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A & c k & G ~~ I b ( > 1 UDR-TR-03-00044 Final Report - LaboratoryScale Thermal Degradation of Perfluoro-Octanyl Sulfonate and Related Substances June 2003 002039 Final Report Laboratory-Scale Thermal Degradation of Perfluoro-Octanyl Sulfonate and Related Precursors This report covers the efforts performed by the University of Dayton Research Institute (UDRI), Environmental Science and Engineering Group, Dayton, OH 454690132, during the period from March 2001 to December 2002. The work was conducted under a Letter of Agreement dated March 20,2001. The work was administered under the direction of the 3M Environmental Lab, ET&SS, and the Project Monitor was Eric A. Reiner and Dan C. Hakes. The UDRI Program Monitors were Philip Taylor and Tak Yamada. p/uLp Tagln, Dr. Philip Taylor j>M/o3 Date Dr. Tak Yamada Date 002040 TABLE OF CONTENTS SECTION Executive Summary 1 Background 2 Phase I: Objectives and Test Protocol 3 Phase : Method Development 4 Phase III: Revised Test Protocol 5 Experimental Results 5.1 SO2 Transfer Efficiency Test 5.2 Laboratory Spike Analysis for PFOS 5.3 Heated Blank Combustion Analysis 5.3.1 In-line GC/MS Analysis 5.3.2 Off-line GC/MS Analysis 5.3.3 Reactor/Transfer Line Extraction and LC-MS Analysis 5.4 Combustion Tests 5.4.1 PFOS Combustion Tests 5.4.1.1 In-line GC/MS Analysis 5.4.1.2 Off-line GC/MS Analysis 5.4.1.3 LC-MS Analysis o f Extracts 5.4.1.4 LC-MS Analysis o f PUF Cartridges 5.4.2 FC-1395 Combustion Test 5.4.2.1 In-line GC/MS Analysis 5.4.2.2 Off-line GC/MS Analysis 5.4.2.3. LC-MS Analysis o f Extracts 5.4.2.4. LC-MS Analysis of PUF 5.4.3 FC-807A Combustion Test 5.4.3.1. In-line GC/MS Analysis 5.4.3.2. Off-line GC/MS Analysis 5.4.3.3. LC-MS Analysis of Extracts 5.4.3.4. LC-MS Analysis o f PUF PAGE viii 1 3 6 8 9 9 9 9 10 11 12 13 13 15 16 17 18 18 19 20 21 21 22 23 24 25 25 002041 1 TABLE OF CONTENTS (continued) 5.5 2nd Heated Blank Combustion Analysis 5.5.1. In-line GC/MS Analysis 5.5.2. Off-line GC/MS Analysis 5.5.3. LC-MS Analysis o f PUF Cartridges 5.6 Transport Efficiency Tests for PFOS 5.6.1 1st Transport Efficiency Test 5.6.2 2nd Transfer Efficiency Test 5.6.3 3rd Transfer Efficiency Test 5.7 Sulfur Recovery Rate as SO2, SOF2, and SO2F2 5.8 Extracted Ion Analysis Discussion Conclusions References APPENDICES 26 26 27 28 28 28 29 30 32 34 38 41 42 u LIST OF FIGURES FIGURE 2.1. Schematic o f the System for Thermal Diagnostic Studies 5.3.1. In-line GC/MS Ion Chromatogram for Heated Blank at 600C 5.3.2. In-line GC/MS Ion Chromatogram for Heated Blank at 900C 5.3.3. Off-line GC/MS Ion Chromatogram for Heated Blank at 600C 5.3.4. Off-line GC/MS Ion Chromatogram for Heated Blank at 900C 5.4.1.1. In-line GC/MS Ion Chromatogram for PFOS at 600C 5.4.1.2. In-line GC/MS Ion Chromatogram for PFOS at 900C 5.4.1.3. Off-line GC/MS Ion Chromatogram for PFOS at 600C 5.4.1.4. Off-line GC/MS Ion Chromatogram for PFOS at 900C 5.4.2.1. In-line GC/MS Ion Chromatogram for FC-1395 at 600C 5.4.2.2. In-line GC/MS Ion Chromatogram for FC-1395 at 900C 5.4.2.3. Off-line GC/MS Ion Chromatogram for FC-1395 at 600C 5.4.2.4. Off-line GC/MS Ion Chromatogram for FC-1395 at 900C 5.4.3.1. In-line GC/MS Ion Chromatogram for FC-807A at 600C 5.4.3.2. In-line GC/MS Ion Chromatogram for FC-807A at 900C 5.4.3.3. Off-line GC/MS Ion Chromatogram for FC-807A at 600C 5.4.3.4. Off-line GC/MS Ion Chromatogram for FC-807A at 900C 5.5.1. In-line GC/MS Ion Chromatogram for Heated Blank at 600C 5.5.2. In-line GC/MS Ion Chromatogram for Heated Blank at 900C 5.5.3. Off-line GC/MS Ion Chromatogram for Heated Blank at 600C in PAGE 4 11 11 12 12 16 16 17 17 20 20 21 21 24 24 25 25 27 27 27 002043 FIGURE 5.5.4. 5.7.1. 5.8.1. 5.8.2. 5.8.3. 5.8.4. LIST OF FIGURES (continued) Off-line GC/MS Ion Chromatogram for Heated Blank at 900C SO2 Calibration Curve (Molar Number vs. Peak Area) Total Ion Chromatogram and Corresponding HFID Signal for Combustion of PFXS at 600C (off-line sample) Extracted Ions (CF2H-51, SOF-67, CF3-69, CF2CF2H-101, and C2F5-119) and Corresponding HFID Signal for Combustion o f PFXS at 600C (off-line sample) HFID Signal for PFOS Combustion at 600C (off-line sample) HFID Signal for PFOS at 900C (off-line sample) PAGE 28 33 35 36 37 37 002044 IV LIST OF TABLES TABLE 3.1. 3.2. 5.1.1. Linear Fit Equations and Detection Limits Transport Efficiency Transport Efficiency Test Results 5.2.1. 5.2.2. Net Amount o f Sample Loaded PFOS Laboratory Spike Analysis 5.3.1. Flow Rate Profile for Heated Blank Analysis at 600C 5.3.2. Flow Rate Profile for Heated Blank Analysis at 900C 5.3.3. Methanol Extraction Results for Heated Blank Analysis at 900C 5.3.4. PUF Extraction Results for Heated Blank Analysis 5.4.1.1. Net Amount o f Gasified Sample for PFOS Combustion Test 5.4.1.2. Flow Rate Profile for PFOS Combustion Test at 600C 5.4.1.3. Flow Rate Profile for PFOS Combustion Test at 900C 5.4.1.4. Methanol Extraction Results for PFOS Combustion Test 5.4.1.5. PUF Extraction Results for PFOS Combustion Test 5.4.2.1. Net Amount o f Gasified Sample for FC-1395 Combustion Test 5.4.2.2. Flow Rate Profile for FC-1395 Combustion Test at 600C 5.4.2.3. Flow Rate Profile for FC-1395 Combustion Test at 900C 5.4.2.4. Methanol Extraction Results for FC-1395 Combustion Test 5.4.2.5. PUF Extraction Results for FC-1395 Combustion Test PAGE 6 7 9 9 9 10 11 13 13 14 14 14 17 18 18 19 19 21 22 00r045 V LIST OF TABLES (continued) Net Amount of Gasified Sample for FC-807A Combustion Test Flow Rate Profile for FC-807A Combustion Test at 600C Flow Rate Profile for FC-807A Combustion Test at 900C Flow Rate Profile for Blank Analysis between 600 and 900C Methanol Extraction Results for FC-807A Combustion Test PUF Extraction Results for FC-807A Combustion Test Flow Rate Profile for Heated Blank Analysis at 600C Flow Rate Profile for Heated Blank Analysis at 900C PUF Extraction Results for Heated Blank Analysis Net Amount o f Gasified Sample for 1st Transfer Efficiency Test Flow Rate Profile for 1st Transfer Efficiency Test PUF Extraction Results for 1st Transfer Efficiency Test Net Amount of Gasified Sample for 2nd Transfer Efficiency Test Flow Rate Profile for 2nd Transfer Efficiency Test Methanol Extraction Results for 2nd Transfer Efficiency Test PUF Extraction Results for 2nd Transfer Efficiency Test Net Amount o f Gasified Sample for PUF Collection Flow Rate Profile for PUF Collection (PFOS Gasification with Air) Flow Rate Profile for PUF Collection (PFOS Gasification with He) Reactor/Valve Transfer Line Extraction Results PUF Extraction Results VI 23 23 25 26 26 26 28 28 29 29 29 30 30 30 31 31 31 31 TABLE 5.7.1. 5.7.2. 5.7.3. 5.8.3. 5.8.4. LIST OF TABLES (continued) SO2 Calibration Results Using PLOT Column Standard SO2 Transfer Efficiency Sulfur Recovery Rate as SO2 Integrated HFID Peak Area ofPFXS and PFOS at 600C Integrated HFID Peak Area o f PFOS at 900C PAGE 32 33 34 37 37 002047 vii EXECUTIVE SUMMARY 3M requested that the Environmental Sciences and Engineering Group at UDRI evaluate the incineration o f CgFnSOsTC* (PFOS) and two Cg perfluorosulfonamides (FC-1395 and FC-807A), potential sources o f PFOS to the environment upon incineration. The overall goal o f this study was to determine if incineration is a potential source of perfluoroalkyl sulfonates, e.g., perfluorooctanyl sulfonates (PFOS), which has been found in a number o f wildlife tissue samples (Giesy, et al., 2001; Kannan, et al., 2001). A laboratory-scale study simulating a full-scale hazardous waste incinerator was envisioned. Based on prior experience with halogenated compounds, initial plans were to use relatively modest conditions in the primary combustion zone (ca. 400C) to gasify the materials with more severe high-temperature (600 - 900C), oxidative conditions representing a secondary combustion zone. TGAs o f the active ingredient indicated that higher temperatures (ca. 600C) were necessary to gasify this material. The sponsor also requested that the experiment be designed to detect low-levels (0.1%) o f PFOS in the exhaust gases. These factors necessitated the use of large amounts o f material (milligram quantities) and high-temperature, long duration exposures (ca. 1250C, 40 sec) in a specially designed pyroprobe to fully gasify the material. These conditions, while representing quite severe conditions in the primary zone o f an incinerator, e.g., a rotary kiln, are representative of the range o f conditions that occur in a fullscale system. As such, the approach employed in the laboratory-scale combustion study is a reasonable extrapolation of a full-scale incineration study of PFOS. Combustion tests for PFOS, FC-1395, and FC-807A were completed as requested by the sponsor. In-line and off-line GC/MS analyses, reactor effluent sample collection using PUF cartridges followed by LC-MS analysis, and chemical extraction o f various transfer lines throughout the reactor system including the reactor itself followed by LC-MS analysis were conducted to investigate the following: 1) the extent o f conversion o f the active ingredients, 2) the formation of fluorinated organic incomplete combustion byproducts, and 3) the extent o f conversion o f the sulfur to sulfur oxides. The data presented herein clearly show that incineration of FC-1395 and FC-807A does not release PFOS to the environment. This conclusion is based mainly on the LC/MS measurements, but was substantiated by the extracted ion analysis that showed negligible 67-SOF ion indicating negligible amounts o f volatile sulfonate-containing degradation products. Sulfur recoveries were quite good, 10025%. The dominant sink for sulfur was SO2. GC/MS analysis o f perfluorinated alkyl sulfonate precursors indicated that such precursors were not present in the reactor effluent. This finding is consistent with the LC/MS measurements, and strongly suggests that the C-S bond was completely destroyed (and did not reform) in the combustion tests. High levels o f conversion o f the PFOS were observed from the incineration tests. This conclusion was based on LC/MS measurements of the reactor effluent and a thorough analysis of the transport o f the material through the combustion system. Sulfur recoveries varied from 50 to 60%, depending on the reactor temperature. The dominant sink for sulfur was SO2. GC/MS analysis of perfluorinated alkyl sulfonate precursors indicated that such precursors were not present in the reactor effluent. This finding is consistent with the LC/MS measurements, and 002048 VUl strongly suggests that the C-S bond was completely destroyed (and did not reform) in the combustion tests. Fluorinated organic intermediates were observed in the reactor effluent. These compounds were limited to fluorobenzene (FC-1395 and FC-807A only), Ci or C2 fluoroalkanes (likely products are either CHF3, CF4, or C2F6), 1,1-difluoroethene (PFOS only), and 1,2-difluoroethene (FC1395 only). Higher molecular weight fluorinated polycyclic aromatic hydrocarbons were not observed. The data from this laboratory-scale incineration study indicates that properly operating full-scale incineration systems can adequately dispose o f PFOS and the Cg perfluorosulfonamides. Incineration o f these fluorinated compounds is not likely to be a significant source o f PFOS into the environment. With the exception o f stable Ci and C2 fluorocarbons, fluorinated organic intermediates are also unlikely to be emitted from these facilities during the incineration of these materials. 002049 6/19/2003 Laboratory-Scale Thermal Degradation of Perfluoro-Octanyl Sulfonate and Related Substances Final Report Prepared by: Takahiro Yamada and Philip H. Taylor Environmental Sciences and Engineering Group University o f Dayton Research Institute 300 College Park Dayton, OH 45469-0132 In response to a verbal and written request from: Eric A. Reiner and Dan C. Hakes 3M Environmental Lab, ET&SS US-MNSP02, 0002-03-E-09 P.O. Box 33331 St. Paul, MN 55133-3331 002050 1. Background The destruction efficiency (DE) of principal organic hazardous constituents (POHCs) is dominated by the temperature, time, fuel (waste)/air mixing, and fuel/air stoichiometry (excess air) experienced by the POHCs in the high temperature zones o f incinerators (Dellinger, et al., 1991). Numerous calculations and experiments have shown that emissions o f undestroyed, residual POHCs are kinetically, not thermodynamically controlled (Tsang and Shaub, 1982; Trenholm, et al., 1984; Dellinger, et al. 1991). A s a result, accurate assessment o f POHC emissions require thermal stability testing and cannot be accurately modeled based on thermodynamic equilibrium calculations. Simple conceptual and more complex computer models indicate that gas-phase residence time and temperature in the post-flame zones o f incinerators control the relative emissions o f most POHCs (Clark, et al., 1984; Dellinger, et al., 1986; Dellinger, et al. 1991). This is because all molecules entering the flame zone of an incinerator are destroyed completely to thermodynamic endproducts and only the minute fraction escaping the flame zone is actually emitted from the facility. Once in the post-flame zone, gas-phase thermal decomposition reactivity in the presence o f the major gas-phase constituents of this zone control the rate o f POHC destruction and formation and destruction o f products o f incomplete combustion (PICs). If all POHCs in a given waste stream are volatilized at approximately the same rate, they will experience the same post-flame gas-phase residence time, temperature, and stoichiometry history (relative concentrations of POHC, oxygen, and other major gas-phase constituents as the POHCs traverse this zone). This means that gas-phase thermal stability o f POHCs (as determined under a standardized set o f conditions) may be used to predict their relative incinerability. The temperature for 99% destruction at 2.0 seconds gas-phase residence time, [T99 (2)(C)] has been used previously to rank the thermal stability o f POHCs (Taylor, et al., 1990). Other residence times or levels of destruction may be used to develop a ranking. However, laboratory data indicate that although absolute POHC DEs are dependent upon time and temperature, relative DEs are largely insensitive to these parameters (Dellinger, et al., 1984; Graham, et al., 1986; Taylor and Dellinger, 1988). On the other hand, stoichiometry has been shown to be a significant variable in determining relative stability (Graham, et al., 1986; Taylor and Dellinger, 1988; Taylor, et al., 1991). Experimental and theoretical considerations suggest that various flame zone failure modes exist that may cause residual POHCs to be emitted from a facility. The most prominent of these are thermal quenching and waste/air mixing failure modes. Even though a facility may be operating under nominal excess air conditions, poor waste/air mixing or thermal quenching zones due to poor heat transfer at incinerator surfaces will result in conditions where the rate of POHC destruction is low and PIC formation is favored. Consequently, it is believed that gas-phase thermal stability as characterized under oxygen-starved conditions is an effective predictor o f POHC relative incinerability. The UDRI thermal stability-based incinerability ranking was initially published in 1990 with further development published inl991 (Taylor, et al. 1990; Dellinger, et al., 1991). The US-EPA has evaluated the UDRI gas-phase thermal decomposition kinetic rankings on both the pilot and 002051 1 full-scale as a basis for determining POHC incinerability. Pilot-scale studies (Carroll, et al., 1992) o f an eleven-component hazardous waste mixture under thermal failure and worst-case conditions (encompassing three failure-promoting conditions resulting in lower kiln-exit temperature, larger charge mass, and lower H/Cl ratio than the baseline set of conditions) both produced statistically significant correlations between product emission concentrations and their gas-phase thermal stability rankings. For the thermal failure tests, correlations above the 99% confidence interval were observed. Full-scale studies (Dellinger, et al., 1993) o f a sevencomponent hazardous waste mixture indicated that thermal failure and waste/air mixing failures also produced statistically significant correlations. Based on median destruction and removal efficiencies (DREs), the data indicated that both the mixing and thermal failure modes produced statistically significant correlations between product emission concentrations and their gas-phase thermal stability rankings. 