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BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Study Title Indirect Photolysis of Gaseous Perfluorooctanesulfonyl Fluoride (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). 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 S u m m a ry ...................................................................................................................................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 R eferen ces.............................................................................................................................. 18 Signatures...............................................................................................................................19 Appendix A: Plots of Infrared D ata.......................................................................................20 Appendix B: 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. Characterizations of the Test and Reference Substances................................ 13 Table 2. Run Designations and Experimental Conditions................................................ 13 Table 3. Least Squares Estimates of the Rate Constants and R atios............................ 15 Table 4. Estimated Minimum Atmospheric Half-Life of POSF Due to Gas Phase Reaction with 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 perfluorooctanesulfonyl fluoride (hereafter, POSF) with the gaseous hydroxyl radical (hereafter, OH) at one atmosphere total pressure and 33 C. Several publications1,2| 3' 4 describing related measurements formed 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 gaseous concentrations of POSF and the reference compound monochloromethane (hereafter, CH3CI) in the presence of 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 CH3CI 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 Environmental Laboratory 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 1 illustrates 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 investigation of the indirect photolysis of POSF. The gas test matrix employed in this study consisted of percent levels of 0 2, H20 , 0 3, and He, as well as the compounds CH3CI and POSF at levels below 100 ppm. The matrix was subject to UV and visible radiation in the X > 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 l: O F -----------------------------S ------------F FF FFO 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 laboratory gas matrices. However, the concentration of the OH radical in a well-characterized test matrix can be indirectly determined from behavior of a reference compound R (in this study, CH3CI) for which the first-order OH reaction rate constant k R1 is already well known. As described below, this approach allows an estimate of the first-order rate constant k A1 for the analyte A (in this study, POSF). In the experiments described here, we introduced ozone ( 0 3) and water (hfeO) into a series of the test matrices containing POSF and CH3CI; when subject to ultraviolet (UV) radiation, these first two molecules react to form the OH radical.1 The OH radical can then react with and photolytically degrade the analyte and the reference compounds. We noted minor losses in the concentrations of ozone [ 0 3] , 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 => (Products)A Rate k A, [A ] [OH] Eqs. (1), (2) A => (Wall Losses )A R + OH => (Products ^ k A2 [A ] k R1 [r ] [ o h ] Eqs. (3), (4) Eqs. (5), (6) R => (Wall Losses )R k R2 [R] Eqs. (7), (8) 0 3 + H 20 + h v => 2 0 H + 0 2 k 01 [0 3] Eqs. (9), (10) 0 3 => (Wall Losses)0 k 02 [0 3] Eqs. (11), (12) 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 Environmental Laboratory 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 < t < t'a n d non-zero for times t > t ' . Equations describing the measured quantities [ 0 3] , [ 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 0 3 concentrations are d [0 3], = - [ 0 3], k 0J dt (0<t<t') Eq. (13a) d [0 3] , = - [ 0 , ] , ( k ol + k 02 ) dt (t> t') Eq. (13b) where the subscript t denotes the concentrations at all times. The solutions to these equations are [ 0 3], = [ O 3] 0 e x p {-k 02t}03 [ 0 3] t = [ 0 3] t, exp{- (k 01 + k 02 )(t - t')} (0< t <t') 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 0 3 concentration. 