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BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Study Title Indirect Photolysisof Gaseous PerfluorooctanesulfonylFluoride (POSF) by Fourier Transform Infrared (FTIR) Spectroscopy Data Requirement: Based on Literature Review Author Grant M. Plummer, Ph.D. Study Completion Date June 12,2001 Performing Laboratory 3M Environmental Laboratory Building 2-3E-09,935 Bush Avenue St. Paul, MN 55106 Project Identification 3M Laboratory Report No. E01-0739 Total Number of Pages 38 Page 1 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 This page has been reserved for specific country requirements. Page 2 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Statement of Non-Compliance Study Title: Indirect Photolysis of Gaseous Perfluorooctanesulfonyl Fluoride (POSF) by Fourier Transform Infrared (FTIR) Spectroscopy Study Identification Number: E01-0739 This study does not comply with the requirements of the US EPA Good Laboratory Practices (GLP) Standards at 40 CFR Part 792 (TSCA). a6 / h / o , Date ' Page 3 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Table of Contents Statement of Non-Compliance ............................................................................................ 3 List of Tables ........................................................................................................................ 5 List of Figures....................................................................................................................... 5 Study Personnel and Contributors....................................................................................... 5 Location of Archives............................................................................................................. 5 Summary.............................................................................................................................. 6 Introduction .......................................................................................................................... 7 Kinetics Model...................................................................................................................... 8 Materials and Methods....................................................................................................... 12 Method Summary.......................................................................................................... 12 Chemical Characterizations.......................................................................................... 13 Sample Preparation and Analysis................................................................................. 13 Results and Discussion ..................................................................................................... 14 Statistical Methods and Calculations............................................................................ 14 Data Summary and Discussion..................................................................................... 15 Conclusions........................................................................................................................ 17 References......................................................................................................................... 18 Signatures .......................................................................................................................... 19 Appendix A: Plots of Infrared Data .................................................................................... 20 Appendix 8:Plots of Least Squares Analyses Data and Results..................................... 28 Appendix C: Infrared Reference Spectra and Analytical Regions .................................... 36 Page 4 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 List of Tables Table 1. Characterizationsof the Test and Reference Substances................................ 13 Table 2. Run Designationsand ExperimentalConditions ............................................... 13 Table 3. Least Squares Estimates of the Rate Constants and Ratios ............................ 15 Table 4. Estimated Minimum Atmospheric Half-Life of POSF Due to Gas Phase Reactionwith the Hydroxyl Radical Based Only on Run C4 Data..................... 16 List of Figures Figure 1. Structure of POSF .............................................................................................. 