3M requested that the Environmental Sciences and Engineering Group at UDRI evaluate the thermal decomposition o f the following fluorocarbon-based compounds: FC-807A and FC 1395 (Cs perfluoroalkyl sulfonamides), and CgFi7S03'K+ (PFOS). The overall goal o f this study was to determine if incineration is a potential source o f perfluorooctanyl sulfonates (PFOS), which has been found in a number o f wildlife tissue samples (Giesy, et al., 2001; Kannan, et al., 2001). This report describes the experimental studies of PFOS, FC-807A, and FC-1395. This report is broken into eight sections. The first four sections describe the background of our experience in incineration research, phase I: the initial test protocol and project objectives, phase II: the method development work, and phase ID: the revised test protocol. Sections five and six describe the experimental results followed by an interpretation of the results, respectively. Section seven gives conclusions and recommendations. Section eight provides a list of references. An appendix contains the following auxiliary information that pertains to all experiments conducted in this study including those involving PFOS incineration: 1) a timeline o f the phase I, phase n , and phase ID studies and the actual dates o f the combustion tests, 2) Sample descriptions and Certificate of Analysis (C of A) for PFOS sample, 3) the phase II final report and raw data, 4) the phase III test protocol and addendum, 5) the 3M analytical report and 6) a spreadsheet linking the UDRI combustion tests with the 3M Analytical results. U 0C 052 2 2. Phase I: Objectives and Test Protocol The objectives of this program were the following: 1. Determine if Cg perfluorosulfonamides form combustion products that either are perfluorooctanyl sulfonate (PFOS) or precursors o f perfluoro-octanyl sulfonate. 2. Determine the extent o f conversion o f PFOS under conditions representative o f hazardous or municipal waste incineration, 3. Identify the major fluorinated combustion products, 4. Determine if the sulfur present in the PFOS is quantitatively converted to sulfur dioxide and/or thionyl fluoride (SOF2) and sulfuryl fluoride (SO2F2) at high temperature, fuel-lean combustion conditions. The development o f the test protocol was based on the use of batch-charged continuous flow reactors developed at UDRI to study the thermal stability o f organic materials (Rubey and Carnes, 1985, Rubey and Grant, 1988). Briefly, these systems accept a small quantity o f material (typically less than 1 mg). The sample and its decomposition products are volatilized, mixed with flowing dry air, transported through a high temperature quartz tubular reactor where the sample vapors are thermally stressed under controlled conditions of time, temperature, and excess air level. The materials surviving this exposure are then passed onto an in-line gas chromatography/mass spectrometry (GC/MS) system for analysis. Quantification o f parent species is based on transport and analysis o f known quantities under non-destructive conditions. Typically, products are quantified using the response factor of the parent compound or the major parent compounds if from a complex mixture. In this study, the analytical focus will be identification of stable fluorinated organic intermediates and the quantification o f sulfur oxides in an attempt to recover 100% o f the initial sulfur in the sample. Sulfur quantification will be performed using a mass selective detector (MSD). Consideration was also given to the use o f a sulfur-specific detector that responds only to sulfur atoms. However, due to the universal nature of the MSD, i.e., its ability to detect both sulfur and fluorinated organic compounds, it was decided that the MSD would be satisfactory for these experiments. Every sample presents its own unique set o f challenges. In the case o f PFOS, the unknowns in establishing the test protocol centered around the issue of transportability. Specifically, transporting the sample to the reactor from the sample inlet and the products from the reactor to and through the analytical sub-systems. For example, it is likely that the test sample will decompose rather than evaporate and the central issue becomes whether the products from this decomposition process can be transported under acceptable conditions. Consequently, developing the test protocol for the 3M samples focused on the issues o f sample feed and product transport and analysis. 002053 3 The first step in any gas-phase thermal stability analysis is converting the sample into a vapor where it is mixed with the desired carrier gas and transported through the reactor system by the bulk flow of the process stream. W hen working with a relatively uncharacterized sample, it is common practice to perform a thermogravimetric analysis (TGA) in oxidizing (air) and inert (nitrogen or helium) atmospheres to determine the temperature range needed to gasify the sample. This preliminary information was used to determine if the phase change is simple evaporation or decomposition and to determine if the sample deposits a non-volatile residue. With the temperature range needed to gasify the sample established, a series o f relatively simple tests was performed to determine if the gasification products could be transported under nominal flow reactor conditions. While the sample inlet systems of the UDRI reactors can be routinely heated to 400C (with transient heating as high as 600C), the sample transport lines to and from the reactors are typically limited to 250-300C. Experience has shown that under these conditions most organic compounds of interest can be transported without inducing thermal reactions thereby preserving the fidelity o f the samples flowing from the inlet system to the reactor and the product stream flowing from the reactor to the analytical sub-systems. A key issue to be evaluated in this study will be the transport of the PFOS from the gasification system to the high-temperature reactor and from the reactor to the analytical sub-systems. The System for Thermal Diagnostic Studies (STDS) was used to perform the incineration study described herein. An overall schematic o f the system is shown in Figure 2.1. The STDS is a modular, continuous, in-line reactor system that allow researchers to simulate incineration processes and perform exhaustive analyses of the output for about one-tenth the cost o f full-scale tests. The instrument consists of several major components: a thermal reaction compartment; a transfer line; an analytical gas chromatograph (GC), a mass selective detector and a computer workstation. The STDS has been used to perform many types of combustion studies. The STDS has been very successful at predicting air emissions from the incineration o f hazardous materials, allowing prior knowledge o f the risks associated with burning a given waste. System for Thermal Diagnostic Studies (STDS) K MS SC -CTIt M l - MS GC MS *M $ Figure 2.1. Schematic of the System for Thermal Diagnostic Studies 002054 4 Initially, the Advanced Thermal Photolytic Reactor System (ATPRS) was selected for this study. To satisfy the analytical requirements for PFOS detection by LC/MS analysis at 3M Environmental Laboratory, we determined that relatively large amounts o f sample, 0.5 to several mg, had to be gasified in the actual experiments. This amount o f sample was much larger than initially estimated (ca. 10 to 100 jxg) and could not be gasified with the inlet available with the ATPRS. Preliminary experiments also demonstrated that higher gasification temperatures (> 400C) were necessary to rapidly gasify the fluorocarbon-based samples. As such, the STDS, equipped with a high-temperature pyroprobe that can gasify milligram quantities of material, was selected for the actual combustion tests. In the original protocol, we originally planned sample combustion with a liquid hydrocarbon fuel (e.g., n-octane). Subsequently, it was determined that a substitute was necessary because the liquid hydrocarbon fuel originally proposed required a much larger amount o f oxygen (air) to obtain stoichiometric oxidation and it was impossible to maintain the required residence time of 1-2 seconds in the reactor under stoichiometric or excess air environments. Methane has the lowest chemical oxygen demand of any hydrocarbon fuel and is a satisfactory replacement. We decided instead to use methane as a fuel if the sample is hydrogen deficient and requires hydrogen source to convert F to HF, otherwise fuel will not be introduced to the reactor. In the original protocol, we also proposed to conduct combustion tests at three temperatures (600,750, and 900C). Preliminary combustion tests with several samples indicated that many combustion byproducts were formed at 600C, but those combustion byproducts were not observed at higher temperature (750 and 900C) and the GC/MS total ion chromatograms for these higher temperatures were very similar. Therefore it was decided that two temperatures are sufficient to analyze the combustion phenomena of the selected samples (600 and 900C). 002055 5 3. Phase II: Method Development The following method development tests were performed in phase II: 1. Verify that PFOS can be gasified and transported through the UDRI thermal instrumentation system. 2. Establish recovery efficiencies and detection limits for stable sulfur compounds and PFOS precursors. The sulfur compounds would include but not be limited to SO2, SOF2, and SO2F2. PFOS precursors would include but not be limited to perfluoro-octane sulfonyl fluoride (POSF). 3. Establish recovery efficiencies and detection limits for volatile C1-C4 fluorocarbons. 4. Develop a quantitative method of sampling the reactor effluent. ORBO PUF cartridges (Supelco, Inc.) will be used for sampling PFOS and its precursors from the reactor effluent. This section summarizes the results. Calibration curves and detection limits for SO2, SOF2, SO2F2, POSF and C3F6 (hexafluoropropene (HFP)) have been established. The transport efficiency for each compound through the STDS was also examined. Verification that the Cg perfluoroalkyl sulfonates can be gasified and transported through the system was performed following the completion of the combustion tests. This decision was made based on the potential contamination o f die system had the transport tests been done prior to the combustion study. PUF cartridge sampling o f the reactor effluent was established as part o f the revised phase III protocol. HFP was selected as the surrogate volatile fluorocarbon due to the lack of availability o f CF4 and CF3H from gas suppliers. The linear fit equations for each sample, their linear correlation coefficients (R) and detection limits are tabulated in Table 3.1. Further details regarding these calibration curves are available in the Phase II report. Sample Name S02 SOF2 SO2F2 POSF HFP Table 3.1. Linear Fit Equations and Detection Limits Linear Fit R Detection Limit (Y: peak area, X: concentration (ppm)) (ppm) Y = 5.8813E3* X - 3.8541E5 0.9971 78.5 Y = 8.3335E3* X - 7.0267E4 0.99941 30.3 Y = 1.0331E4*X+ 1.8273E6 0.99708 20.1 Y = 1.0423E5*X - 8.4043E5 1.0 14.1 Y = 1.4975E4*X - 2.8253E6 0.9997 3.9 The transport efficiency of each standard was estimated by comparing the measured sample peak area obtained when the sample was injected into injection port in GC1 and passed through combustion reactor and transfer line (system transport) with that obtained when the sample was injected directly into the injection port o f GC2 (direct injection). 0 0 2 0 S6 6 Sample S02 SOF2 SO2F2 POSF HFP Table 3.2. Transport Efficiency System Transport Direct Injection Peak Area Peak Area 1st 2nd AVG (1) 1st AVG (2) 9130332 8980717 9055525 11952302 11762267 11857285 25244352 25203780 25224066 24862639 24773683 24818161 86850304 85572809 86211557 84435720 79738316 82087018 1280370 1228718 1254544 1064431 1067947 1066189 148679354 145606343 147142849 148372504 142271896 145322200 Efficiency (%) (l)/(2)xl00 76.4 101.6 105.0 117.7 101.3 As illustrated in Table 3.2, the transport efficiencies for SOF2, SO2F2, and HFP were within analytical error. An uncertainty of 10% is reasonable for this type o f analysis. That for POSF was slightly higher, but is nonetheless acceptable. That for SO2 was around 76%. The SO2 standard was analyzed as a two-component mixture with SOF2. Since the transport efficiency for SOF2 was nearly 100%, the results indicate some sample losses for SO2 through the reactor and transfer lines. Because SO2 is expected to be one o f the major combustion byproducts, we will repeat the efficiency test at the onset o f the actual combustion tests (see section 5.1: SO2 Transfer Efficiency Test). We will estimate a SO2 correction factor based on SO2 efficiency test results to compensate for its measured concentration during the Phase III study. Further details o f the initial calibration and transport efficiency tests can be found in the Phase II report provided in the Appendix. 002057 7 4. Phase III: Revised Test Protocol The combustion tests consisted o f 8 separate tests as listed below: 1. SO2 Transfer Efficiency Tests, 2. Laboratory Spike Analysis for PFOS, 3. Heated Blank Combustion Test, 4. Combustion Tests for PFOS and two Cs perfluorosulfonamides, 5. Heated Blank Combustion Test (repeat), 6. Transfer Efficiency Test for PFOS, 7. Sulfur Recovery Analysis as SO2, 8. Extracted Ion Analysis. Specific attention was being given to the sampling of PFOS during incineration. In-line and off line GC/MS analysis, PUF (polyurethane foam) collection of the reactor effluent and chemical extraction o f the reactor and associated transfer lines were conducted. In the latter two tests, the PUF cartridges and the extracts were delivered to 3M for analysis of PFOS by LC/MS. Prior to the sample combustion analysis, the transfer efficiency for SO2 was re-examined and the laboratory spike analysis for PFOS was performed. A heated blank line analysis was performed at the onset of the sample combustion tests. After the combustion tests, another heated blank line analysis was performed. Transfer efficiency tests for PFOS were performed at the conclusion of the combustion tests. Due to resolution issues regarding the in-line sampling approach, the sulfur recovery rate as SO2 was re-analyzed using off-line GC/MS analytical results. Further details are provided in the Phase m test protocol and addendum that are given in an appendix to this report. The 3M analytical report (LIMS Nos. E02-0820, E02-0821, E02-0822, E02-0839, E02-0840, E02-0867, E02-0895, E02-0896, E02-0898, E02-0899, E02-0916, E020917, E02-0926, E02-0968, E02-0969, E02-0970, and E02-0971) is also provided in an appendix to this report. It should also be noted that the PFOS data were not corrected for recovery from the PUF cartridges. Spike recoveries for PFOS were ca. 80% with 1 pg addition o f these compounds and ca. 90% with 10 pg addition o f these compounds. 