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]t =0 (0< t< t') Eq. (15a) [OH] t = a [ 0 3] t, exp{- (k01 + k 02Xt - t ' )} Eq. (15b) where a is constant and we have employed the initial condition [ O H ] = a [ 0 3] t, 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 d [ A ] t = 4 A ] t (kA2)dt (0< t< t') Eq. (16a) d[A] t = - [A] t (kA2 + k A,[OH] t,) dt = - [A ] t (kA2 + k A1oc[03] t' exp { - (k oi + k 02X* - 1' ) }) dt (t> t') Eq. (16b) Direct integration of Equation 16a gives the solution for 0 < t < t ' (UV = 0): in [ A ] , - k A2t [A] o (0 < t < t') Eq. (17) under initial condition [A ] t = [A ] 0 at time t = 0. Subject to the condition that k 01 + k 02 * 0, direct integration of Equation 16b gives the general solution of Equation 16b for t > t ' (UV *0): kA1 a [ 0 3] t, r , , ,, ln[A]t = C - k A2t + -- ------------exp{-(k01 + k 02X t - t )} k 01 + k o2 ( t > t' ) Eq. (18) and evaluation the constant of integration C at time t = t ' yields the specific solution [A] t In = - k A2( t - 1 ' ) - ** ^ 3^* i1- exp{- (koi + k 02X t - t ' )}] [A], ^01 ^02 ( t > t' ) Eq. (19) Using the same assumptions and analogous initial conditions, the reference compound concentrations are given by [R]t h [R]0 --k R2t (0< t< t') Eq. (20) and [R], In = - k R2(t - 1') -- ^ [ i _ exp { - (k o, + k 02 Xt - 1' )}] [R] koi k 02 (t> t') Eq. (21) 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 A1/ k R1: k A1 .l n ( [ A ] t / [ A ] 1,) + k A2( t - t /) k R1 l n ( [ R ] t / [ R ] t, ) + k R2( t - t ' ) Eq. (22) in which the four quantities related to [A ] and [R ] are experimentally accessible. When k A2 = k R2 = 0 , an estimate of the ratio k A1/ k R] can be directly calculated from the observed concentrations3. In our experiments, the conditionkA2 = k R2 = 0 did not hold. Therefore, Equation 22 and our experimental data do not provide an accurate estimate of the ratio k A1/ k R1. Accordingly, we used Equations 3,4,11, and 13 in a series of direct least-squares analyses. In these analyses, we adjusted the parameters representing the rate constants of Equations 2,4, 6, 8,10, and 12 according to the differences between the observed and calculated values of the concentrations [ A ] , [ R ] , and [ 0 3]. 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) Eq. (23) m, J where the index m indicates the three observed compounds POSF, CHsCl.and 0 3 (m = 1 to 3, respectively) and the index j enumerates the normalized concentrations A ]m and their least squares estimates A ^ . The normalized concentrations are the observed concentrations divided by each compound's initial (t = 0) concentration. The analysis yield the four least-squares rate constant estimates k 01, k 02, k A2, and k R2, as well as estimates of the two quantities (see Equations 19 and 21) _ k]*A a [O 3] t' Eq. (24) and k RJ cl [ 0 3] t * Eq. (25) An experimental estimate of the quantity k R1 =3 .6 x10 '14cm3sec'1 Eq. (26) Page 11 of 38 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 k A1 is (see Equation 23) k A, ~ | ^ k R1 . ^R1 Eq. (27) Using the estimated value of Equation 27, the analyte concentration in the absence of wall effects (i.e. when k A2 = 0 ) and in the presence of a constant hydroxyl radical concentration [O H ] (for instance, in the Earth's lower atmosphere) obeys [ A ] t = - [ A ] 0e x p { - k A1[ O H ]t }. Eq. (28) Under these conditions, our experimental estimate of the analyte half-life is given by Jn(2) k A1[OH] ' Eq. (29) 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 measurements described here in a combination reaction chamber and infrared absorption cell developed and patented by 3M Corporation5. For this study, the cell w as equipped with a capacitance barom eter (Kurt J. Lesker Company, Model