7 Study Personnel and Contributors Author Grant M. Plummer, Ph.D. Rho Squared PO Box 61536 Durham, NC 27715 (919) 682-4761 Sponsor William K. Reagen, Ph.D. 3M Environmental Laboratory Bldg. 2-3E-09,35 Bush Avenue St. Paul, MN 55133-3331 (651) 778-6565 3M Environmental Laboratory and Professional Services Contributing Personnel Timothy Gutzkow Pace Analytical Services, Inc., 1700 Elm St., Minneapolis, MN 55144 Location of Archives The 3M Environmental Laboratory will retain the original data documents and digital copies of the original data related to this work for at least 10 years following the effective date of any related final ruling. Information may be obtained through written inquiry addressed as follows: 3M Environmental Laboratory Building 2-3E-09 935 Bush Avenue St. Paul, MN 55106 Page 5 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Summary The primary goal of this study was to determine the first order reaction rate of gaseous pefluorooctanesulfonylfluoride (hereafter, POSF) with the gaseous hydroxyl radical (hereafter, OH) at one atmosphere total pressure and 33" C. Several publications''2* 3* describing related measurementsformed the experimental and theoretical basis of this study. Members of the 3M Environmental Laboratory and other contributing personnel developed the equipment and analytical techniques required to perform the study. Our results are based on the relative.gaseousconcentrationsof POSF and the reference compound monochloromethane(hereafter, CH&l) in the presenceof the OH radical. We performed the concentration measurements using continuous, in-situ Fourier transform infrared (FTIR) spectroscopic techniques. The study data generally indicate that no reactions between POSF and the OH radical occur in the gas phase. Within first order kinetic theory, and in conjunction with the results of independent studies of Cl-hCl and OH, the results of one run (only)performed in this study establish an estimated minimum half-life of POSF related to its reactions with the QH radical. That estimate is, under typical tropospheric conditions, 3.7 years. Page 6 of 38 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E01-0739 Introduction The environmental mobility and fate of a chemical are controlled by a number of natural processes,including volatilization, bioaccumulation,biodegradation,oxidation, reduction, hydrolysis, and photolysis. This work concerns the rate of indirect photolysis of the gaseous form of the compound POSF through its reactions with the gaseous hydroxyl radical OH. Figure Iillustrates the structure of POSF. "Indirect photolysis" is the process by which gas phase radicals are formed in the atmosphere in presence of ultraviolet (UV) radiation and subsequently react with other chemical species. The gas phase reaction with the hydroxyl radical OH is one of several mechanisms by which organic compounds, both natural and synthetic, decompose in the environment. The radical OH and other radicals are present in the troposphere, but only at concentrations below the detection limits of most continuous analytical methods. This work describes an experimental investigationof the indirect photolysis of POSF. The gas test matrix employed in this study consisted of percent levels of 02H,20,03, and He, as well as the compounds C&Cl and POSF at levels below 100 ppm. The matrix was subject to UV and visible radiationin the h 2 200 nm wavelength range. Reference 1 describes in detail the reactions by which the OH radical is produced under such conditions. Figure 1. Structure of POSF F F F F F F F F 0 Page 7 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Kinetics Model As mentioned above, OH radicals exist in the troposphere at concentrations below the detection limits of most continuous analytical methods; this is often true even in the most carefully prepared laboratorygas matrices. However, the concentrationof the OH radical in a well-characterizedtest matrix can be indirectlydeterminedfrom behavior of a reference compound R (in this study, Cl-hCI) for which the first-order OH reaction rate constant k,, is already well known. As described below, this approach allows an estimate of the first-order rate constant k,, for the analyte A (in this study, POSF). In the experiments described here, we introducedozone (03a)nd water (bo)into