002058 8 5. Experimental Results 5.1. S 0 2 Transfer Efficiency Test The SO2 transfer efficiency tests conducted in Phase II was repeated in Phase m to confirm the Phase II results. The results are shown in Table 5.1.1. The S 0 2 standard was analyzed as a twocomponent mixture with SOF2. SO2 transport efficiency was 83.7%, slightly higher than previous results, 76.4%, which gives average value o f 80.1%. The transport efficiency for SOF2 was again nearly 100%. Sam ple S02 SOF2 Table 5.1.1. Transport Efficiency Test Results System Transport Direct Injection Peak Area Peak Area 1st 2^ A verage (1) 1st 2 aa A verage (2) 8300590 8433620 8367105 10134575 9995499 10065037 21346398 20309703 20828051 19612747 20444301 20028524 E fficien cy (% ) (M 2 )x l0 0 83.7 101.9 5.2. Laboratory Spike Analysis for PFOS PFOS was dissolved with 10 ml methanol (Aldrich, HPLC grade) and 1 pi o f solution was placed into a reactor (4 mm (i.d.) x 6 mm (o.d.) x 7 cm length) and dried by blowing high purity nitrogen. The amount o f sample used is shown in Table 5.2.1. After the drying process, the transfer lines were assembled and the samples were extracted using 5.5 ml of methanol that was also used to dissolve the samples. Sample PFOS Net Weight (mg) 10.02 Table 5.2.1. Net Amount of Sample Loaded Solvent Amount Amount Injected Net Amount of Sample (ml) (uO Loaded (pg) 10 1.0 1.0 Table 5.2.2 shows the extraction results for PFOS laboratory spike analysis, respectively. The combined first and second extracts recovered 188% o f the PFOS. This single spike result suggests that an error likely occurred during preparation, extraction or analysis. Nevertheless, this spike result confirms that PFOS can be extracted from reactor/transfer lines. Sample Extracts PFO S 1st Extracts PFOS 2nd Extracts PFOS ipg/ul) 232 40.5 PFOS (pg) 1 .6 0.28 5.3. Heated Blank Combustion Analysis The heated blank reactor/transfer tubing was analyzed to examine if there was any system contamination (including background levels o f PFOS) for the reactor temperature at 600 and 900C prior to series o f combustion tests. Four analyses, in-line GC/MS analysis, PUF collected off-gas sample analysis, off-line GC/MS analysis using Tediar bag, and reactor/transfer line 002059 9 system extraction using methanol were conducted. The PUF sample collection and methanol extraction of condensed phase material were prepared and sent to 3M Environmental Laboratory for analyses. The in-line GC/MS was mainly used to analyze compounds equal to or heavier than C6 compounds and off-line GC/MS was used for lighter compounds including SO2. PUF sample and methanol extracts were analyzed for PFOS detection. The experimental setup, reactor/transfer-line configuration, and experimental procedure followed the Phase ID test protocol. The Phase E l test protocol and addendum can be found in the appendix to this report. 5.3.1. In-line GC/MS Analysis Table 5.3.1 and 5.3.2 show the flow profile and carrier flow volume used for the heated blank analysis at 600 and 900C, respectively. O f the total gas flow, 1 ml/min was introduced to the in-line GC/MS and the remainder introduced to either the PUF cartridge or the Tedlar bag for off-line analyses. A simple 1/16 in. tee was used as the flow splitter. Air was flowed to both the pyroprobe and reactor during the test except during the last time period, where helium was necessary to purge the pyroprobe and to perform the in-line GC/MS analysis. A HP5890A/ 5970B series GC/MS with a DB-5 MS capillary column (30 m length, 0.25 mm i.d., Agilent Technologies, Inc.) was used for the in-line GC/MS analyses. The in-line GC/MS was operated at constant pressure (10 psi). The MS was auto-tuned with perfluorotributylamine (PFTBA) and operated at an electron multiplier setting o f 2000 in the scanning mode sweeping a mass range from 45 to 550 m/z. Figures 5.3.1 and 5.3.2 show total ion chromatograms for reactor temperatures of 600 and 900C, respectively. The chromatogram shows only background noise and no contamination was found for either temperature. The background noise dropped to an apparent zero level due to the relatively high signal threshold (2500). This high threshold was used in anticipation of a high background noise level that arises from the presence of significant amounts o f condensed phase combustion byproducts. This expectation was confirmed and is consistent with the large amounts of fluorochemicals that were injected into the combustion system. Table 5.3.1. Flow Rate Profile for Heated Blank Analysis at 600C Time Period Reactor Flow Pyroprobe Flow Total Flow Rate Total Sampled (sec) Rate (ml/min) Rate (ml/min) (ml/min) Volume Volumed (ml) (ml) 0 -1 2 0 10.5 0.80 11.30 22.60 20.60 120-130 10.5 0.80 - 4.63" 11.30 14.63 2.16 1.99 130-140 10.5 4.63 15.13 2.52 2.35 140-160 9.03 (He)b 4.53 (He)c 13.56 4.52 4.19 Total Volume (ml) 31.80 29.13 a"Lt i.near i!nc_rease (approximate). bb.,ccS0 _w i_t_c_h_ed1 txo h1 elium for sweep. d Sam pled volum e for PUF and Tedlar bag collection. 002060 10 Table 5.3.2. Flow Rate Profile for Heated Blank Analysis at 900C Time Period Reactor Flow Pyroprobe Flow Total Flow Rate Total Sampled (sec) Rate (ml/min) Rate (ml/min) (ml/min) Volume Volume*1 (ml) (ml) 0-150 150- 160 160-170 170- 190 ar _ ? 7.60 7.60 7.60 6.54 (He)b 0.70 8.30 0.70 4.63a 8.30 12.23 4.63 12.23 4.53 (He)c 11.07 Total Volume (ml) b,c r i. -j. i___ i . i 20.75 1.71 2.04 3.69 28.19 18.25 1.54 1.87 3.36 25.02 and Tediar bag collection. 2000 - 0.00 10.00 5.00 2 0 .0 0 5.00 2 0 .0 0 Figure 5.3.1. In-line GC/MS Ion Chromatogram for Heated Blank at 600C Figure 5.3.2. In-line GC/MS Ion Chromatogram for Heated Blank at 900C 5.3.2. Off-line GC/MS Analysis A 0.5 L Tedlar bag (SKC, Inc.) was used to collect the off-gas. The samples were analyzed within 15 minutes after collection. The flow profile was identical to the in-line GC/MS analysis and PUF collection except the last time period, which was not necessary for Tedlar bag analysis. HP5890A/5970B series GC/MS with SPEL-Q PLOT (Porous Layer Open Tubular) column (30 m length, 0.53 mm i.d., Supelco, Inc.) was used for the analyses. The off-line GC/MS was operated in the constant flow mode with 28 ml/min split flow. The MS was auto-tuned with perfluorotributylamine (PFTBA) and operated at an electron multiplier setting o f 1600 in the 002061 it scanning mode sweeping a mass range from 35 to 550 mix. The Tediar bags were moderately heated to ca. 50 - 60C with a heat gun to minimize condensation on the bag surfaces. 1 ml sample volumes were injected using a gas-tight syringe (Hamilton Co.). Figure 5.3.3 and 5.3.4 show total ion chromatograms for the heated blank at 600 and 900C, respectively. Large peaks associated with air were observed at 0.65 and 0.75 minute (argon and carbon dioxide, respectively). There was no other peaks observed, which indicates the lack o f any measurable contamination. Figure 5.3.3. Off-line GC/MS Ion Chromatogram for Heated Blank at 600C Figure 5.3.4. Off-line GC/MS Ion Chromatogram for Heated Blank at 900C 5.3.3 Reactor/Transfer Line Extraction and LC-MS Analysis Following PUF sample collection and in- and off-line GC/MS analysis at 900C, extraction of the reactor/transfer line tubing was performed. The reactor was cut in half prior to the extraction. The second half o f the reactor and the transfer lines between the reactor and switching valve 1 were extracted. Further details regarding the extraction procedure are presented in the Phase EH test protocol. The extractions were performed twice using 5.5 ml o f methanol ((Aldrich, HPLC grade). The extracts were analyzed for PFOS at 3M Environmental Laboratory. Table 5.3.3 shows the analytical results. A very small amount o f PFOS, 0.08 pg, was found in the reactor/transfer line extract in the first heated blank combustion test. The amount found 12 equal to 0.016% of the maximum amount that could have passed through the system as PFOS or that could have been formed from any o f the fluorochemical products at levels added in the combustion tests. The amount of PFOS extracted in the second heated blank combustion test was below detection limits. Table 5.3.3. Methanol Extraction Results for Heated Blank Analysis at 900C PFOS (pg/ul) PFOS (ug) 14.9 0.10 Table 5.3.4 shows the analytical results for the two PUF sample collections. No cross contamination was detected. Table 5.3.4. PUF Extraction Results for Heated Blank Analysis Temp (C) PFOS (pg/pl) PFOS (pg) 600 <10.0 <0.25 900 <10.0 <0.25 5.4. Combustion Tests This section presents the combustion test results for PFOS and two Cg perfluorosulfonamides, FC -1395 and FC-807A. 5.4.1. PFOS Combustion Tests Combustion product analyses were performed at reactor temperatures o f 600 and 900C. Four distinct analyses were conducted for each test. Two GC/MS analyses were conducted at UDRI: in-line GC/MS analysis and off-line GC/MS analysis using Tedlar bags. The chemical extractions of the reactor transfer lines were performed at UDRI. The PUF cartridges were extracted at the 3M Environmental Lab. The experimental setup, reactor/transfer-line configuration, and experimental procedure followed the Phase III test protocol. The GC/MS operating conditions for the in-line and off-line analyses were the same as those used for heated blank analyses described in Section 5.3. In these combustion tests, the samples were first volatilized in a pyroprobe chamber. This chamber is considered analogous to the primary combustion chamber in an incinerator. The gases or air-entrained particulate matter then passed through transfer tubing, a heated tubular reactor, and additional transfer tubing and a valve to PUF cartridges. The heated reactor is considered roughly analogous to a secondary combustion chamber or afterburner in a full-scale incinerator. Table 5.4.1.1 shows net amount o f sample gasified for PFOS combustion tests. The sample probe was weighed before and after the combustion tests. 002063 13 Table 5.4.1.1. Net Amount of Gasified Sample for PFOS Combustion Test Temperature Usage Loaded Remaining Net Amount (C) Mass (mg) of Gasified (mg) Sample (mg) 600 PUFa 0.47 0.02 0.45 TBb 0.48 0.10 0.38 900 PUF 0.50 0.00 0.50 TB 0.50 0.00 0.50 *In-line GC/MS analysis and off-gas collection using P\TUTFT?. bbOff-lMine_G- C/MS analysis using Tedlai Bag. Tables 5.4.1.2 and 5.4.1.3 show flow rate profiles used for PFOS combustion tests at 600 and 900C, respectively. Table 5.4.I.2. Flow Rate Profile for PFOS Combustion Test at 600C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (sec) Rate (ml/miri) (ml/min) (ml/min) (ml) Air Air CH, 0-60 9.86 0.85 0.21 10.92 10.92 60 - 85a 0.00 0.00 0.00 0.00 0.00 85-157 157 -167 9.86 0.85 0.21 10.92 13.10 9.86 0.85 -> 4.63b 0.21 10.92 14.70 2.14 167-177 177 -197 9.86 8.61 (He)* 4.63 4.53 (He)d 0.21 0.00 14.70 13.14 2.45 4.38 Total volume passed through reactor (ml) 32.99* Total volume passed through PUF (ml) 30.12f _________Total volume used for off-line GC/MS SO2 quantitative analysis (ml) 22.078 *System opened due to sample insertion. Assuming no outlet flow. bLinear increase (approximate). c,dSwitched to helium for sweep. *Total carrier flow volume that passed through the reactor. f Total carrier flow volume that passed through PUFs. gVolume used to calculate total amount of S 02 recovered using off-line GC/MS system. Table 5.4.I.3. Flow Rate Profile for PFOS Combustion Test at 900C Time Period Reactor Flow (sec) Rate (ml/min) Pyroprobe Flow Rate (ml/min) Total Flow Rate Volume (ml/min) (ml) 0-60 60-85* 85 -1 7 9 179-189 189-199 199-219 Air 7.12 0.00 7.12 7.12 7.12 6.15 (He)* Air 0.65 0.00 0.65 0.65 4.63b 4.63 4.53 (He)d CH 0.16 0.00 0.16 0.16 0.16 0 7.93 0.00 7.93 7.93 11.91 11.91 10.68 7.93 0.00 12.42 1.65 1.99 3.56 Total volume passed through reactor (ml) 27.55* Total volume passed through PUF (ml) 24.32f Total volume used for off-line GC/MS S 0 2 quantitative analysis (ml) 19.62s *System opened due to sample insertion. Assuming no outlet flow .bLinear increase (approximate). ",dSwitched to helium for sweep. *Total carrier flow volume that passed through the reactor. f Total carrier flow volume that passed through PUFs. 8 Volume used to calculate total amount o f S 02 recovered using off-line GC/MS system. 0G064 14 Identical combustion conditions were repeated for PUF collection with in-line GC/MS analysis and off-line GC/MS analysis for each temperature. The first total volume (3rd row from the bottom) is the summation o f all flow steps. A flow o f 1 ml/min was always supplied to the in line GC/MS system. Therefore, the volume passed through the PUF cartridge can be calculated by subtraction of the volume to the in-line GC/MS system from the total volume passed through the reactor as shown in the 2nd row from the bottom. For example, the total volume passed through PUF in Table 5.4.1.2 can be obtained as follows: 32.99 ml - 1 ml/min. x (197 - 85) sec. / [60 sec./min.] = 30.12 ml To calculate the total amount o f SO2 recovered using the off-line GC/MS system, the volume supplied to the in-line GC/MS system also needs to be counted as well as the volume collected by Tedlar bag. This total volume can be calculated by subtraction of the first time step volume from the total volume passed through the reactor. The last line in Table 5.4.1.2 can be obtained by subtracting the first time step volume (10.92 ml) from total volume (32.99 ml). At the onset o f the experiment, the methane/air mixture was flowed through the entire system for 1 minute prior to sample gasification. Methane was introduced to supply hydrogen to consume excess fluorine during combustion and also to serve as a fuel source. The pyroprobe/transfer line system was then opened to insert the sample probe within the pyroprobe. At that time, there was no appreciable gas flow through the system. The sample was then gasified for 40 seconds at 1250C. During and following this gasification, methane/air flow swept the gasified products from the pyroprobe to the reactor. For the 600C combustion test, for example, the methane/air flow rate was 1.06 mL/min at 23C for 1 min. 12 sec. At 260C, the temperature o f the oven containing the pyroprobe, the methane/air flow would have expanded to sweep the volume of the pyroprobe approximately 1.3 times. However, the 40 sec. heating to 1250C to gasify the sample during this flow period would have also forced approximately 1.9 pyroprobe volumes o f gas from the pyroprobe to the reactor. During cooling from 1250C to 260C following gasification, there was likely also a temporary back flow o f air into the pyroprobe as the gas pressure inside it dropped. To purge the pyroprobe/transfer line, flow of air to the pyroprobe chamber was then increased to the maximum rate and held for 10 sec. The pyroprobe was additionally purged with He for 20 sec. For the 600C combustion test, for example, the air flow rate was 4.63 mL/min at 23C and the He flow was 4.53 ml/min. The total volume of the purging methane, air, and helium was 2.78 ml at 23C, which corresponds to 5.0 ml at 260C. Since the effective volume o f the pyroprobe chamber with the sample probe inserted is 1.5 cm3 (bottom o f page 10 in Phase HI protocol), this volume completely flushes the pyroprobe chamber 3.3 times. This purging procedure was applied for the combustion test at 900C and the blank between 600 and 900C. For in-line GC/MS analysis, the head o f the GC column was held at the temperature of -60C during the entire combustion period to concentrate effluent gas that was introduced at 1 ml/min flow rate. The GC/MS temperature programming was started after the final helium purge. 