KJL-902056) and a polished, semi-conductor-grade quartz window (Glass Tech Supplies, Inc.) through which UV radiation from a broad-band discharge lamp (Ariel Inc., Model #6269) was introduced to the reagent gases. The temperature of 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 reagents to the chamber after first evacuating it to pressures below 100 mTorr, and determined the resulting mixture concentrations from the original gas standard concentrations and the barometric measurements. We generated 0 3 by illuminating a 40% - 60% gaseous mixture of 0 2 and helium (He) with a shortwavelength UV source in a separate reaction chamber (Thermo Environmental, Inc. NOx Analyzer, Model 42C) and transferred the resulting gas, which contained approximately 1% 0 3, to the reaction chamber/IR absorption cell. Page 12 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Chem ical Characterizations Table 1 lists the properties the test and reference materials used in this study. Table 1. Chiiracterizations of the Test and Reference Substances Test or Reference Substance Source Expiration Date Storage Conditions Cylinder or Lot Number POSF ChIHe ChbCI/He He H2O 3M Environmental Laboratory N/A Silcosteel canister, ambient T, 30 psig 12517LB Oxygen Services Company 7/27/2001 steel cylinder, ambient temperature, -2 1 0 0 psig 00-564-L Oxygen Services Company 7/27/2001 steel cylinder, ambient temperature, -2 1 0 0 psig S G 9 123566 Oxygen Services Company N/A steel cylinder, ambient temperature, -2 1 0 0 psig OSC38878 3M Environmental Laboratory N/A Pyrex sample tube, ambient T and P N/A Sam ple Preparation 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 R eagent Pressures (T orr) R un D esignation C IA C1B C o n tro l/ S am ple C o n dition uv =o H igh UV D ata UV S et (W atts) T11A 0 tu b 600 o 3a 16 16 h 2o 6 6 O j/H e 655 655 P O S F C H 3C I/H e 9 100 9 100 C2A C2B C3A [A]= 0; UV = 0 [A] = 0 [R]= 0; UV = 0 T12A T12B T13A 0 300 0 17 17 19 6 664 0 6 664 0 6 755 9 100 100 0 C3B C4A [R ]-0 H igh [R]; UV = 0 T13B T14A 300 0 19 9 6 755 9 6 355 9 0 400 C4B C5A H igh [R] H igh [A]; U V = 0 T14B T15A 300 0 9 16 6 355 9 400 6 628 36 100 C5B SIA H igh [A] T15B Sample Run #1; UV = 0 T 8A 300 0 16 16 6 628 36 6 655 9 100 100 SIB S am ple R un #1 T8B 300 16 S2A Sample Run #2; UV = 0 T17A 0 16 6 655 9 6 655 9 100 100 S2B Sam ple Run #2 T17B 300 16 6 655 9 100 AE stim ated from the input O 2 concentration and m an ufactu rers' stated o zon ato r efficiency for air at flow rates of one liter per minute (2.5% ). Page 13 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Results and Discussion S tatistical Methods and Calculations Using functions provided in Microsoft Excel software, we have used the kinetics model described above to form estimates of the rate constants k 01, k 02, k A2, and k R2, as well as estimates of the two quantities K A1 and K R1(see Equations 24 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 concentrations described in Equation 23. In our performance of these least-squares analyses, we constrained the parameter K A1 to non-negative values, and found no other parametric constraints necessary. The reaction chamber/IR absorption cell provides an infrared absorption pathlength of 10 meters for monitoring the reagent concentrations. We used a MIDACTM Model 12001 FTIR spectrometer and associated software (AutoQuantTM V3.11) to acquire infrared absorbance spectra of the gaseous mixtures. The nominal spectral resolution of the system is 0.5 cm '1, 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 Institute for Standards and Technology (NIST) spectral database spectrum of ethylene. We determined relative concentrations of POSF, CH3CI, and 0 3 using a classical least squares (CLS) spectral analysis technique within AutoQuantTM. The analytical regions employed (in cm'1) 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 representation of the concentration trends, and do not represent the actual concentrations. The actual volumetric part-per-million