a series of the test matrices containing POSF and Ci-&CI; when subject to ultraviolet (UV) radiation, these first two molecules react to form the OH radical.' The OH radical can then react with and photolyticallydegrade the analyte and the reference compounds. We noted minor losses in the concentrations of ozone [0,] ,the analyte [A], and the reference compound [R]in the absence of UV radiation;we assume below that these losses were caused by adsorption to or reactions between these compounds and the reaction chamber walls. A model describing the reactions, the first order (or pseudo-first order) rate laws, and the rate constants considered in this work are described below. Reaction A + OH 3 (Products), Rate kAI R (Wall Losses), 0, + H,O +hv 3 2 0 H + 0, We note that this model assumes that the reference and analyte compounds do not undergo direct photolysis, that is, that their concentrations are unaffected by the Page 8 of 38 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E01-0739 presence of the UV radiation except through the described mechanisms involving the hydroxyl radical. Equation 10 also assumes that water is present in excess. In each experimental run, the UV intensity and the concentration [OH] were zero for the period 0 I t I t'and non-zero for times t > t' . Equations describing the measured quantities [O,] , [R] , and[A] as a function of time for each of these conditions are derived below. According to Equations 9 through 12, the differential equations governing the O3 concentrations are ( 0 It It') Eq. (13a) (t>t') Eq. (13b) where the subscript t denotes the concentrations at all times. The solutions to these equations are (0 It It') Eq. (14a) (t>t') Eq. (14b) where the subscripts 0 and t' and denote the concentrations at times t = 0 and t = t' . We assume below that, under each experimental condition and only in the presence of UV radiation, the OH concentration is proportional to the O3concentration. Although the radical OH is extremely reactive, this is a reasonable assumption for our description of the reactions of Equations 1 and 5. The hydroxyl radical concentration is then given by the following expressions: [OH] = 0 (0 It It') Eq. (15a) where a is constant and we have employed the initial condition [OH]tt = a[03t,] at time t = t'. Page 9 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 According to the reaction model and assumptions described above, the differential equations governing the analyte concentrations are (0 I t It') Eq. (16a) Direct integrationof Equation 16a gives the solutionfor 0 It It' (UV = 0): ( 0 I t It') under initial condition[A] = [A] , at time t = 0. Eq. (17) Subject to the conditionthat ko, +ko2 # 0 , direct integrationof Equation 16b gives the general solution of Equation 16b for t > t' (UV $0): M A ] = C - k A 2 t + kA1 a [03"' exp{- (kol +ko2)(t -t')} k01 + k02 and evaluation the constant of integration C at time t = t' yields the specific solution Using the same assumptions and analogous initial conditions, the reference compound concentrations are given by and Page 10 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 For t > t' , Equations 19 and 21 yield the following expression for the ratio k,,/k,, : - =._. in which the four quantities relatedto [A] and [R] are experimentallyaccessible. When k,, = k,, = 0 , an estimate of the ratio k,,/kR1can be directly calculatedfrom the observed concentrations3. In our experiments, the conditionk,, = k,, = 0 did not hold. Therefore, Equation 22 and our experimental data do not provide an accurate estimate of the ratio k,,/k,, . Accordingly, we used Equations 3,4, 11, and 13 in a series of direct least-squares analyses. In these analyses, we adjusted the parameters representingthe rate constants of Equations2,4,6,8, I O , and 12 accordingto the differences between the observed and calculated values of the concentrations [A] , [R] , and [O,] . Equations 14, 17, 19,20, and 21 generated the calculated concentrations, and values of the parameters were varied to the minimize the sum square error (SSE) where the index m indicates the three observed compounds POSF, CH&l,and O3(m = 1 to 3, respectively)and the indexj enumerates the normalized concentrationsAh and their least squares estimates Ah. The normalized concentrationsare the observed concentrations divided by each compound's initial (t = 0) concentration. N