5.4.1.1. In-line GC/MS Analysis Figures 5.4.1.1 and 5.4.1.2 show total ion chromatograms for PFOS combustion at 600 and 900C, respectively. A single sulfur dioxide peak was the only identifiable peak for both combustion tests. Tetrafluorosilane, a common intermediate in the other combustion tests, was 002065 15 not observed for the PFOS combustion tests. It is not clear why the total ion chromatograms for PFOS combustion at 600 and 900C differ so dramatically from the other results. The MSD source might have suffered from a loss o f sensitivity due to the repetitive, heavy-duty use. No attempts were made to clean the MSD source because the cleaning process requires MS signal tuning and the recalibration of all standard gases previously conducted, which was not feasible at this stage o f the testing. Figure 5.4.I.I. In-line GC/MS Ion Chromatogram for PFOS at 600C Abundanco Figure 5.4.I.2. In-line GC/MS Ion Chromatogram for PFOS at 900C 5.4.I.2. Off-line GC/MS Analysis Figure 5.4.1.3 shows the total ion chromatogram for off-line GC/MS analyses for PFOS combustion at 600C. The largest peak at the beginning is associated with air. The second peak at 1.0 min. was identified as 1,1-difluoroethene. The peak at 3.0 min. was identified as sulfur dioxide. Figure 5.4.1.4 shows the total ion chromatogram for off-line GC/MS analyses for PFOS 002066 16 combustion at 900C. Similar results were obtained. The largest peak at the beginning is associated with air. The second peak at 3.0 min. corresponds to sulfur dioxide. Abu r>dno Figure 5.4.I.4. Off-line GC/MS Ion Chromatogram for PFOS at 900C 5.4.I.3. LC-MS Analysis of Extracts Table 5.4.1.4 shows the analytical results of the reactor/ transfer line extraction samples. Extracts o f reactor/transfer line tubing after the 900C test summed to only about 0.04% o f the PFOS added. Table 5.4.1.4. Methanol Extraction Results for PFOS Combustion Test Extraction PFOS (pg/ul) PFOS (pg) 1st 15.4 0.11 2nd 8.61 0.059 002067 17 5.4.1.4. LC-MS Analysis of PUF Cartridges Table 5.4.1.5 shows the analytical results for the PUF sampling cartridges. The amount of PFOS captured in the PUF was 0.49% of the PFOS added at 600C. Only 0.07% was captured by the PUFs at 900C. Surprisingly, somewhat larger amounts o f PFOS were extracted from the second PUF in a two-PUF series at both 600C and 900C. This suggests that some PFOS could have passed completely through the system, but in the third transfer efficiency tests, much larger amounts of PFOS were captured in the first PUF in the series showing that the first PUF typically collects more. An amount of carryover equivalent to 0.026% o f PFOS added in the preceding 600C tests was extracted from the PUF in the PFOS interim blank. Table 5.4.I.5. PUF Extraction Results for PFOS Combustion Test Temp Extraction PFOS PFOS (C) (Pg/ld) (Pg) 600 PUF (1st) 25.1 0.62 PUF (2nd) 64.0 1.6 900 PUF (1st) 4.31 0.11 PUF (2nd) 9.01 0.22 5.4.2. FC-1395 Combustion Test Table 5.4.2.1 shows net amount o f sample gasified for FC-1395 combustion tests. The sample probe was weighed before and after the combustion tests. Table 5.4.2.I. Net Amount of Gasified Sample for FC-1395 Combustion Test Temperature Usage Loaded Dried Remaining Net Amount of (C) Mass (mg) Mass0 (mg) Gasified (mg) Sample (mg) 600 PUFa 2.14 0.56 0.04 0.52 TBb 2.22 0.58 0.06 0.52 900 PUF 2.20 0.57 0.02 0.55 TB 2.23 0.58 0.15 0.43 *In-line GC/MS analysis and off-gas collection using PUF. Off-line GC/MS analysis using Tedlar Bag. c Calculated based on the water contents (74%). Table 5.4.2.2 and 5.4.2.3 shows flow rate profiles used for FC-1395 combustion tests at 600 and 900C, respectively. The detailed explanation for each value can be found in section 5.4.1. 0 0 iw 0 S 8 18 Table 5.4.2.2. Flow Rate Profile for FC-1395 Combustion Test at 600C Time Period Reactor Flow (sec) Rate (ml/min) Pyroprobe Flow Rate (ml/min) Total Flow Rate (ml/min) Volume (ml) 0 -6 0 60-85* 8 5 -1 5 7 157 -1 6 7 167-177 177 -1 9 7 A ir 9.53 0 .0 0 9.53 9.53 9.53 8.20 (He)c Air CH4 0.85 0.16 10.54 0.0 0 0.85 0.85 4.63b 0 .0 0 0.16 0.16 0.0 0 10.54 10.54 14.32 4.63 0.16 14.32 4.53 (He)d 0 12.73 Total volume passed through reactor (ml) 10.54 0 .0 0 12.65 2.07 2.39 4.24 31.89* Total volume passed through PUF (ml) Total volume used for off-line GC/MS S 0 2 quantitative analysis (ml) 29.02f 2 1 .35g 1 System opened due to sample insertion. Assuming no outlet flow.b Linear increase (approximate). c,i Switched to helium for sweep.e Total carrier flow volume that passed through the reactor. f Total carrier flow volume that passed through PUFs. 8 Volume used to calculate total amount of S 02 recovered using off-line GC/MS system. Table 5.4.23. Flow Rate Profile for FC-1395 Combustion Test at 900C Time Period Reactor Flow (sec) Rate (ml/min) Pyroprobe Flow Rate (ml/min) Total Flow Rate (ml/min) Volume (ml) 0 -6 0 60-85* 85 - 1 7 9 179-189 189-199 199-219 A ir 7.14 0 .0 0 7.14 7.14 7.14 6.14 (He)c A ir 0.63 0 .0 0 0.63 0.63 - 4.63b 4.63 4.53 (He)d CH4 0.1 2 0 .0 0 0.1 2 0 .1 2 0.1 2 0 7.89 0 .0 0 7.89 7 .8 9 - 11.89 11.89 10.67 7.89 0.0 0 12.36 1.65 1.98 3.56 Total volume passed through reactor (ml) 27.44* Total volume passed through PUF (ml) 24.20f __________ Total volum e used for off-line GC/M S SO2 quantitative analysis (m l) 19.558 *System opened due to sample insertion. Assuming no outlet flow .bLinear increase (approximate). cdSwitched to helium for sweep. *Total carrier flow volume that passed through the reactor. f Total carrier flow volume that passed through PUFs. 8 Volume used to calculate total amount o f SO2 recovered using off-line GC/MS system. 5.4.2.I. In-line GC/MS Analysis Figure 5.4.2.1 shows the total ion chromatogram for FC-1395 combustion at 600C. The first peak at 0.4 to 1.0 min. was not clearly identified. The second peak at 1.7 to 2.4 corresponds to sulfur dioxide. The peak at 7.1 min, was identified as carbon disulfide and the largest peak at 10 minutes was identified as benzene followed by fluorobenzene at 11.1 min. The wide peak appeared at 10 to 13 minutes corresponds to tetrafluorosilane. The peaks after tetrafluorosilane include benzonitrile at 17.7 min. and naphthalene at 21.1 min. Figure 5.4.2.2 shows the total ion chromatogram for FC-1395 combustion at 900C. The first peak at 2.2 min. was identified as sulfur dioxide and the peak at 11 min. was identified as benzene. The sharp peak at 14.2 minutes and the subsequent wide peak both show a strong 85 signal that is attributed to tetrafluorosilane. 002069 19 Abundarte T IC : FC 3-6Q -1.D Figure 5.4.2.I. In-line GC/MS Ion Chromatogram for FC-1395 at 600C Figure 5.4.2.2. In-line GC/MS Ion Chromatogram for FC-1395 at 900C 5.4.2.2. Off-line GC/MS Analysis Figure 5.4.2.3 shows the total ion chromatogram for off-line GC/MS analyses for FC-1395 combustion at 600C. The large peak at the beginning is associated with air. The next peak at 0.9 min. was identified as 1,2-difluoroethene followed by sulfur dioxide at 3 min., difluorodimethylsilane at 4.8 min., benzene at 9.9 min. and fluorobenzene at 10.1 min. Difluorodimethylsilane also is likely produced during the gasification process. Figure 5.4.2.4 shows the total ion chromatogram for off-line GC/MS analyses for FC-1395 combustion at 900C. The largest peak is associated with air. Sulfur dioxide at 3 min. was the only identifiable product. 002070 20 4000007 300000 300000 - -3 4 0 0 0 0 i3 2 0 0 0 0 Figure S.4.2.3. Off-line GC/MS Ion Chromatogram for FC-1395 at 600C 5.4.2.3. LC-MS Analysis of Extracts Table 5.4.2.4 shows the analytical results o f the reactor/ transfer line extractions. No detectable amount of PFOS was found. Table 5.4.2.4. Methanol Extraction Results for FC-1395 Combustion Test Extraction PFOSipg/ul) PFOS(ug) 1st <5.00 <0.035 2nd <5.00 <0.035 5.4.2.4. LC-MS Analysis of PUF Table 5.4.2.5 shows the analytical results for the PUF sampling cartridges. No detectable amount of PFOS was found. 002071 21 Table 5.4.2.5. PUF Extraction Results for FC-1395 Combustion Test Temp Media PFOS PFOS (C) (Pg/M-I) (pg) 600 PUF (1st) <5.00 <0.12 PUF (2nd) <5.00 <0.12 900 PUF (1st) <5.00 <0.12 PUF (2nd) <5.00 <0.12 5.4.3. FC-807A Combustion Test Table 5.4.3.1 shows net amount o f sample gasified for FC-807A combustion tests. The sample probe was weighed before and after the combustion tests. Table 5.4.3.I. Net Amount of Gasified Sample for FC-807A Combustion Test Temperature Usage Loaded Dried Remaining Net Amount of (C) Mass Massc (mg) Gasified _________________________ (mg) (mg)_______________Sample (mg) 600 PUFa 2.68 0.59 0.00 0.59 TB5 2.68 0.59 0.00 0.59 900 PUF 2.43 0.53 0.08 0.45 TB 2.55 0.55 0.02 0.53 *In-line GC/MS analysis and off-gas collection using PUF. b Off-line GC/MS analysis using Tedlar Bag. c Calculated based on the water contents (78%). Tables 5.4.3.2,5.4.3.3, and 5.4.3.4 show the flow rate profiles used for FC-807A combustion tests at 600 and 900C, and the blank test between 600 and 900C, respectively. The detailed explanation for each value can be found in section 5.4.1. PUF samples were collected from the blank runs between the 600 and 900C test runs. The unheated valve/transfer line tubing downstream of the reactor/transfer line tubing was also extracted after the combustion test at 600C. The purpose o f these analyses was to measure the carryover between the tests on a single fluorocarbon product done at 600 and 900C. Table 5.4.3.2. Flow Rate Profile for FC-807A Combustion Test at 600C Time Period Reactor Flow (sec) Rate (ml/min) Pyroprobe Flow Rate (ml/min) Total Flow Rate Volume (ml/min) (ml) 0-60 60-85* 85-157 157-167 167 -177 177 -197 Air 9.70 0.00 9.70 9.70 9.70 8.89 (He)c Air CH 0.84 0.15 10.69 0.00 0.00 0.00 0.84 0.15 10.69 0.84 - 4.63b 0.15 10.69 14.48 4.63 0.15 14.48 4.53 (He)d 0 13.42 Total volume passed through reactor (ml) Total volume passed through PUF (ml) 10.69 0.00 12.83 2.10 2.41 4.47 32.50* 29.64f _________Total volume used for off-line GC/MS S02quantitative analysis (ml) 21.81* *System opened due to sample insertion. Assuming no outlet flow.b Linear increase (approximate). c,dSwitched to helium for sweep. *Total carrier flow volume that passed through the reactor. f Total carrier flow volume that passed through PUFs. gVolume used to calculate total amount of SO2 recovered using off-line GC/MS system. 002072 22 Table 5.4.3.3. Flow Rate Profile for FC-807A Combustion Test at 900C Time Period Reactor Flow (sec) Rate (ml/min) Pyroprobe Flow Rate (ml/min) Total Flow Rate Volume (ml/min) (ml) 0-60 60 - 84* 84-178 178-188 188-198 198-218 Air 7.25 0.00 7.25 7.25 7.25 6.27 (He)c Air CH4 0.66 0.12 8.03 0.00 0.00 0.00 0.66 0.12 8.03 0.66 4.63b 0.12 8.03 12.00 4.63 0.12 12.00 4.53 (He)d 0 10.80 Total volume passed through reactor (ml) 8.03 0.00 12.58 1.67 2.00 3.60 27.88* Total volume passed through PUF (ml) 24.65f Total volume used for off-line GC/MS S 0 2 quantitative analysis (ml) 19.858 *System opened due to sample insertion. Assuming no outlet flow .b Linear increase (approximate). c,dSwitched to helium for sweep. *Total carrier flow volume that passed through the reactor. f Total carrier flow volume that passed through PUFs. gVolume used to calculate total amount of S 0 2 recovered using off-line GC/MS system. Table 5.4.3.4. Flow Rate Profile for Blank Analysis between 600 and 900C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate (sec) Rate (ml/min) (ml/min) (ml/min) Volume (ml) 0-120 120-130 130-140 140 -160 Air 9.70 9.70 9.70 8.89 (He)b Air 0.84 0.84 4.63* 4.63 4.53 (He)c CH4 0.00 0.00 0.00 0.00 10.54 10.54 - 14.33 14.33 13.42 21.08 2.07 2.39 4.47 `Linear increase (approximate). b.c ci Total Volume (ml) 30.01 5.4.3.I. In-line GC/MS Analysis Figure 5.4.3.1 shows the total ion chromatogram for FC-807A combustion at 600C. The first peak at 0.6 to 1.3 min. was not clearly identified. The second peak at 1.9 to 2.4 min. was identified as sulfur dioxide. The peak at 7.1 min. was identified as carbon disulfide. The peak at 8.1 min. which shows strong spectra at m/z = 69 and 51 was not clearly identified. Peaks at 10.3 and 11.1 min. were identified as benzene and fluorobenzene, respectively. The wide peak that appeared at 11.2 to 12.6 min and the subsequent background correspond to tetrafluorosilane. The two major peaks after tetrafluorosilane were not clearly identified. Figure 5.4.3.2 shows the total ion chromatogram for FC-807A combustion at 900C. The first peak at 2.0 to 2.8 min. corresponds to sulfur dioxide. The largest peak at 15.4 min, and the subsequent high background correspond to tetrafluorosilane. 002073 sooooo- Figure 5.4.3.I. In-line GC/MS Ion Chromatogram for FC-807A at 600C Abundance TIC: FC4-90-1.D Figure S.4.3.2. In-line GC/MS Ion Chromatogram for FC-807A at 900C S.4.3.2. Off-line GC/MS Analysis Figure 5.4.3.3 shows the total ion chromatogram for off-line GC/MS analyses for FC-807A combustion at 600C. The largest peak at the beginning is associated with air. The second peak at 3.0 min. and the third peak at 4.8 min. were identified as sulfur dioxide and difluorodimethylsilane, respectively. There were no further identifiable peaks. Figure 5.4.3.4 shows the total ion chromatogram for off-line GC/MS analyses for FC-807A combustion at 900C. Similar results were obtained. The largest peak at the beginning is associated with air. The second peak at 3.0 min. and the third peak at 4.8 min. correspond to sulfur dioxide and difluorodimethylsilane, respectively. 002074 -340000 -3 2 0 0 0 0 -3 0 0 0 0 0 2 3 0 0 0 0 -2 3 0 0 0 0 -2 4 0 0 0 0 220000 200000 -1 3 0 0 0 0 -j1 3 0 0 0 0 -1 4 0 0 0 0 120000 1o o o o o - Figure 5.4.3.3. Off-line GC/MS Ion Chromatogram for FC-807A at 600C Figure 5.4.3.4. Off-line GC/MS Ion Chromatogram for FC-807A at 900C 5.4.3.3. LC-MS Analysis of Extracts Table 5.4.3.5 shows the analytical results o f the reactor/transfer line extractions. No detectable amount of PFOS was found. Table 5.4.3.5. Methanol Extraction Results for FC-807A Combustion Test Extraction PFOS(pg/ul) PFOS (pg) 1st <5.00 <0.035 2nd <5.00 <0.035 5.4.3.4. LC-MS Analysis of PUF Table 5.4.3.6 shows the analytical results for the PUF sampling cartridges. No detectable amount of PFOS was found. 002075 25 Table 5.4.3.6. PUF Extraction Results for FC-807A Combustion Test Temp Media PFOS PFOS (C) (Pg/pl) (Pg) 600 PUF (1st) <5.00 <0.12 PUF (2nd) <5.00 <0.12 900 PUF (1st) <5.00 <0.12 PUF (2nd) <5.00 <0.12 5.5. 2ndHeated Blank Combustion Analysis After the combustion tests were completed, the heated blank reactor/ transfer line tubing was analyzed again to examine system cross contamination at temperatures of 600 and 900C. In line GC/MS analysis, off-line GC/MS analysis using Tediar bags, and PUF cartridge sampling were conducted. The same process used for the first heated blank analysis before the sample combustion tests was performed for this second heated blank analysis. The PUF samples were sent to 3M Environmental Laboratory for LC/MS analysis. 