concentrations of the three compounds on 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 concentration value 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 Environmental Laboratory Report No. E01 -0739 Data Sum m ary and Discussion Table 3 lists the results of the least squares analyses of the normalized concentration data for POSF, CH3CI, and 0 3under four control conditions and two sample conditions. Table 3. Least Squares Estimates of the Rate Constants and Ratios Run/Control Control Designation Condition ^A2 (A) k a1 (B) ^R2 (A) K R1 (B) ^02 (A) ^01 (A) C1 High U V 1 .7 8 X 1er3 0 2.31 X 1 0 '2 3 .5 2 X 10 '3 2 .0 0 X 10 '3 9 .5 8 X 1 0 '2 C2 [A] = 0 N/A N /A 5 .4 6 X 1 0 '3 1 .3 8 X 1 0 -2 1.51 X 1 0 `3 5 .7 5 X 1 0 `2 C3 [R]= 0 1 .0 6 X 1 O'3 0 N /A N /A 1.11 X 1 0 `3 5 .2 8 X 10 '2 C 4 High [R] 9 .1 5 X 1 0 `4 2 .1 7 X 1 0 -3 3 .1 2 X 1 0 '3 1 .2 9 X 10 '2 1.0 5 X 1 0 `3 6 .0 9 X 1 0 `2 C 5 High [A] 1.0 7 X 1 0 `3 0 8 .3 0 X 1 0 `3 2 .7 2 X 1 0 `3 6 .0 9 X 1 0 '4 4 .0 9 X 1 0 '2 S1 None 1 .5 2 X 10 -3 0 5.73 X 10 '3 1.28 X 10'2 3.28 X 10 '3 4.90 X 10'2 S2 None 7 .8 4 X 10`4 0 8 .8 6 X 10`3 7 .1 4 X 1 0 '3 1.45 X 10`3 5.39 X 10'2 Aln units min'1. Bln units cm3 min'1. Table 3 demonstrates the variability in the parameters k A2, k R2, and k 02 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, th a tK A1was required to remain non-negative. In all but one case (that of control condition C4) the value of K A1 leading to the least squares solutions was "bound" to the value zero. This means that, in these cases, the value K a1= 0 leads to the minimum model error ( SSE) under the (single) constraintKA1 > 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 o f the hydroxyl radical. The available data do not explain why the results of control condition C4, under which the concentration of the reference compound (G-feCI) 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 Cl radical) that do react with and lead to the degradation of POSF. Such an effect might only be apparent under conditions such as those of run C4, with relatively high CH3CI 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. Estimated Minimum Atmospheric Half-Life of POSF Due to Gas Phase Reaction with the Hydroxyl Radical Based Only on Run C4 Data. Quantity Dimensions Value Reference Run C4 rate ratio K R1 cm 3 m in'1 1.29E-02 Eq. (25) Run C4 rate ratio K A] cm3min'1 2.17E-03 Eq. (24) Known Rate Constant k R1 cm 3s e c '1 3.60E-14 (2) Calculated Rate Constant k A] Known [OH] in lower atmosphere Rate { k R1 [OH]} cm 3 s e c '1 cm '3 sec'1 6.06E-15 9.70E+05 5.87E-09 Eq. (27) (3) Eq. (29) f 1/2for POSF seconds 1.18E+08 Eq. (29) T1/2for POSF years 3.74E+00 Eq. (29) Because only the Run C4 data indicate a non-zero value of K A1, we consider the f 1/2 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 photolysis of perfluorooctanesulfonyl fluoride (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 (CH3CI) 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 CH3CI observed in this single run, in conjunction with as a previously published1rate for the CH3CI - OH reaction, are consistent with a POSF half-life of 3.7 years in the presence of typical tropospheric concentrations of the OH radical.4 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 3M Environmental Laboratory Report No. E01 -0739 References12345 1T.J. Wallington et al, J. Chem. Phys. A 101, pp. 8264-8274 (1997), and references therein. 2W.B. DeMore et al, NASA Jet Propulsion Laboratory, JPL Publication No. 94-26 (1994). 3 M.J. Molina et a l, "Atmospheric Lifetime Studies of Some Halogenated Ethers L-14055, L-14056, and L-14093," report to the 3M Specialty Chemicals Division (March 1996). 4 R.G. Prinn et al, Science 269. pp. 187-192 (1995). 