N N -The analysis yield the four least-squaresrate constant estimates ko, , ko2, k,, , and k,, , as well as estimates of the two quantities (see Equations 19 and 21) and k R l a LO31 t' KRI = ko, + k02 An experimental estimate of the quantity CR1 = 3.6 xIO-l4cm3sec-' BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 is available in the literature2,so our experimental estimate of the first-order reaction rate constant CAI is (see Equation23) - KAI* k,, z-kR1 . KRI Using the estimated value of Equation 27, the analyte concentration in the absence of wall effects (i.e. when k,, = 0) and in the presenceof a constant hydroxyl radical concentration [OH] (for instance, in the Earth's lower atmosphere) obeys Under these conditions, our experimental estimate of the analyte half-life is given by Materials and Methods Method Summary We prepared and analyzed the samples included in this study between August 8 and August 24,2000; our techniques were based on those described in References 1,2,3, and 4. We performed all the measurementsdescribed here in a combination reaction chamber and infrared absorption cell developed and patented by 3M Corporation5. For this study, the cell was equipped with a capacitance barometer (Kurt J. Lesker Company, Model KJL-902056) and a polished, semkonductor-grade quartz window (Glass Tech Supplies, Inc.) through which UV radiation from a broad-band discharge lamp (Ariel Inc., Model#6269) was introducedto the reagent gases. The temperatureof the chamber was maintained at 33C. Except for the infrared mirror faces, we manually cleaned the interior surfaces of the cell with acetone before each sample preparation. We added reagentsto the chamber after first evacuating it to pressuresbelow 100 mTorr, and determined the resulting mixture concentrationsfrom the original gas standard concentrations and the barometric measurements. We generated O3by illuminating a 40% - 60% gaseous mixture of O2and helium (He) with a short- wavelength UV source in a separate reaction chamber (Therm0 Environmental, Inc. NO, Analyzer, Model 42C) and transferred the resulting gas, which contained approximately 1% OB,to the reaction chamber/lR absorption cell. Page 12 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Chemical Chamctetions Table 1 lists the properties the test and reference materials used in this study. Table 1. Characterizations of the Test and Reference Substances I Expiration Date I Storage Conditions Cylinder or Lot Number Laboratory N/A Silcosteel ambient T, 30 Psig 12517LB I Company I Company I Company I Laboratory I 7/27/2001 I 7/27/2001 1 N/A I steel cylinder, steel cylinder, steel cylinder, ambient ambient ambient Ns/Aamplep te-2m1p0e0raptusrige, te-2m1p0e0raptusrige, te-2m1p0e0raptusrige, tube,aanmdbPient 00-564-L 8G9123566 OSC38878 N/A Sample Prepamtion and Analysis We prepared all the samples used in this study using barometric measurements; all reagents were introduced into the experimental apparatus as gases. Table 2 describes the control conditions and concentrations. Table 2. Run Designations and Experimental Conditions Reagent Pressures (Torr) AEstimated from the input 0 2 concentration and manufacturers' stated ozonator efficiency for air at flow rates of one liter per minute (2.5%). Page 13 of 38 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E01-0739 Results and Discussion Statistical Methods and Calculations - Usingfunctions provided in Microsoft@Excel@software, we have used the kinetics model described above to form estimates of the rate constants ioilo, ,f,,, , and k,, , as well as estimates of the two quantities gAa1nd E, (see Equations24 through 27). The estimates presented below for each sample and control condition described in Table 3 are those leading to a minimum in the related sum square error in the normalized concentrationsdescribed in Equation23. In our performanceof these least-squares analyses, we constrained the parameter parametric constraints necessary. to non-negative values, and found no other The reaction chamber/lR absorption cell provides an infrared absorption pathlength of 10 metersfor monitoringthe reagent concentrations. We used a MIDACTMModel 12001 FTlR spectrometer and associated software (AutoQuanP V3.11) to acquire infrared absorbance spectra of the gaseous mixtures. The nominal spectral resolution of the system is 0.5 cm-', and it employs a