5.5.1. In-line GC/MS Analysis Tables 5.5.1 and 5.5.2 show flow rate profiles and carrier flow volumes used for heated blank analysis at 600 and 900C, respectively. Figures 5.5.1 and 5.5.2 show total ion chromatograms for reactor temperatures at 600 and 900C, respectively. The chromatograms show only background noise and no contamination was found for either temperature. Table 5.5.1. Flow Rate Profile for Heated Blank Analysis at 600C Time Period Reactor Flow (sec) Rate (ml/min) Pyroprobe Flow Rate Total Flow Rate (ml/min) Total Sampled Volum e Volume*1 0-120 120-130 130-140 140-160 10.0 10.0 10.0 8.83 (He)b (ml/min) 0.81 0.81 - 4.631 4.63 4.53 (He)c 10.81 10.81 - 14.63 14.63 13.36 (ml) 21.62 2.12 2.44 4.45 (ml) 19.62 1.95 2.27 4.12 Total Volume (ml) 30.63 27.97 atL:i_n_e_ar*in_c_rease (approximate). bb.,cc oS_w_it_c_h_e_di to helium for sw ee p .d Sam pled volum e for PUF and Tedlar bag collection. Table 5.5.2. Flow Rate Profile for Heated Blank Analysis at 900C Time Period Reactor Flow (sec) Rate (ml/min) 0 - 150 150-160 160-170 170-190 ar : : _ 7.11 7.11 7.11 6.16 (He)b Pyroprobe Flow Rate (mi/min) 0.62 0.62 - 4.63a 4.63 4.53 (He)c b ,c , Total Flow Rate (ml/min) 7.73 7 .7 3 - 11.74 11.74 10.69 Total Volume (ml) Total Volume (ml) 19.33 1.62 1.96 3.56 26.47 Sampled V olum ed (m l) 16.83 1.46 1.79 3.23 23.30 and Tedlar bag collection. 002076 26 Figure 5.5.1. In-line GC/MS Ion Chromatogram for Heated Blank at 600C 5.5.2. Off-line GC/MS Analysis Figures 5.5.3 and 5.5.4 show total ion chromatograms for the heated blank at 600 and 900C respectively. The large peaks at the beginning are associated with air. No other peaks were observed. Figure 5.5.3. Off-line GC/MS Ion Chromatogram for Heated Blank at 600C 00Z077 27 Abundano Figure 5.5.4. Off-line GC/MS Ion Chromatogram for Heated Blank at 900C 5.5.3. LC-MS Analysis of PUF Cartridges Table 5.5.3 shows the analytical results for the PUF sampling cartridges. No cross contamination was detected. Table 5.5.3. PUF Extraction Results for Heated Blank Analysis Temp PFOS (pg/pl) PFOS (pg) c o _____________________________ 600 <10.0 <0.25 900 <10.0 <0.25 5.6. Transport Efficiency Tests for PFOS Sample transfer efficiency tests were conducted to investigate how efficiently PFOS would be transferred through reactor/transfer line system. Three types o f tests were conducted as described in the Phase HI protocol and its addendum. 5.6.1. l 5t Transport Efficiency Test In the first transfer efficiency test, PFOS was volatilization in the pyroprobe chamber and the reactor and transfer lines were heated to 260C. PUF cartridge sampling o f the off-gases was performed. This test examines the transfer efficiency o f samples gasified in the pyroprobe and transported through reactor. Table 5.6.1.1 shows the net amount o f gasified sample for the 1st transfer efficiency test. Table 5.6.1.2 shows the flow profiles. Sample PFOS Loaded Mass (mg) 0.53 Remained after Gasification (mg) 0.05 Net Amount of Gasified Sample (mg) 0.48 O O C078 28 Table 5.6.I.2. Flow Rate Profile for 1st Transfer Efficiency Test* Time Period Reactor Flow (sec) Rate (ml/min) 0 -6 0 6 0 -8 4 16.0 0.00 Pyroprobe Flow Rate (ml/min) 0.82 0.00 Total Flow Rate (ml/min) 16.82 0.00 Total Volume (ml) 16.82 0.00 Sampled V olum e' (ml) 15.82 8 4 -1 5 6 16.0 0.82 16.82 20.18 18.98 156-166 16.0 0.82 - 4.53b 16.82 20.53 3.11 2.95 166-186 16.0 4.53 20.53 6.84 6.51 Total Volume (ml) 46.95 44.26 "H elium w as used for all carrier nflo_w..b"rL:inea.r increase (approxim ate).c Sam pled volum e for PUF collection. Table 5.6.1.3 shows the PUF cartridge sampling results for PFOS. No sample was recovered from the PUF cartridge. This result indicates that die sample was either thermally dissociated in the pyroprobe chamber or the gasified sample was completely condensed in the pyroprobe/reactor transfer line tubing. Table 5.6.1.3. PU F E xtraction Results fo r l 8t T ran sfer Efficiency Test Sample PUF ____________Extracts PFOS PFOS (pg/j-il) (pg) PFOS 1st <5.00 <0.12 2nd <5.00 <0.12 5.6.2. 2nd T ransfer Efficiency Test To investigate the possibility that the sample condensed on the walls of the pyroprobe/reactor transfer line, the sample was collected directly from the pyroprobe upstream o f the reactor. PUF sample cartridges were connected to the pyroprobe using the shortest possible transfer line heated to 260C. The pyroprobe and transfer line were extracted using methanol. Table 5.6.2.1 shows the net amount o f gasified sample for 2ndtransfer efficiency test. Table 5.6.2.2 shows the flow profiles. T able 5.6.2.I. N et A m ount o f Gasified Sam ple fo r 2nd T ran sfer Efficiency T est Sample Loaded Remained after Net Amount of Mass (mg) Gasification (mg) Gasified Sample (mg) PFOS 0.47 0.00 0.47 oqz079 29 Table 5.6.2.2. Flow Rate Profile for 2nd Transfer Efficiency Test* Time Period (sec) Pyroprobe Flow Rate (ml/min) Volume (ml) 0 -6 0 6 0 -8 2 0.63 0.00 0.63 0.00 82 - 1 7 6 176-186 186-216 0.63 0.63 4.53b 4.53 0.99 0.43 2.27 Total Volume (ml) 4.32 "Helium was used for carrier flow. bLinear increase (approximate). Table 5.6.2.3 shows the analytical results for the extracts. Table 5.6.2.4 shows the analytical results for PUF cartridge samples. This test shows that measurable amounts o f PFOS survive pyrolysis conditions o f the pyroprobe, and enter the heated transfer lines up to the reactor. However, none o f the PFOS survives transit to the PUF sampling cartridge. Table 5.6.2.3. Methanol Extraction Results for 2nd Transfer Efficiency Test Sample Extracts PFOS PFOS PFOS (pg/ftl) (Mg) 1st 897 21 2s3 <10.0 <0.24 Table 5.6.2.4. PUF Extraction Results for 2nd Transfer Efficiency Test Sample PUF PFOS PFOS PFOS Extracts 1st (Pg/pl) <10.0 (Mg) <0.25 2s3 <10.0 <0.25 5.6.3. 3rd Transfer Efficiency Test A 3rd transfer efficiency test was conducted to examine how much PFOS can be transferred through the reactor/transfer line tubing and sampled by PUF cartridges if these samples were formed in the reactor. Two methanol extracts were obtained: 1) the heated reactor/transfer line tubing and 2) the unheated valve and associated transfer line tubing upstream o f the PUF cartridges. Table 5.6.3.1 shows the net amount o f gasified sample for each test. The experiments were carried out using both air and helium to compare the results. After a sample was placed in the reactor and the system was closed, the temperature o f GC oven was increased to prevent the condensation o f gasified sample. When the GC oven temperature reached 260C, the furnace temperature was set to the temperature shown in Tables 5.6.3.2 and 5.6.3.3. The off gas collection using PUF cartridges was initiated when the GC oven started heating. 002080 30 Table 5.6.3.I. Net Amount of Gasified Sample for PUF Collection Sample Carrier Gas Loaded Mass Remained after Gasification Net Amount of Gasified Sample (mg) PFOS Air 0.48 PFOS He 0.50 (mg) 0.00 0.04 (mg) 0.48 0.46 Tables 5.6.3.2 and 5.6.3.3 also show flow rate profiles PFOS gasification under oxygen-rich and oxygen-deficient conditions. Table 5.6.3.2. Flow Rate Profile for PUF Collection (PFOS Gasification with Air) Time Period (sec) Temperature Condition (C) Carrier Gas U sed and Flow Rate (ml/min) Total Volume (ml) Sampled Volume1 (ml) 0 -4 3 9 439-637 637-937 937-997 GC Oven 25 -> 260 Furnace 103 -> 575 GC = 260, Furnace = 575 GC = 260, Furnace = 575 Air 10.7 Air 10.7 Air 10.7 He 8.6 Total (ml) 78.29 35.31 53.50 8.60 175.70 70.97 32.01 48.50 7.60 159.08 a Sampled volume for PUF collection. Table 5.6.3.3. Flow Rate Profile for PUF Collection (PFOS Gasification with He) Time Period (sec) Temperature Condition (C) Carrier Gas U sed and Flow Rate (ml/min) Total Volume (ml) Sampled Volume* (ml) 0-410 GC Oven 30 -> 260 H e 10.8 73.80 66.97 410-615 615-975 Furnace 140 -> 575 GC = 260, Furnace = 575 He 10.8 He 10.8 Total (ml) 36.90 64.80 175.50 33.48 58.80 159.25 a Sampled volume for PUF collection. Tables 5.6.3.4 and 5.6.3.5 show the amount of recovered sample from the extracts and the PUF cartridges, respectively. The 3rdtransfer efficiency test showed quite clearly that some measurable PFOS (5.2% air, 12.8% He) could pass from the heated reactor where it was volatilized in this test to the PUFs. Larger amounts o f PFOS (5.6% air, 39.4% He) also accumulated in the reactor/transfer lines upstream of the PUF cartridges. The majority of the PFOS accumulated in the portion o f the transfer line heated to 260C, suggesting that this compounds could condense, or were in a particulate form, at this temperature. Table 5.6.3.4. Reactor/Valve Transfer Line Extraction Results Sample Gasification Location Extracts PFOS PFOS ____________________________________________ (pg/pl) Reactor I s* 1908 (wO 24 PFOS A ir _____________ 2nd V alv e 1st ______________________ Reactor 1st 35.4 696 2nd 22.8 13530 0.45 2.4 0,079 171 He _____________ 2nd Valve 1st 150 2218 1.9 7.7 ____________________________________ 2nd 102 0,35 002081 31 Table 5.6.3.5. PUF Extraction Results Sample Carrier Cartridge PFOS PFOS PFOS Gas He (pg/jxl) (ng) 1st 2330 58 253 44 1.1 Air 1st 997 25 2 <10.0 <0.12 5.7. Sulfur Recovery Rate as S 0 2, SOF2, and S 0 2F2 Based on the in- and off-line GS/MS analyses, sulfur was found mainly as S 0 2. No SOF2 and S 0 2F2 were detected. The sulfur recovery rate as S 0 2 using in-line GC/MS system was not quantitatively repeatable. This was due primarily to the low S 0 2 peak resolution using the cryogenic focusing method at -60C with a holding time o f ca. 4 min. Because the S 0 2 peaks using the off-line GC/MS system were much sharper than S 0 2peaks observed using in-line GC/MS, we decided to use off-line GC/MS analytical results to quantitatively analyze the sulfur recovery analysis as S 0 2. The detailed operational procedures were described in Section 5.4. Table 5.7.1 and Figure 5.7.1 show the calibration results. The sulfur recovery rate is reported on a molar basis. The formula obtained from this calibration was: S 0 2 (Mol) =[Area + 494980] / [1.7997x 1014] Table 5.7.1. SQ2 Calibration Results Using PLOT Column Cone, (ppm) M ol.# Area 1 Area 2 Area (Avg) 1000 4.09E-08 7191079 6980771 7085925 700 2.86E-08 4414365 4366705 4390535 400 1.63E-08 2304594 2295497 2300046 100 4.09E-09 425431 416699 421065 0UZ082 32 8.0 10 7.0 10 6.0 10- (0 5.0 10' 52 4.0 106 <<D0 CL 3.0 10 2.0 10 1.010 y = -4.9498e+05 +1.7997e+1 lx R=0.996 >6 y / y / y / / 0.0 10 1 1 r 1 1 1 1 1 i 1 1 1 "1 1 1 1 1 11t 0 110 2 10" 3 10" 410' 510' Mol Figure 5.7.1. SO2 Calibration Curve (Molar Number vs. Peak Area) Prior to the sulfur recovery analysis as SO2, a third SO2 transfer efficiency test was conducted using the off-line analysis approach. Table 5.7.2 shows the results. Air was flowed through the reactor at 8.85 ml/min for 2 min. 30 sec. while the SO2 standard was being injected and the off gas was collected using a Tedlar bag. The average recovery rate was 75.6%. This is very similar to the recovery rates obtained from the in-line analysis, i.e. 83.7 and 76.4%, suggesting that the lack in 100% recovery is due to sample losses in the combustion system and not the sampling and analysis procedures. Table 5.7.3 shows sulfur recovery rate as SO2 for PFOS, FC-1395 and FC-807A. The last column shows the sulfur recovery rate taking into account a transfer efficiency rate o f 75.6%. Results for the Cg perfluorosulfonamides were quite reasonable, 10025%. Results for PFOS were not as good, with recovery rates o f only 50-60%. ____________ Table 5.7.2. Standard SO2 Transfer Efficiency____________ Volume (ml) Area Calculated Mol. # # of Mol. Used Transfer Efficiency (%) 22.13 10591947 1.36E-06 1.63E-06 83.4 22.13 8515987 1.11E-06 1.63E-06 67.8 Average 75.6 002083 33 Compound PFOS FC-1395 FC-807A Temp. (C) 600 900 600 900 600 900 Table 5.7.3. Sulfur Recovery Rate as SO2 Volume (ml) Area Calculated Gasified # o f Mol. of M ol.# Mass Gasified (mg) Sample Recovery Rate (%) 22.07 2169830 3.27E-07 0.38 7.06E-07 46.3 19.62 2676600 3.46E-07 0.50 9.29E-07 37.2 21.35 4159651 5.52E-07 0.52 7.15E-07 77.2 19.55 3402701 4.23E-07 0.43 5.91E-07 71.6 21.81 6587251 8.58E-07 0.59 9.15E-07 93.8 19.85 6354547 7.55E-07 0.53 8.22E-07 91.9 Recovery Rate after Efficiency Correction ( % ) 61.2 49.2 102.1 94.7 124.0 121.5 5.8. Extracted Ion Analysis The following ions (69-CF3,119-C2F5, and 67-SOF) were extracted from the total ion chromatograms o f the PFOS and Cs perfluorosulfonamide tests (in-line and off-line GC/MS analyses) to analyze for the presence o f perfluorinated and sulfonate-containing intermediates. The purpose o f this analysis was to provide additional information regarding the potential formation of volatile fluorocarbons and volatile fluorinated oxysulfur compounds that were not identified in the GC/MS approach outlined in the previous sections. The analyses indicated that the 67 ions exist in negligible amounts thus indicating that all gas-phase sulfur compounds were indeed accounted for in the analysis of the total ion chromatograms as sulfur dioxide and carbon disulfide. This analysis further indicated that 69 and 119 ions were present in most if not all o f the total ion chromatograms. Most notable here was the presence of these ions in the GC signals at short retention times, thus indicating that other volatile fluorocarbons were present that were not identified in the analysis of the total ion chromatograms. In contrast to tests results for other fluorocarbon compounds (Yamada and Taylor, 2002), no 69 ion was detected from the PFOS combustion chromatograms obtained from either the in-line or off-line sampling procedures. During the analysis of the off-line samples, hydrogen flame ionization detector (HFID) as well as mass spectral data were collected. Due to the suspect results from the extracted ion analysis of the total ion chromatograms generated from PFOS combustion, the HFID data for the combustion products o f another compound with perfluoroalkyl moieties having less than 8 carbons, labeled as PFXS, was analyzed in addition to the HFID data for PFOS combustion products. Analysis o f these HFID data showed the formation of volatile fluorocarbons. This analysis did not give quantifiable results, but due to the structural similarity o f PFXS and PFOS, this analysis substantiates the potential formation of volatile fluorocarbons from the combustion of PFOS. Figure 5.8.1 shows the total ion chromatogram and the corresponding HFID signal for PFXS off line GC/MS analysis at 600C. A HFID peak appears with same retention time as the "air" peak for the total ion chromatogram. Since the HFID does not respond to the molecular constituents in air (N2,02, Ar, CO2) but does respond to fluorocarbons, it is apparent that volatile fluorocarbons are eluting from the GC column simultaneously with the air constituents. Mass spectral ions corresponding to volatile fluorinated compounds, including CF2H-5I, SOF-67, CF369, CF2CF2H-IOI, and C2F5-119, were extracted from the total ion chromatogram and are shown in Figure 5.8.2 along with the HFID signal. The results indicate that the HFID peak at a retention time o f 0.8 min. corresponds to a mass spectral signal that contains the following 002084 34 fluorocarbon ions: 51,69, and 119. The 51 ion occurs near the tail o f the HFID signal while the 69 and 119 ions occur near the peak o f the FID signal. Likely candidates that can be attributed to the 51 and 69 ions are tri- and tetrafluoromethane. Likely candidates for the 119 ion are penta or hexafluoroethane. Pentafluoroethane is detected at longer retention times and also contains a strong 