5The IR absorption cell/reaction 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 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 In { (Relative Concentrations)} BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Figure A1. Observed Relative Concentrations For Control Conditions C1A and C1B (High UV). UV = 0 for t < 62 min. 4 -- CH3CI UV OFF -- CH3CI UV ON -Q-- 0 3 UV OFF -- 0 3 UV ON A -- POSF UV OFF A -- POSF UV ON Page 21 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Figure A2. Observed Relative Concentrations For Control Conditions C2A and C2B (High UV). UV = 0 for t < 59 min. *-- CH3CI UV OFF - - O - -CH3CI UV ON B-----0 3 UV OFF - - -O - - 0 3 UV ON In { (Relative Concentration)} Page 22 of 38 In { (Relative Concentration) } 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 for t < 127 min. a-----0 3 UV OFF - - O - - 0 3 UV ON A-- POSF UV OFF A -- POSFUVON Page 23 of 38 In { (Relative Concentration)} BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure A4. Observed Relative Concentrations For Control Conditions C4A and C4B (High Reference Concentration). UV = 0 for t < 83 min. ----- CH3CI UV OFF - * ^ -CH3CI UV ON G----- 0 3 UV OFF - -D - - 0 3 UV ON -A-- POSF UV OFF - - A - - P 0 S F UV ON Minutes Page 24 of 38 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 for t < 62 min. * ----- CH3CI UV OFF - - -O - -CH3CI UV ON e -----0 3 UV OFF - - -Q - - 0 3 UV ON A-- POSF UV OFF A POSF UV ON In { (Relative Concentration)} Page 25 of 38 In { (Relative Concentratio n )} BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Figure A6. Observed Relative Concentrations For Sample Conditions S1A-S1B. UV = 0 for t < 82 min. -----g-- - CH3CI UV OFF -----g-- - CH3CI UV ON -- e-- - 0 3 UV OFF --- -- - 0 3 UV ON -- & --- POSF UV OFF -- & - -F O S F U V O N Page 26 of 38 In { (Relative C oncentration)} BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Figure A7. Observed Relative Concentrations For Sample Conditions S2A-S2B. UV = 0 for t < 63 min. e----- CH3CI UV OFF O' - -CH3CI UV ON e -----0 3 UV OFF - - -O - - 0 3 UV ON A-----POSF UV OFF - - O - - POSF UV ON Page 27 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Appendix B: Plots of Least Squares Analyses Data and Results Page 28 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Figure B1. Observed and Calculated Concentration Ratios For Control Conditions C1A and C1B (High UV). UV = 0 for t < 62 min. POSF Observed POSF Calculated o CH3CI Observed -- CH3CI Observed A 0 3 Observed 0 3 Calculated Page 29 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure B2. Observed and Calculated Concentration Ratios For Control Conditions C2A and C2B (High UV). UV = 0 for t < 59 min. o CH3CI Observed CH3CI Calculated A 0 3 Observed 0 3 Calculated Page 30 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Figure B3. Observed and Calculated Concentration Ratios For Control Conditions C3A and C3B (Zero Reference Concentration). UV = 0 for t < 127 min. Page 31 of 38 In (C/Co) 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 for t < 83 min. POSF Observed 'OSF Calculated O CH3CI Observed " X CH3CI Observed A 0 3 Observed 0 3 Calculated Page 32 of 38 In (C/C0) BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure B5. Observed and Calculated Concentration Ratios For Control Conditions C5A-C5B (High Analyte Concentration). UV = 0 for t < 62 min. In (C/Co) POSF Observed -- -P O S F Calculated o CH3CI Observed ---* -- CH3CI Observed A 0 3 Observed 0 3 Calculated - ------------------------------------- 1--------------------------------------J 0 20 40 II 60 80 Minutes I1 100 120 140 Page 33 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Figure B6. Observed and Calculated Concentration Ratios For Sample Conditions S1A-S1B. UV = 0 for t < 82 min. POSF Observed POSF Calculated o CH3CI Observed X CH3CI Observed A 0 3 Observed 0 3 Calculated Page 34 of 38 In (C/C0) BACK TO MAIN 3M Environmental Laboratory Report No. E01-0739 Figure B7. Observed and Calculated Concentration Ratios For Sample Conditions S2A-S2B. UV = 0 for t < 63 min. o POSF Observed " POSF Calculated o CH3CI Observed - CH3CI Calculated A 0 3 Observed - 0 3 Calculated 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 Page 37 of 38 BACK TO MAIN 3M Environmental Laboratory Report No. E01 -0739 Page 38 of 38