mercury-cadmium-telluride (MCT) detector operated at 77K. We confirmed the system absorption pathlength through comparisons of experimental spectra to those of the National Institutefor Standards and Technology (NIST) spectral database spectrum of ethylene. We determined relative concentrations of POSF, CH&I, and O3using a classical least squares (CLS) spectral analysis technique within AutoQuantnV'.The analytical regions employed (in cm-') were 1101.6 - 1320.7,2824.5- 3012.7, and 2052.5- 2141.7, respectively; all these analyses employed linear baseline corrections. Appendix A portrays the CLS results; Appendix B illustrates the reference spectra and analytical regions. The concentration values of Appendix A have been independently and arbitrarily scaled to allow a clear graphical representationof the concentrationtrends, and do not represent the actual concentrations. The actual volumetric part-per-millionconcentrationsof the three compoundson which we have based our results varied greatly over the required control and sample conditions. To avoid bias in the least squares analyses, which are sensitive to the absolute concentration values, we normalized each concentration by dividing it by the first concentrationvalue used in the analyses. These normalized concentrations are represented in the figures of Appendix C, which also illustrate our analytical results. Page 14 of 38 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E01-0739 Data Summary and Discussion Table 3 lists the results of the least squares analyses of the normalized concentration data for POSF, CH3CI,and O3under four control conditions and two sample conditions. I Table 3. Least Squares Estimates of the Rate Constants and Ratios I E N u N N Run/Control Control kA2 A, kR 2 ERI k02 k0l Designation Condition (A) (B) (A) (B) (A) (A) c1 High UV I.78x 1 0 2.31 X 3.52 X 2.00 X 9.58 X IO-' c2 [A] = 0 N/A 5.46X I O " 1.38X 10.` 1.51X I O F 3 5.75X IO-' c3 IRl= 0 1.06 X10-3 0 NIA N/A 1.11 x i o " 5 . 2 8 ~IO-* c4 1 c5 High[Rl High [AI 9.15X 1.07 x 2.17X 0 3.12X 8.30 x 1.29X IO-' 1.05X I O " 6.09X IO-' I 2.72 x 6.09 x 4.09 x IO-^ SI None 1.52 X 10" 0 5.73 X 1.28X lo-' 3.28 X 10" 4.90 X IO-' s2 None 7.84X 0 8.86X 7.14X 1.45X 5.39X `In units cm3 min-' Table 3 demonstratesthe variability in the parameters cA,,, f,, , and Ko2 over the course of our experiments. These parameters describe losses of the compounds that are not related to the presence of UV radiation, and may have been caused by interactions with the sample chamber walls. As described above, the magnitude and variability of these parameters prevent accurate application of Equation 22. The least squares results of Table 3 are based on a single mathematical constraint, namely, thatKAwl as required to remain non-negative. In all but one case (that of control condition C4) the value of leading to the least squares solutions was "bound" to the value zero. This means that, in these cases, the value kA=l 0 leads to the minimum model error ( SSE) under the (single) constraintEAl1 0, and that the majority of the experimental data (three control runs and two sample runs) show no degradation of POSF. Therefore, the main finding of this work is that POSF does not undergo indirect photolysis in the presence of the hydroxyl radical. The available data do not explain why the results of control condition C4, under which the concentration of the reference compound (CI-hCI) was elevated, should lead to a detectable decrease in the POSF concentration. A plausible explanation is that the reference compound, through either direct or indirect photolysis, produced other radicals (including, possibly,the CI radical) that do react with and lead to the degradationof POSF. Such an effect might only be apparent under conditions such as those of run C4, with relatively high C&Cl concentration. If we nonetheless assume that the observed (Run C4) degradation was caused by the hydroxyl radical alone, then an estimate of the half-life of POSF related to its gas phase Page 15 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 reactions with the hydroxyl radical alone is available. Table 4 presents the details of the related calculation. Table 4. EstimatedMinimumAtmosphericHalf-Life of POSF Due to Gas Phasc Reaction with the Hydroxyl Radical Based Only on Run C4 Data. Quantitv Run C4 rate ratio E,, Dimensions cm3 min-l Value Reference 1.29E-02 cR1 Run C4 rate ratio gAl Known Rate Constant Calculated Rate Constant LA, &,, .