equivalent to 107.3 micrograms/ml of MeFOSEA. The formular weight of Methyl FOSEA is equal to 611.27 This makes the initial concentration of MeFOSEA equal to 1.7554E-4 Molar. pH 1.5 Data A verage M eFOSEA Day (PPm ) [M eFOSEAl (M olar) 0 9.90 1.619E-04 0.94 8.33 1 .3 6 3 E -0 4 1.92 7.68 1.257E-04 6.72 5.45 8 .9 1 2 E -0 5 13.90 4.62 7 .5 6 1 E -0 5 >0?1 4.34 7 .0 9 8 E -0 5 27.77 3.20 5 235F.-05 |M eF O S E A |t,[M eFO SE A l, 0.922 0.777 0,716 0.508 0.431 0.404 0.298 n atu ral log o f IM eFO SEA l. [M eFO SEA ],, -0.081 -0.253 -0.334 -0.678 -0.842 -0.905 -1.210 A verage S tandard Dev. k - 0.2690 0.1738 0.1008 0.0606 0.0437 0.0436 0.1152 0.0900 tin (days) - 2.6 4.0 6.9 11.4 15.9 15.9 9.4 5.8 pH 5 Data A verage M eFOSEA [M eFOSEA] D ay (PPb) m easured (M olar) 0 10.34 1 692E-04 0.94 9.36 1 .5 3 2 E -0 4 1.92 8.59 1 405E-04 6.72 8.15 1 333E-04 13.90 7.60 1 243E-04 20.71 5.69 9 .3 1 0 E -0 5 27.77 5.45 8 923E-05 IM eFO SEA U M eFO SE A l. 0.964 0.873 0.801 0.760 0.708 0.530 0.508 n atu ral log o f IM eFO SEA l, [M eFO SEA l, -0.037 -0.136 -0.222 -0.275 -0 345 -0.634 -0.676 A verage S tandard Dev. k - 0.1445 0.1159 0.0409 0.0248 0.0306 0.0244 0 .0 6 3 5 0 .0 5 2 8 tu t (d*ys) - 4.8 6.0 16.9 27.9 22.6 28.4 17.8 10.5 60000 Page 1 pH 7 Data A verage M eFOSEA (M eFOSEAl Day (ppb) m easared (M olar) 0 10.53 1.723E-04 0.94 8.69 1 .4 2 1 E -0 4 6.72 6.02 9.844E-05 13.90 4.88 7 .9 8 4 E -0 5 20.71 4.02 6.569E-05 27.77 2.02 3.305E-05 pH 9 Data A verage M eFOSEA [M eFOSEA] Day (Ppb) aeaMreii (M o la r) 0 10.08 1.650E-04 0.94 10.16 1.662E-04 1.92 7.99 1 3G7E-04 6.72 5.49 8 .9 8 9 E -0 5 13.90 3 96 6 .4 7 8 E -0 5 20.71 2.41 3 .9 5 0 E -0 5 27.77 2.38 3 .9 0 1 E -0 5 pH 11 Data 0 -0.94 -1.92 -6.72 -13.9 -20.71 -27.77 D ay 0 0.94 1.92 6.72 13.90 20.71 27.77 A verage M eFOSEA (PPb) 10.47 8.82 8.50 5.50 3.46 2.54 2.39 [M eFOSEA] m easured (M olar) 1 712E-04 1.444E-04 1.391E-04 8 .9 9 7 E -0 5 5 .6 6 1 E -0 5 4 .1 6 3 E -0 5 3 9 0 7 E -0 5 000094 Kinetics IM eFO SEA l,,{M eFO SEA l. 0.982 0.810 0.561 0.455 0.374 0.188 IM eF O S E A y M eFOSF.A I. 0.940 0.947 0.745 0.512 0,369 0.225 0.222 sturai log o f IM eFOSEAl. (M eFOSEAJ, -0.018 -0.211 -0.578 -0.788 -0.983 -1.670 A verage S tandard Dev. k 0.2246 0.0860 0.0567 0.0474 0.0601 0.0950 0.0739 t m (days) - 3.1 8.1 12.2 14.6 11.5 9.9 4.5 n atu ral log o f IM eFOSEAl. [M eFO SEA J,, -0.062 -0.054 -0.295 -0.669 -0.997 -1.491 -1.504 A verage S tandard Dev. k - 0.0578 0 .1 5 3 5 0.0996 0.0717 0 .0 7 2 0 0.0541 0.0848 00373 tin (day) - 12.0 4.5 7.0 9.7 96 12.8 9.3 3.1 IM eFO SEA yM eFO SEA l. 0.976 0.823 0.792 0.513 0.323 0.237 0.223 starai log o f IM eFO SEA l. [M eFOSEAJ, -0.025 -0.195 -0.233 -0.668 -1.131 -1.439 -1.502 A verage S taadard Dev. k - 0.2078 0.1212 0.0994 00814 00695 0.0541 0 .1 0 5 6 0.0552 in (days) - 3.3 5.7 7.0 8.5 10.0 12.8 7.9 3.3 Page 2