101 ion that is not present in the unknown peak. It is plausible that hexafluoroethane would elute earlier than pentafluoroethane due to its lower boiling point. Thus, the most probable candidates that correspond to the HFID signal at 0.8 min. are tri- and tetrafluoromethane and/or hexafluoroethane. Figure 5.8.1. Total Ion Chromatogram and Corresponding HFID Signal for Combustion of PFXS at 600C (off-line sample) 002085 35 Abundant 80000 60000 40000 20000 o Tim a--= Abundance Ion 51.00 <50.70 to 51.70): FC5-GOT.D 80000 80000 40000 O20000 Tim a-- Abundance lor 67.00 (66.70 to 67.70): FC5-60T.D 80000 60000 40000 O20000 Abundance 0.50 lor 69.00 (68.70 to 69.rO>: FC5-60T.D 80000 60000 40000 20000 O*--------->---1---1---'---' 0.50 Tim e-- Abundance lor* 1 0 1 .0 0 (1 0 0 .7 0 to 101.70): F C 5 - 6 0 T .D ' '---1--->---1-------1---1---- *1.00 -1.50 '---'---1---'---'----------1---1---'----------1-----------------1---1-------1---1---1----1---1---1------1----- 2.00 2.50 3.00 3.50 4.00 4.50 80000 60000 40000 O20000 Tim e--=Abundance lor 1 19.00 <1 18.70 to 119.70): R G S-6 0 T .D Figure 5.8.2. Extracted Ions (CF2H -5l, SOF-67, CF3-6 9 , CF2CF2H-IOI, and C2F5- I I 9) and Corresponding HFID Signal for Combustion of PFXS at 600C (off-line sample) Figure 5.8.3 shows the HFID signal for PFOS combustion at 600C, and the integrated HFID peak areas for PFXS and PFOS are shown in Table 5.8.3. The retention time o f the HFID response from PFOS combustion is nearly identical to the HFID response from PFXS combustion (see Fig. 5.8.1), strongly suggesting that the same combustion products are forming from these two different compounds. The HFID signal and integrated HFID peak area for PFOS combustion at 900C are shown in Figure 5.8.4 and Table 5.8.4. The peak is ca. l% o f the 002086 36 response obtained at 600C, thus indicating nearly complete destruction of fluorinated compounds under these conditions. Abundance Figure 5.8.3. HFID Signal for PFOS Combustion at 600C (off-line sample) FC7-90T.D\FID1 A Figure 5.8.4. HFID Signal for PFOS at 900C (off-line sample) Table 5.8.3. Integrated HFID Peak Area o f PFXS and PFOS at 600C Sample Peak Area Net Amount o f Gasified ______________________ Sample (mg) PFXS 1190193 0.52 PFOS 3547614 0.38 Table 5.8.4. Integrated HFID Peak Area of PFOS at 900C Sample Peak Area Net Amount o f Gasified ________________ ______ Sample (mg) _______ PFOS_____ 39041 0.50 37 0 0 ^ .0 8 7 6. Discussion The motivation of this study was to determine the incinerability of perfluoro-octanyl sulfonate (PFOS) and if other perfluoro-octanyl compounds could be transformed to PFOS during the incineration process. A laboratory-scale study simulating a full-scale hazardous waste incinerator was envisioned in the phase I test protocol. Based on prior experience with halogenated compounds, we initially planned to use relatively modest conditions in the primary combustion zone (ca. 400C) to gasify the materials with more severe high-temperature (600 900C), oxidative conditions applying to the secondary combustion zone. TGAs of the active ingredients indicated that higher temperatures (~ 600C) were necessary to gasify these unique materials. The sponsor also requested that the experiment be designed to detect low-level (0.1%) concentrations of PFOS in the exhaust gases. These factors necessitated the use o f large amounts o f material (milligram quantities) and high-temperature, long duration exposures (ca. 1250C, 40 sec) in a specially designed pyroprobe to fully gasify the material. These conditions, while representing quite severe conditions in the primary zone of an incinerator, e.g., a rotary kiln, are representative of the range of conditions that occur in a full-scale system. As such, the approach employed in the laboratory-scale combustion study described in the phase HI test protocol is a reasonable extrapolation of a full-scale incineration study o f PFOS and its potential precursors. Combustion tests for PFOS and two Cg perfluorosulfonamides, FC-1395 and FC-807A, were completed as requested by the sponsor. In-line and off-line GC/MS analyses, reactor effluent sample collection using PUF cartridges followed by LC-MS analysis, and chemical extraction of various transfer lines throughout the reactor system including the reactor itself followed LC-MS analysis were conducted to investigate the following: 1) the extent o f conversion o f the active ingredients, 2) the formation of fluorinated intermediate organic products, and 3) the extent of conversion o f the sulfur to sulfur oxides. There was no indication that PFOS was generated from FC-1395 and FC-807A combustion. No quantifiable amount of PFOS was detectable at a detection limit o f ca. 10 ng/ml. Dining PFOS combustion, small amounts o f PFOS were detected in the reactor/transfer line system and the PUF sample cartridges, specifically, 0.04% o f gasified sample in the reactor/transfer line system, less than 0.4% in the PUF cartridges at 600C, and 0.05% in the PUF cartridges at 900C. High levels of PFOS destruction were thus achieved at temperatures of 900C. To validate the experimental results pertaining to the sampling and analysis o f PFOS where in many instances the analytical results were below the level o f quantitation, a series o f transfer efficiency tests were conducted. The goals o f the transport (or transfer) efficiency tests were: 1) to see if PFOS could pass through the combustion system under nondestructive conditions and reach the PUF cartridges and, 2) to determine recovery efficiencies and analytical detection limits. In the 1st transfer efficiency test where the ability o f the combustion system to transport PFOS was assessed, analysis of the PUF cartridges indicated the lack o f any detectable material. This result indicated that PFOS was either thermally destroyed in the pyroprobe chamber (1250C) or the gasified sample condensed in the pyroprobe/reactor transfer lines and never reached the PUF sample cartridge. Based on the results o f 1st transfer efficiency test, a 2'nd transfer efficiency test was conducted to investigate the latter possibility. In these tests, 002088 38 substantial amounts, 3.4% of PFOS gasified, were indeed found in the pyroprobe/transfer line extracts. However, once again, analysis o f the PUF cartridges positioned downstream o f the pyroprobe/transfer line were negative for PFOS. The 2nd test showed that measurable amounts o f PFOS survive pyrolytic conditions in the pyroprobe and the heated (260C) transfer lines. The unanswered question was how much PFOS was transferred through the reactor/transfer line tubing and sampled by PUF cartridges if this material was formed in the combustion chamber. A 3rd transfer efficiency test was thus conducted to address this question. In this test, PFOS was placed in the combustion chamber and not into the pyroprobe. The temperature o f the combustion chamber and transfer line system was then heated to 260C. This is the temperature o f the transfer lines within the oven during the actual combustion tests. At this temperature, TGAs indicated there would be no PFOS volatilization, so there would be no PFOS movement through the system (the TGAs were conducted at UDRI during the Phase I protocol development). The combustion chamber was then heated to 600C while the transfer lines remained as 260C. When the combustion chamber was heated, some o f the PFOS was likely entrained into the gas stream, and a larger proportion was probably destroyed. Nevertheless, a substantial portion o f the PFOS was transported through the transfer lines to the PUFs where it was detected. PFOS was also found in the transfer lines. Specifically, results showed that measurable PFOS (3.8% air, 11% He) passed from the combustion chamber to the PUF sampling cartridges. Results also showed that slightly larger amounts o f PFOS (4.4% air, 30% He) accumulated in the reactor/transfer lines upstream of the PUF cartridges. These results demonstrated that if PFOS was formed in the combustion chamber, it would be detected in the PUFs. Therefore, when no PFOS was observed in the transfer lines or PUFs downstream o f the combustion chamber in the combustion tests, one could conclude that there must have been very little, if any, PFOS formed during combustion. A sulfur mass balance was attempted based on the premise that all o f the sulfur in the samples would be oxidized to SO2, SOF2, and SO2F2 under high-temperature oxidative conditions. The GC/MS analyses indicated that the sulfur was recovered as SO2. No SOF2 or SO2F2 was detected. Recovery rates were variable. Nearly 100% sulfur recovery was obtained from FC-1395. The recovery rate obtained from FC-807A was approximately 120%. Recovery rates were 50-60% for PFOS. There are two potential sources o f error in the sulfur mass balance. The most likely is the condensation o f the active ingredients and their primary degradation products in the pyroprobe and the pyroprobe/reactor transfer lines. The sulfur mass balance does not take into account this potential source of sulfur in the system as these lines were not extracted and analyzed for sulfur compounds. Another potential source o f error is the lack of complete quantitative transport o f the SO2. Three SO2 transport efficiency tests yielded an efficiency o f 78.64 %. The SO2 transport efficiency was accounted for in the sulfhr mass balance. The high repeatability o f these recovery tests suggests that this source o f error is small compared to potential condensation o f the active ingredients and their primary degradation products including SO2 on the walls o f the reactor and transfer lines. GC/MS analysis of the reactor effluent was conducted to assess the formation of combustion intermediates, i.e., products of incomplete combustion. The most abundant combustion byproduct was benzene. Benzene was observed for the all o f the samples except PFOS. Fluorobenzene was also observed from the combustion o f FC-1395 and FC 807A. For PFOS, the intermediate in highest concentration at 600C was a Ci or C2 fluorocarbon alkane, most 00C 0& 9 39 likely tri- or tetrafluoromethane or hexafluoroethane. At 900C, the concentration o f this compound was much lower in comparison with the 600C results. The nature of this byproduct and its thermal stability is consistent with other tests we have conducted on fluorinated samples that show that perfluorinated alkanes are stable intermediates and require temperatures in the secondary combustion zone in excess o f 900C for high levels of destruction (Ciba Special Chemicals Corp., 2002). Small amounts o f 1,1-difluoroethene (PFOS only) and 1,2difluoroethene (FC-1395 only) were also observed at 600C. The formation o f perfluoroalkanes and alkenes was not unexpected and is consistent with the molecular structure o f the starting material, where a Cs saturated fluorocarbon chain is present. There was no evidence to suggest that fluorinated acids were significant combustion products. Fluorinated acids have been observed by GC/MS analysis in combustion studies o f other fluorinated materials (Ciba Specialty Chemicals Corp., 2002), but were not observed in this study. The potential formation of fluorinated sulfonic acids could not be ascertained using gas chromatographic techniques. There was no evidence for the formation o f more highly fluorinated aromatic compounds, i.e., di- through hexafluorobenzene nor was there evidence to suggest that polyfluorinated biphenyls or dioxins could have formed under these conditions. Further analytical testing was conducted to verify that the following compounds, potential precursors to PFOS, were not formed during the combustion tests: POSF and C8F17SO2NH2. There was no evidence that these precursors formed during PFOS combustion. Further examination o f the total ion chromatograms for the SOF ion also indicated the lack of formation o f secondary amine precursors, i.e., N-MeFOSE alcohol (CgFnS02N(CH3)C2H40H), during the combustion of PFOS, FC-807A, and FC-1395. A small amount of undestroyed PFOS was observed in the LC/MS analyses. It is unlikely that PFOS reformed during the combustion process due to the presence of large amounts o f methane as the fuel for the combustion process. The presence o f excess methane fuel relative to fluorochemical product results in significant concentrations of H atoms that efficiently scavenge F atoms as HF and prevent the reformation of long perfluoroalkyl chains. The hydrocarbon fuel to fluorochemical ratio will likely be even higher under actual incineration conditions, further limiting the reformation of perfluoroalkyl chains. Perfluorinated alkanes, necessary building blocks to the formation of precursors to PFOS, were limited to Ci and C2 compounds, further indicating that reformation o f PFOS, requiring Cg perfluoroalkyl chains, did not occur in the combustion system. 002090 40 7. Conclusions The data presented herein clearly show that incineration o f FC-1395 and FC-807A does not release PFOS to the environment. This conclusion is based mainly on the LC/MS measurements, but was substantiated by the extracted ion analysis that showed negligible 67-SOF ion indicating negligible amounts of volatile sulfonate-containing degradation products. Sulfur recoveries were also quite good, 10025%. The dominant sink for sulfur was SO2. GC/MS analysis of perfluorinated alkyl sulfonate precursors indicated that such precursors were not present in the reactor effluent. This finding is consistent with the LC/MS measurements, and strongly suggests that the C-S bond was completely destroyed (and did not reform) in the combustion tests. High levels o f conversion of the PFOS were observed from the incineration tests. This conclusion was based on LC/MS measurements o f the reactor effluent and a thorough analysis of the transport of the material through the combustion system. Sulfur recoveries varied from 50 to 60%, depending on the reactor temperature. The dominant sink for sulfur was SO2. GC/MS analysis of perfluorinated alkyl sulfonate precursors indicated that such precursors were not present in the reactor effluent. This finding is consistent with the LC/MS measurements, and strongly suggests that the C-S bond was completely destroyed (and did not reform) in the combustion tests. Fluorinated organic intermediates were observed in the reactor effluent. These compounds were limited to fluorobenzene (FC-1395 and FC-807A only), Q or C2 fluoroalkanes (likely products are either CHF3, CF4, or C2F6), and 1,1-difluoroethene (PFOS only) and 1,2-difluoroethene (FC1395 only). Higher molecular weight fluorinated polycyclic aromatic hydrocarbons were not observed. The data from this laboratory-scale incineration study indicates that properly operating full-scale incineration systems can adequately dispose o f PFOS and the Cs perfluorosulfonamides. Incineration o f these fluorinated compounds is not likely to be a significant source o f PFOS into the environment. Furthermore, the finding that the C-S bond was completely destroyed indicates that reformation o f PFOS in the atmosphere from the emitted combustion byproducts (fluorinated organic compounds, SO2) is highly unlikely. With the exception o f stable Ci and C2 fluorocarbons, fluorinated organic intermediates are also unlikely to be emitted from these facilities during the incineration o f these materials. 