<nown[OH] in lower atmosphere Rate { [OH] } TI/ for POSF TI/ for POSF cm3 min-' cm3s e d cm3s e d -3 sed seconds years 2.17E-03 3.60E-14 6.06E-15 9.70E+05 5.87E-09 1.18E+08 3.74E+00 Because on/y the Run C4 data indicate a non-zerovalue of EA,w, e consider the TI,, value presented in Table 4 (3.7 years) as the minimum value POSF half-life supported by the study data. Page 16 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Conclusions We have performed a study of the indirect photolysisof perfluorooctanesulfonylfluoride (POSF) in the gas phase. The primary goal of this study was to determine a first order reaction rate constant describing the gas phase reactions between POSF and the hydroxyl radical at 33" C and one atmosphere total pressure. Our results are based on the relative gaseous concentrations of POSF and the reference compound monochloromethane (CH&I) in the presence of OH and ultraviolet (UV) radiation. We performed the concentration measurements using continuous, in-situ Fourier transform infrared (FTIR) spectroscopic techniques. Six of the seven control and sample runs we performed indicated no degradation of POSF in the presence of the OH radical. Therefore, our main finding is that reactions between POSF and the OH radical do not occur in the Earth's atmosphere. However, in one control run only, we observed a slight decrease in the POSF concentration. The relative rates of degradation of POSF and Cl-hCl observed in this single run, in conjunction with as a previously published' rate for the CI-&Cl- OH reaction, are consistent with a POSF half-life of 3.7 years in the presence of typical tropospheric concentrations of the OH radicaL4 It is likely that the actual atmospheric POSF half-life is longer, and potentially much longer, than 3.7 years. Page 17 of 38 BACK TO MAIN 3 M Environmental Laboratory Report No. E01 -0739 References ' T.J. Wallington et al, J, Chem. Phys. A 101,pp. 8264-8274 (1997), and references therein. W.B. DeMore et at, NASA Jet Propulsion Laboratory, JPL Publication No. 94-26 (1994). M.J. Molina et al , "Atmospheric Lifetime Studies of Some Halogenated Ethers L-14055, L-14056, and L-14093," report to the 3M Specialty Chemicals Division (March 1996). R.G. Prinn et al, Science=, pp. 187-192 (1995). The IR absorption cellheaction chamber is described in United States Patent No. 5,777,735 (1998). Page 18 of 38 Signatures grant M. Plummer, Ph.D., Author BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 I Ob lZb I bate William K. Reagen, Ph.D., Laboratory Management Date Page 19 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Appendix A: Plots of Infrared Data Page 20 of 38 8.0 7.0 6.0 A BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure A I . Observed Relative Concentrations For Control Conditions C I A and C I B (High UV). UV = 0 fort C 62 min. B ----1 ... .. .. .. -- L C H 3 C I UV OFF I ~ ~ II --4--CH3CI UV ON I - Y E 2.0 1.o 0.0 0 \ b , 20 40 60 80 100 120 140 Minutes Page 21 of 38 8.0 7.0 6.0 A S 0 .-.cI E 5.0 .cI 6 S a 0 S 4.0 .*a>- Q 5 3.0 pc Y - c 2.0 1.o 0.0 0 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E01-0739 Figure A2. Observed Relative Concentrations For Control Conditions C2A and C2B (High UV). UV = 0 fort 59 min. 4 P e C H 3 C I UV OFF - - 8 4 -CH3CI UV ON *03 UV OFF * - 43 - - 0 3 UV ON 20 40 60 80 100 120 140 Minutes Page 22 of 38 8.0 7.0 6.0 A A E 0 .-U E 5.0 U E 0 0 0 4.0 .-0> U tu 5 3.0 c Y E - 2.0 1.o 0.0 0 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure A3. Observed Relative Concentrations For Control Conditions C3A and C3B (Zero Reference Concentration). UV = 0 fort 127 min. --8-03 UV OFF - 0 - -03 UVON e---POSF UV OFF A- POSF UV ON 50 100 150 200 250 Minutes Page 23 of 38 8 .O -.-n 6.0 E 0 c 5m, 5.0 E 60, 0 E 4.0 .->0, 5cm, 3.0 w Y --E 2.0 1 .o 0.0 20 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E01-0739 Figure A4. Observed Relative Concentrations For Control Conditions C4A and C4B (High Reference Concentration). UV = 0 for t < 83 min. e C H 3 C I UV OFF , - 4- -CH3CI UV ON +03 UV OFF -I- 0 3 UV ON A POSF UV OFF - 4 - -POSF uv ON 40 60 80 100 120 140 160 Minutes Page 24 of 38 8.0 7.0 A .5-A 6.0 E U c) S 6Q) 0 E 5.0 .->Q) -U m d Z 4.0 - E 3.0 2.0 0 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure A5. Observed Relative Concentrations For Control Conditions C5A-C5B (High Analyte Concentration). UV = 0 fort 62 min. Q. e C H 3 C I UV OFF - 4 - -CH3CI UV ON +03 UV OFF -a--03UVON -&-POSF UV OFF - - -8.--POSF UV ON 20 40 60 80 100 120 140 Minutes Page 25 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure A6. Observed Relative Concentrations For Sample Conditions SIA-SI B. UV = 0 for t 82 min. 8.0 7.0 -S- C H X I W OFF 6.0 A A .5S0- 5.0 .c) S 6Q, 0 C 4.0 .-Q>, ca , 5 3.0 E S 2.0 *CHXI W ON +0 3 W OFF -03WON +~FWOFF -+--POSFWON 10.0 I 0 I I I I I I I 20 40 60 80 100 120 140 160 180 Minutes I Page 26 of 38 8.0 7.0 .-* 6.0 h c 0 .CI 0 b 5.0 c scQ) 0 4.0 .->Q) .CI 2I? 3.0 v =v 2.0 1 .o 0.0 0 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure A7. Observed Relative Concentrations For Sample Conditions S2A-S2B. UV = 0 fort 63 min. e C H 3 C I UV OFF - - 4 - -CH3CI UV ON +03 UV OFF - 0 - -03 UV ON *POSF UV OFF . - A - -POSF UVON 20 40 60 80 100 120 140 Minutes Page 27 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Appendix 6: Plots of Least Squares Analyses Data and Results Page 28 of 38 1.o -1.o -2.0 h $- -3.0 C -4.0 -5.0 -6.0 -7.0 0 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure B1. Observed and Calculated Concentration Ratios For Control ConditionsC I A and CIB (High UV). UV = 0 fort e 62 min. "\ A A A POSFObserved I - I 1 POSF Calculated iI! i 0 CHBClObserved ++CH3CI Observed A 03Obsetved -0 3 Calculated A 20 40 60 80 100 120 140 Minutes Page 29 of 38 1.o 0.0 -1 .o g h -2.0 - E -3.0 -4.0 -5.0 0 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure 82. Observed and Calculated Concentration Ratios For Control Conditions C2A and C2B (High UV). UV = 0 fort 59 min. 0 CHXlObsewed --st CH3CI Calculated A 03Obsewed -0 3 Calculated 20 40 60 80 100 120 140 160 Minutes Page 30 of 38 1 .o 0.0 -1 .o -2.0 -2Yh 0 E -3.0 -4.0 -5.0 -6.0 0 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure 63. Observed and Calculated Concentration Ratios For Control Conditions C3A and C3B (Zero Reference Concentration). UV = 0 fort 127 min. I I I I 50 100 150 Minutes 0 POSFObsewed -POSF Calculated A 03Obsewed -0 3 Calculated Page 31 of 38 0.5 0.0 -0.5 -1.o -1.5 h 0g" -2.0 - E -2.5 -3.0 -3.5 -4.0 -4.5 0 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure B4. Observed vs. Calculated Concentration Ratios For Control Conditions C4A and C4B (High Reference Concentration). UV = 0 fort e 83 min. 0 POSF Observed V O S F Calculated 0 CH3CI Observed +CH3CI Observed A 03Observed A A -0 3 Calculated I I I I I I I 20 40 60 80 100 120 140 160 Page 32 of 38 0.5 0.0 -0.5 -1 .o - h 0 Y2 -1.5 c -2.0 -2.5 -3.0 -3.5 0 BACK TO MAIN 3M EnvironmentalLaboratory Report No.E01-0739 Figure 85. Observed and Calculated Concentration Ratios For Control Conditions C5A-C5B (High Analyte Concentration). UV = 0 fort 62 min. A A A 0 POSFObserved -POSF Calculated 0 CH3CI Observed --ic CH3CI Observed A 03Observed -0 3 Calculated 20 40 60 80 100 120 140 Minutes Page 33 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 I Figure B6. Observed and Calculated Concentration Ratios For Sample Conditions SlA-S1B. UV=Ofort<82min. 0.0 -1.o 5 h -2.0 - E -3.0 -4.0 0 POSFObserved -POSF Calculated 0 CH3CI Observed ++CH3CI Observed A 03Observed -0 3 Calculated -5.0 ! 0 I I I I I I 1 1 20 40 60 80 100 120 140 160 180 Minutes Page 34 of 38 0.5 0.0 -0.5 -1 .o -1.5 h 0 Y2 -2.0 -2.5 -3.0 -3.5 -4.0 -4.5 0 BACK TO MAIN 3M EnvironmentalLaboratory Report No. E01-0739 Figure 67. Observed and Calculated Concentration Ratios For Sample Conditions S2A-S2B. UV = 0 fort e 63 min. 0 POSFObserved -POSF Calculated 0 CH3CIObserved ++CH3CI Calculated A 03Observed -0 3 Calculated A 20 40 60 80 100 120 140 Minutes Page 35 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Appendix C: Infrared Reference Spectra and Analytical Regions Page 36 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 POSF Analytical Region -I__ T------- ---i----17-----1-.-,.--.--^--?l_____l_ - - - 1 50 1400 1350 1300 1250 1200 1150 1100 10 Absorbance I Wavenumber (cm-1) I CH3CI Analytical Region .01 ---~-.---r'._I_ ----lr _____.I_--TI 7--.B 3200 3100 3000 2900 2800 2700 Absorbance I Wavenumber (cm-1) Page 37 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 0 3 Analytical Region I I -4 j j--*-----.-7- 1_7____1__ -7--.-----7---.p^.....-.-.-.-- 2200 2180 2160 2140 2120 2100 2080 2060 2040 Absorbance I Wavenumber (cm-1) Page 38 of 38