002091 41 8. References Carroll, G.J., Thumau, R.C., Lee, J. W., Waterland, L.R., Dellinger, B., and Taylor, P.H., J. Air Waste Manage. Assoc., 1992,42, 1430. Ciba Specialty Chemicals Corporation, Final Report, 2002. Clark, W., Heap, M., Richter, W. and Seeker, R., The Prediction o f Liquid Injection Hazardous Waste Incinerator Performance, ASME/AIChE 22nd National Heat Transfer Conference, 1984. Dellinger, B., Torres, J., Rubey, W., Hall, D., Graham, J., and Carnes, R., Hazard. Waste Hazard. Mater., 1984, 1,137. Dellinger, B., Rubey, W., Hall, D., and Graham, J., Hazard. Waste Hazard. Mater., 1986, 3,139. Dellinger, B., Graham, M., and Tirey, D.A., Hazard. Waste Hazard. Mater., 1986, 3,293. Dellinger, B., Taylor, P.H., and Tirey, D.A., Minimization and Control of Hazardous Combustion By-Products, Final Report and Project Summary, EPA/600/S2-90/039,1991. Dellinger, B., Taylor, P.H., and Lee, C.C., J. A ir Waste Manage. Assoc., 1993, 43,203. Giesy, J. P. and Kannan, K., Environ. Sci. Technol., 2001, 35, 1339. Graham, J., Hall, D., and Dellinger, B., Environ. Sci. Technol., 1986, 20,703. Kannan, K., Koistinen, J., Beckmen, K., Evans, T., Gorzelany, J.F., Hansen, K.J., Jones, P.D., Helle, E., Nyman, M., and Giesy, J.P., Environ. Sci. Technol, 2001, 35, 1593. Rubey, W.A., and Carnes, R.A., Rev. Sci. Instrum., 1985, 56,1795. Rubey, W.A., and Grant, R.A., Rev. Sci. Instrum., 1988, 59, 265. Sidhu, S., Graham, J., and Striebich, R., Chemosphere, 2001,42,681. Taylor, P.H. and Dellinger, B., Environ. Sci. Technol., 1988,22,438. Taylor, P.H., Dellinger, B., and Lee, C. C., Environ. Sci. Technol., 1990,24, 316. Taylor, P.H., Dellinger, B., and Tirey, D. A., Int. J. Chem. Kinet., 1991, 23,1051. Taylor, P.H. and Lenoir, D., Sci. Total Environ., 2001,269,1. Yamada, T. and Taylor, P.H., "Laboratory-Scale Thermal Degradation o f Perfluoroalkyl Sulfonates and Perfluoroalkyl Sulfonamides," Final Report prepared for 3M Co., UDR-TR2002-000153. Trenholm, A., Gorman, P., and Jungelaus, G., Performance Evaluation o f Full-Scale Incineration, MRI Report under EPA Contract 68-02-3177, 1984. 002092 42 Tsang, W. and Shaub, W., Chemical Processes in the Incineration o f Hazardous Materials, Detoxification o fHazardous Wastes, J. Exner, Ed., Ann Arbor, 1982,41. 002093 43 Appendix 1 Timeline and Dates o f Testing 002094 Project Time Line Phase I Phase II Phase in March 2001 - October 2001 February 2002 March 2002 - September 2002 Date 2/1,2/4,2/7,2/15, 2/18,2/19,2/24 3/19-7/29 7/30 8/2 8/8, 8/9 8/19, 8/20 8/23, 8/26 8/27 8/28 8/30 9/3-9/5 9/6 9/18-9/20 Combustion Test Schedule - 2002 Description Standard sample calibration Combustion test system and method development PFOS extraction Heated blank extraction before combustion test FC-1395 combustion test FC-807A combustion test PFOS combustion test Heated blank extraction after combustion test PFOS transfer efficiency test PFOS transfer efficiency test Off-line GC/MS SO2 calibration Non-heated blank extraction PFOS transfer efficiency test 002095 Appendix 2 Sample descriptions and Certificate o f Analysis (C o f A) for PFOS sample) 002096 Appendix Sample descriptions and Certificate of Analysis (C of A) for PFOS sample 3M chemical container descriptions as presented on sample container labels: For PFOS 4x4x11.5 cm (w.xd.xh.) square column shape with 2.2x3.0 cm i.d.xo.d.) circular top made o f clear glass with black screw plastic cap Labeled as: C8F17S03-K+ 98-0211-3916-1 Lot 217 For FC-807A 7.5 cm o.d. x 13.5 cm height circular column shape with 5.2x6.0 cm i.d.xo.d.)circular top made o f clear glass with metal screw cap. Labeled as: Material FC-807A 8681 BC AS Time 11:10 Lot No. 30177 Drum T 1 Step 4 Date 12-22-2K Sampled By C. Senior For FC-1395 7.5 cm o.d. x 17.5 cm height circular column shape with 1.9x2.5 cm (i.d.xo.d.) circular top made of amber glass with black screw plastic cap. Labeled as: Name: FC-1395 Lot #: 90086 Date: 11/7/00 002097 Reference Standard Descriptions: The following was retrieved from 3M Environmental Laboratory's sample tracking systems. The original shipment to Univ o f Dayton during April o f '01 was the following: 20.1 PPM Perfluoro octane sulfonyl fluoride, serial # CC79754 4950 PPM Thionyl fluoride, serial # CC43285 10,049 PPM Sulfuryl fluoride, serial # FF 17680 99.9+% Sulfur dioxide, lecture bottle, 3M barcode E0000002106 002098 Centre Analytical Laboratories. Inc. 3048 Research Drive Phone: (814) 231-8032 State College, PA 16801 Fax: (814) 231-1253 or (814) 231-1580 INTERIM CERTIFICATE OF ANALYSIS Revision 1(9/7/00) Centre Analytical Laboratories COA Reference #: 023-018A 3M Product: PFOS, Lot 217 Reference#: SD-018 ____________ Purity : 86.9% Test Name . Specifications P u rity 1 ; Result 86.9% Appearance White Crystalline Powder Identification NMR Metals (ICP/MS) 1. C alcium 2. M agnesium 3. Sodium 4. Potassium1 5. Nickel 6. Iron 7. M anganese Total % Impurity (NMR) ' v; >- ' . ' Total % Impurity (L C /M S) Total % Impurity (G C /M S) ' .^ ,, A w:*1 v Related Compounds - POAA 'S'"'-.' Residual Solvents (TGA) ", -- ,: r':. Purity by DSC ` Inorganic Anions (IC) 1. C hloride: . 2. Fluoride 3. Bromide * "yr^NP v - r. - 4. N itrate - * 'y%v -. 5. N itrite ' ' . , " * * * r 6. P h o s p h a t e * ; ^ , , *l 7. S u lf a te ^ - 5 * p -- Organic Acids 9 1. t f a 2. PFPA - 3. H F B A ' 4. N F P A ' " ; Elem ental A nalysis'^ 1. C a r b o n - " ' 2. H ydrogen 1. Theoretical V alue = 17.8% 2. Theoretical Value = 0% 3. N itrogen * ' 4. Sulfur 3. Theoretical Value = 0% 4. Theoretical Value = 5.95% 5. Fluorine 5. Theoretical Value = 6 0 % y C onform s Positive 1. 0.005 w t./w t.% 2. 0.001 wt./wt.% 3. 1.439 w t/w t.% 4. 6.849 wt./wt.% 5. <0.001 wt./wt.% 6. 0.005 wt./wt.% 7. <0.001 wt./wt.% 1.93 wt./wt.% 8.41 wt./wt.% None Detected 0.33 wt./wt.% None Detected N o t A pplicable-1 1. <0.015 wt./w t.% 2. 0.59w t./w t.% 3. <0.040 wt./\vt.% 4. <0.009 wt./wt.% 5. <0.006 wt./wt.% 6. <0.007 wt./wt.% 7. 8.76 wt./wt.% 1. <0.1 w t./w t.% 2. <0.1 wt./wt.% 3. 0.10w t./w t.% 4. 0.28 wt./wt.% 1. 12.48 wt./w t.% 2. 0.244 wt./wt.% 3. 1.74w t./w t.% 4. 8.84 vvt./wt.% 5. 54.1 wt./wt.% COA023-0I8A 002009 Page 1 o f 3 Centre Analytical Laboratories. Inc 3048 Research Drive Phone: (814) 231-8032 State College, PA 16801 Fax: (814) 231-1253 or (814) 231-158C INTERIM CERTIFICATE OF ANALYSIS Centre Analytical Laboratories COA Reference #: 023-018A Date o f Last Analysis: 08/31/00 Expiration Date: 08/31/01 Storage Conditions: Frozen <-10C Re-assessment Date: 08/31 /0 1 'Purity = 100% - (sum o f metal impurities, 1.45% +LC/MS impurities, 8.41%+Inorganic Fluoride, 0.59%+NMR impurities, 1.93%+organic acid impurities, 0.38%+POAA, 0.33%) Total impurity from all tests = 13.09% Purity = 100% -13.09% = 86.9% 2Potassium is expected in this salt form and is therefore not considered an impurity. 3Purity by DSC is generally not applicable to materials o f low purity. No endotherm was observed for this sample. 4Sulfur in the sample appears to be converted to SO4 and hence detected using the inorganic anion method conditions. The anion result agrees well with the sulfur determination in the elemental analysis, lending confidence to this interpretation. Based on the results, the SO4 is not considered an impurity. 5TFA HFBA NFPA PFPA Trifluoroacetic acid Heptafluorobutyric acid Nonofluoropentanoic acid Pentafluoropropanoic acid th e o re tic a l value calculations based on the empirical formula, C8F|7S 0 3'K+(MW=538) This work was conducted under EPA Good Laboratory Practice Standards (40 CFR 160). roA n?i-oi8A 0 0 2 1 Q0 Pace 2 of 3 Centre Analytical Laboratories, Inc 3048 Research Drive Phone: (814) 231-8032 State College, PA 16801 Fax: (814) 231-1253 or (814) 231-158C INTERIM CERTIFICATE OF ANALYSIS C entre Analytical Laboratories COA Reference #: 023-018A LC/MS Purity Profile: Im purity C4 C5 C6 C? Total w t./wt % 1.22 1.33 4.72 1.14 8.41 Note: The C4 and C6 values were calculated using the C4 and C6 standard calibration curves, respectively. The C5 value was calculated using the average response factors from the C4 and C6 standard curves. Likewise, the C7 value was calculated using the average response factors from the C6 and C8 standard curves. Prepared By: S ' S /te Y 9 / 7/cV O David S. Bell Date Scientist, Centre ical Laboratories Reviewed By: f //2 John Flaherty " Date Laboratory Manager, Centre Analytical Laboratories COA023-018A 0 0 2 10 1 faee 3 of3 Appendix 3 Phase II Final Report and Raw Data 002102 August 1,2002 3M Phase II Final Report: Laboratory-Scale Thermal Degradation of Perfluoro-octanylsulfonate and C8Perfluoroalkyl Sulfonamides Prepared by: Environmental Sciences and Engineering Group University of Dayton Research Institute Summary Calibration curves and detection limits for SO2, SOF2, SO2F2, POSF, and C3F6 (hexafluoropropene (HFP)) have been established. The transport efficiency through the UDRI thermal instrumentation system for each compound was also examined. This report describes experimental setup, operating procedure, analytical methods and their results. The calibration plots, linear fit equations, detection limits, and transport efficiency are provided in this report. Verification that Cg perfluoroalkyl sulfonates can be gasified and transported through the system will be performed following the completion o f the phase III tests. This decision was made based on the potential contamination of the system had the transport tests been done prior to the phase III combustion study. HFP was selected as the surrogate volatile fluorocarbon due to the lack o f availability o f CF4 and CF3H from gas suppliers. Experimental Setup Six standards (SO2, SOF2, SO2F2, POSF and HFP) were injected through the STDS reactor configuration that will be used for the Phase m combustion test. The same samples were also injected directly into the GC/MS system and compared with the earlier tests to derive the transport efficiency for each material. Figure 1 shows a schematic diagram o f reactor and in-line GC/MS system that was used for the Phase II study. Figure 1. Schematic Diagram of Experimental Setup for the Phase II Study. 002103 August 1,2002 The system consists o f two GCs, the first GC (GC1 in Figure 1) was used to maintain reactor and transfer line at 260C to transport samples efficiently and the second GC (GC2 in Figure 1) was used for sample analysis. The furnace in GC1 was also maintained at a temperature o f 260C. Helium (He) was used as carrier flow and flow was set as 21 1 ml/min using a differential flow controller (Porter Instruments). A flow splitter was installed between reactor and GC column to vent excess gas. A 21 ml/min flow rate was used to define a residence time o f 1 sec in the combustion reactor. The combustion reactor used in this study (and the Phase III combustion test) is 4 mm x 6 mm (i.d.xo.d.) with an effective length o f 5 cm. While the sample was being collected, the switching valve was opened toward exhaust line ((1) position in Figure 1. The valve was then switched to (2) position to pressurize GC column when sample analysis was started. The pressure was maintained at approximately 6 psi during sample analysis and the pressure was monitored using a pressure gauge. The GC/MS system used in Phase II analysis was a Hewlett Packard 5890A/5970B incorporating a DB-5 MS capillary column (30 m length, 0.25 mm i.d., Agilent Technologies, Inc.). All samples were diluted in helium (Research Grade, Air Products, Inc.) to establish calibration curves and detection limits. The amount o f sample injected was 1 ml for gas-phase samples (SO2, SO2F, SO2F2, POSF, and HFP). Measurements were performed in duplicate for each sample and concentration. Operating Procedure C a libration Prior to sample injection, the switching valve was set to (1) position to vent excess gas and the second GC oven (GC2) was held at -60C. After sample injection, the flow was vented for approximately 1 min. to purge the sample from the reactor/transport system. The system was then pressurized by turning the switching valve to the (2) position, and the GC oven temperature programming was started. The GC oven was initially held at -60C for 1 min., heated to 50C at 10C/min. and held for 1 min. The GC was heated to 250C for 10 min after each analysis to flush out any residual material from the column. The MS was auto-tuned with perfluorotributylamine (PFTBA) and operated at EMV (2000V) in the scanning mode sweeping from 45 to 550 AMU. D irect Injection All conditions, GC oven temperature programming, total flow, split ratio, injection port temperature, and column pressure, were set at the same condition that was used for the calibration study. The temperature programming was started immediately after sample injection. 00^104 2 August 1,2002 Results Calibration In most cases, calibrations were made based on four even interval concentrations for each sample. The detection limit was determined using a similar approach to EPA's detection limit criteria for identifying an unknown (Method 8260B page 23 - 24). In our approach, the masses o f the most abundant ions comprised the reference mass spectra. We then chose the most abundant ion (target ion) and major ions whose intensities are greater than ca. 20% o f the target ion. The detection limit was then specified as the lowest concentration that has the target ions and all of the major ions whose relative intensity agrees with the reference spectra within ca. 20%. For example, Figure 19 and 20 in the Appendix illustrate the total ion chromatogram and mass spectra for SO2F2 (10,049 ppm). The m/z = 83 ion is the most abundant ion (target ion) and m/z = 48,67, and 102 are the major ions (m/z will not be shown thereafter). The ions o f 102, 83, 67, and 48 correspond to SO2F2, SO2F, SOF, and SO, respectively and it is reasonable to choose these ions to quantify SO2F2. Figures 24 and 25 in the Appendix show the total ion chromatogram and mass spectra for a concentration o f 20.1 ppm. The mass spectra still contain the target ion and the 3 major ions and their relative abundance agrees with the reference spectra (Fig. 20). Figures 26 and 27 show the total ion chromatogram and mass spectra for a concentration o f 4.0 ppm. The 102 ion is not present at this concentration. Therefore, the detection limit for SO2F2 was determined as 20.1 ppm. Similar analysis was conducted for all of standards and the results are briefly discussed below. Figures 2 to 7 show calibration plots for SO2, SOF2, SO2F2, POSF, PBSF, and HFP, respectively. The linear fit equations for each sample, their linear correlation coefficients (R) and detection limits are tabulated in Table 1. Table 1 Linear Fit Equations and Detection Limits Sample Name S02 SOF2 SO2F2 POSF HFP Linear Fit (Y: peak area, X: concentration (ppm)) Y = 5.8813E3* X - 3.8541E5 Y = 8.3335E3* X - 7.0267E4 Y = 1.0331E4*X+ 1.8273E6 ' Y = 1.0423E5*X - 8.4043E5 Y = 1.4975E4*X - 2.8253E6 R 0.9971 0.99941 0.99708 1.0 0.9997 Detection Limit (ppm) 78.5 30.3 20.1 14.1 3.9 The linear fit for each calibration shows reasonable high correlation coefficients. Because only 2 concentrations could be measured above the detection limit for POSF, the R value is 1.0. Based on the linear fit equation, the detection limit for HFP is 189 ppm. However, the detection limit analysis described above indicates a much smaller value (3.9 ppm). This is due to non-linear GC/MS response throughout the concentration range examined. The concentration range used to obtain the SO2 calibration curve was 1570 to 157 ppm. The detection limit was determined as 78.5 ppm. Figure 10 in the Appendix shows the mass spectra 00210s 3 August 1,2002 for S 0 2 (1570 ppm). The ions o f 48 (SO) and 64 (S 0 2) were chosen as target ion and major ion, respectively. The ion o f 64 was not evident at a concentration o f 15.7 ppm. The detection limit was thus determined as 78.5 ppm. S02 Figure 2. Calibration Plot for S 0 2 The concentration range used to obtain the SOF2 calibration was 3034 to 303.4 ppm. Figure 9 in the Appendix shows the mass spectra for SOF2. The ion o f 67 (SOF) was chosen as target ion and the ions o f 86 (SOF2) and 48 (SO) were chosen as major ions. All ions exist at a concentration o f 30.3 ppm. At 6.1 ppm, there was no GC/MS response to the sample. Therefore, the detection limit was determined as 30.3 ppm. 002106 4 August 1,2002 The concentration range used to obtain SO2F2 calibration was 7034.3 to 100.5 ppm. The detection limit was determined as 20.1 ppm as discussed above. 8 107 : 7 io7- 6 107- 5 107- I 4 107- 3 107- 2 107 - S02F2 y* 1.8273 +06 + 1 I331X u y:= 0.997 yy // y / 1 107- V 0 10-: w 0 1000 2000 T 1 1| 3000 4000 5000 6000 7000 Cone, (ppm) Figure 4. Calibration Plot for SO2F2 8000 The concentrations used to obtain the most accurate POSF calibration were 20.1 and 14.1 ppm. This limited range is due to the low concentration o f the standard provided by 3M and the tight detection limit criteria. Figure 29 in the Appendix shows the mass spectra for POSF (20.1 ppm). The 69 ion (CF3) was chosen as target ion and 67 (SOF), 100,119 (C2F5), 131 (C3F5), and 169 002107 5 August 1,2002 (C3F7) were chosen as the major ions. The 100 and 131 ions were not present at a concentration o f 8 ppm (Fig.33), and the detection limit was determined as 14.1 ppm. POSF Cone, (ppm) Figure 5. Calibration Plot for POSF The concentration range used to obtain the HFP calibration was 10,000 to 1,000 ppm. Figure 44 in the Appendix shows mass spectra for HFP (10,000 ppm). The 69 ion (CF3) was chosen as target ion and 50 (CF2), 81 (C2F3), 100,131 (C3F5), and 150 were chosen as major ions. The ion o f 81 was not present at a concentration o f 1.9 ppm (Fig. 51). The detection limit was thus determined as 3.9 ppm. 002108 6 August 1,2002 Cone, (ppm) Figure 7. Calibration Plot for HFP Transport Efficiency The transport efficiency o f each standard was estimated by comparing the measured sample peak area obtained when the sample was injected into injection port in GC1 and passed through combustion reactor and transfer line (system transport) with that obtained when the sample was injected directly into the injection port o f GC2 (direct injection). Table 2. Transport Efficiency Sample S02 SOF2 SO2F2 POSF HFP System Transport Peak Area 1st 2nd AVG (1) 9130332 8980717 9055525 25244352 25203780 25224066 86850304 85572809 86211557 1280370 1228718 1254544 148679354 145606343 147142849 Direct Injection Peak Area 1st 2nd AVG (2) 11952302 11762267 11857285 24862639 24773683 24818161 84435720 79738316 82087018 1064431 1067947 1066189 148372504 142271896 145322200 Efficiency (%) (l)/(2)xl00 76.4 101.6 105.0 117.7 101.3 The transport efficiencies for SOF2, SO2F2, and HFP were within analytical error. An uncertainty o f 10 % is reasonable for this type o f analysis. That for POSF was slightly higher, but is nonetheless acceptable. That for SO2 was around 76%. The SO2 standard was analyzed as a two-component mixture with SOF2. Since the transport efficiency for SOF2 was nearly 100%, the results indicate some sample losses for SO2 through the reactor and transfer lines. Because SO2 is expected to be one o f the major combustion byproducts, we will repeat the efficiency test 002109 7 August 1,2002 as part o f the Phase IE study. We will estimate a SO2 correction factor based on SO2 efficiency test results to compensate for its measured concentration during the Phase III study. 002110 8 August 1,2002 Appendix (Raw Data for Phase II Report) The total ion chromatograms o f the 6 standards (SO2, SOF2, SO2F2, POSF and hexafluoropropene (HFP)) and the mass spectra corresponding to standard peaks are presented below. Mass spectra are shown for the highest, detection limit, and below detection limit concentrations for each standard. Abundanc* TIC: C L SO F 3 .D Figure 8 . Total Ion Chromatogram for SOF2 (3034 ppm) and SO2 (1570 ppm) Abundance 220000 Scan 3 (0.451 min): CLSOF3.D <-) 6(7 200000 180000 160000 - 140000 : 120000 - 1OOOOO 80000 60000 < 40000 20000 11 i 1 1 . . . 1 1 11 1 1 1111 j i i'n p Hi . | n | i . 111 it t |'i ' i~| 11 ri-pri i u p i*i 1 1i i 11 11 m 111 11 rryr r i'i'i m -i j . m r ,, | n >i ),n i f i n rpr, rp rrp i i i p- 384042444648505254S65860626466687072747678808284868890929496 Figure 9. Mass Spectra for SOF2 (3034 ppm) J 002111 1 August 1,2002 Abundance Figure 10. Mass Spectra for SO2 (1570 ppm) TIC: CLSOF5.D Time--> Figure 11. Total Ion Chromatogram for SOF2 (2124 ppm) and SO2 (1099 ppm) A b undance TIC: C L SO F 7 .Q Figure 12. Total Ion Chromatogram for SOF2 (1214 ppm) and SO2 (628 ppm) 0 0 2 1 i 2 2 A bundance TIC: CLSOF9.D August 1,2002 Time--> Figure 13. Total Ion Chromatogram for SOF2 (303.4 ppm) and SO2 (157 ppm) Abundance TIC: C LSO F12.D Time--> Figure 14. Total Ion Chromatogram for SOF2 (151.7 ppm) and SO2 (78.5 ppm) Figure 15. Mass Spectra for SO2 (78.5 ppm) 3 002113 August 1,2002 Figure 16. Total Ion Chromatogram for SOF2 (30.3 ppm) and SO2 (15.7 ppm) Abundano* 1-4-00 -13 0 0 *1200 1 *1OO -IOOO OOO aoo 700 eoo Soan AO (0.613 min): CLSOF ^00 300 3a 40 A 2 A 4 A e A asoa2S 4sa8aeoe3e4eees70737A 7eT S 808284seaaoooa4 Figure 17. Mass Spectra for SOF2 (30.3 ppm) Figure 18. Mass Spectra for SO2 (15.7 ppm) 4 002114 August 1,2002 Figure 19. Total Ion Chromatogram for SO2F2 (10049 ppm) Abundance Figure 20. Mass Spectra for SO2F2 (10049 ppm) Figure 21. Total Ion Chromatogram for SO2F2 (7034 ppm) 002115 5 August 1,2002 Figure 24. Total Ion Chromatogram for SO2F2 (20.1 ppm) 6 V 021X 6 Abundance 2400 2200 2000 *1800 *1800 1400 1200 1000 - 800 eoo 400 200 - O- Sca n 32 <0.373 min): N C L8P 226.D August 1,2002 96 1OO 106 11O Figure 25. Mass Spectra for SO2F2 (20.1 ppm) 000 seo n 20 <0.220 min): MCL.Sf*230.D 200 ISO 1 00 so OO70727476 TOOC Figure 27. Mass Spectra for SO2F2 (4.0 ppm) 7 002117 Atoundano* August 1,2002 Figure 30. Total Ion Chromatogram for POSF (14.1 ppm) 8 002118 Abundance August 1,2002 Abundance Figure 31. Mass Spectra for POSF (14.1 ppm) TIC: N CLPSF6.D Figure 32. Total Ion Chromatogram for POSF (8.0 ppm) Abundance Figure 33. Mass Spectra for POSF (8.0 ppm) 9 A bundance August 1,2002 Time--> Figure 34. Total Ion Chromatogram for Hexafluoropropene (HFP) (10,000 ppm) Abundance m/z--=> Figure 35. Mass Spectra for HFP (10,000 ppm) Figure 36. Total Ion Chromatogram for HFP (7,000 ppm) 10 002120 August 1,2002 Figure 38. Total Ion Chromatogram for HFP (1,050 ppm) Figure 39. Total Ion Chromatogram for HFP (3.9 ppm) li 002121 Abundance August 1,2002 Figure 40. Mass Spectra for HFP (3.9 ppm) Figure 41. Total Ion Chromatogram for HFP (1.9 ppm) 12 Appendix 4 Phase III Test Protocol and Addendum 0 0 ^ .1 2 3 July 30,2002 Phase III Protocol: Laboratory-Scale Thermal Degradation of Perfluoro-octanylsulfonate and C8Perfluoroalkyl Sulfonamides Prepared by: Environmental Sciences and Engineering Group University of Dayton Research Institute Summary The phase HI study will consist o f 6 separate tests as shown in Figure 1. The main objective of this study is the simulation o f the incineration o f seven fluorocarbon-based samples provided by 3M. Specific attention is being given to the potential formation o f PFOS during the incineration of these materials. In-line and off-line GC/MS analysis, PUF (polyurethane foam) sample collection and condensed phase sample extraction will be conducted. In the latter two tests, the PUF cartridges and the extracts will be delivered to 3M for analysis of PFOS by LC/MS. Prior to the sample combustion analysis, the transfer efficiency for SO2 will be reexamined and the laboratory spike analysis for PFOS will be performed. A heated blank line analysis will be performed at the onset of the sample combustion tests. After the combustion tests, another heated blank line analysis will be performed. Transfer efficiency tests for CgFi7S03'K+ will be performed at the conclusion o f the phase HI study. 1. SO? Transfer Efficiency Tests V 2. Laboratory Spike Analysis for PFOS ___________ z _____________________ 3. Heated Blank Combustion Test 4. Combustion Tests for FC-1395, FC-807A, ____________ and C8F i7S 0 3~K+ 5. Heated Blank Combustion Test (repeat) 6. Transfer Efficiency Test for C8FnS03X + Figure 1. Chronological summary of tests to be conducted during Phase III. 002124 1. S 0 2 Transfer Efficiency Tests In the phase II transfer efficiency test, sulfur dioxide (SO2) showed recovery efficiency o f 76.4 %. The SO2 standard was analyzed as a two-component mixture with SOF2 (thionyl fluoride) and the SOF2 recovery rate was nearly 100%. Therefore, it is quite conceivable that SO2 was absorbed on the surface of reactor and transfer line. We will conduct another analysis to confirm this result and to estimate the recovery coefficient for the calculation o f SO2 concentration from the combustion tests. 2. Laboratory Spike Analysis for PFOS A 1 pg sample will be used for the PFOS spike analysis. This is the amount o f PFOS that would be formed if 0.1% o f the perfluoroalkyl portion o f the fluorochemical products used in this study were converted to PFOS in the reactor. Analysis o f the extracts from these spiked reactor/transport systems will show if this amount of PFOS can be extracted and detected accurately, io mg o f PFOS will be dissolved with 10 ml methanol (Aldrich, HPLC grade) and 1 pi o f solution (containing lp g o f PFOS) will be placed into a reactor (4 m m (i.d.) x 6 m m (o.d.) x 7 cm length) and dried by blowing high purity nitrogen, or bottled dry air over it at a rate that won't blow droplets out the other end. After the drying process, the transfer line will be assembled and extraction will be performed using the same lot o f methanol used to dissolve the samples. The total volume o f entire reactor and transfer line is 1.1 ml as shown in detail below. Total volume of transfer line = 0.2 ml: as measured Reactor volume____________= 0.9 ml: as calculated (0.2 cm x 0.2 cm x 3.14 x 7 cm) Total =1.1 ml The concentration o f PFOS in the spike that is extracted with five times volume of reactor/transfer line (using methanol as the solvent) will be 180 ng/ml. This is 18 times 3M 's estimated detection limit for PFOS (ca. 10 ng/ml). Figure 2 shows a schematic of the PFOS laboratory control spike extraction system. The extraction procedure will be based on the perspective that only the condensation o f PFOS subsequent to the high-temperature combustion stage would be indicative o f likely PFOS release to the environment from actual incineration systems. Thus, the extraction procedure will focus on the high-temperature reactor (downstream o f the highest temperature point) and the reaction product transfer lines between the reactor and the various sample collection systems. The following paragraph describes die analytical extraction procedure. The end of a 1/16" tee will be capped prior to extraction. The total amount o f methanol used will be 5.5 ml, five times the volume o f the reactor/transfer line. The methanol will be stored in 40 ml vials (Wheaton CLEAN-PAK, clear certified with pre-cleaned lined cap) and the vials will be connected to the end o f 1/16" tubing using 1/16" stainless tubing. The other end o f reactor will be connected to another 40 ml vial (Wheaton CLEAN-PAK, clear certified with pre-cleaned lined cap) using 1/8" stainless tubing. Methanol will be slowly injected into the system by pressurizing a methanol reservoir by helium gas flow (2.7ml/min) until all methanol is injected into the system. The initial methanol (5.5 ml) level will be marked on the 40 ml vial prior to 002125 2 collection and will be used for confirming that all o f sample introduced is collected. The extraction will be performed twice for each sample. The collected samples will be secured, labeled, and appropriately packaged for overnight delivery to 3M Environmental Laboratory with one blank vial (40 ml) containing 5.5 ml methanol. He Line --Ia o Flow controller q Vent Methanol Reservoir 1/16 lUbing Reactor 1/8 Tubing (4 X 6mm x 7cm) P Iu g G ~ = i----- 1/16 T Collection Vial Figure 2. Experimental set up for PFOS laboratory control spike tests. 3. Heated Blank Combustion Analysis Before and after the sample combustion tests, a heated blank combustion test will be conducted for a reactor temperature at 600 and 900C to examine system contamination. The sample collection will be performed twice for each temperature (one for the sample collection using polyurethane foam (PUF, (Supelco ORBO PUF Cartridge)) and one for die sample collection using Tedlar sampling bags (0.5L, SKC Inc.). Two GC-MS analyses with different GC columns will be conducted for the heated blank exhaust gas analysis (one with in-line GC-MS analysis and one with off-line GC-MS analysis). After the gas-phase collection and analysis, the reactor will be cut in half and condensed phase product extraction will be performed using the method previously outlined in Section 2. Figure 3 shows the schematic diagram of the experimental setup to conduct in-line GC/MS analysis and PUF sample collection for the heated blank combustion test. It also shows the detailed dimensions of the reactor/transfer line system. For off-line GC/MS analysis, the PUF shown in Figure 3 will be replaced by a Tedlar bag. Compressed air will be delivered both to the pyroprobe chamber and the reactor. The total air flow rate will be 10.3 and 7.6 ml/min (with 0.8 and 0.7 ml/min to the pyroprobe chamber) for reactor temperatures of 600 and 900C, respectively. The residence time in the reactor (4 mm i.d. X 6 mm o.d. X 14 cm length with 8 cm effective length) will be ca. 2.0 s. The determination o f the effective length o f the reactor is discussed in Section 4. The flow rate will be controlled within 10 % error. A majority of the 002126 3 effluent will pass through the PUF cartridge for sample collection and 1 ml/min will be directed into the GC column for in-line analysis. In-line GC-MS Analysis: A HP5890A/5970B series GC-MS with DB-5 MS capillary column (30 m length, 0.25 mm i.d., Agilent Technologies, Inc.) will be used for the phase HI study. The initial temperature of GC2 will be held at -60C and sample will be concentrated at the head of the column for 2 and 2.5 (5%) min for reactor temperature o f 600 and 900C, respectively. During this time period, PUF combustion effluent sample collection will also take place. Two PUF cartridges will be placed in series as shown in Figure 3. After the sample collection, switching valve 1 will be turned to (1) position in Figure 3 to pressurize the GC column. As soon as pressurization begins, the temperature programming o f GC2 will be started. The initial temperature will be held for 1 minute and the temperature will be raised at 10C/min up to 260C. The final temperature will be held for 5 minutes. Also after the switching valve 1 is turned to (1) position for the GC column pressurization, the PUF cartridges will be removed from the system. The PUF cartridges will be secured, labeled, and appropriately packaged for next business day delivery to 3M Environmental Laboratory with one blank PUF. Off-line GC-MS Analysis: After the PUF sampling collection, identical sample collection will be performed using a Tedlar sampling bag. The collected off gas will be sampled within 15 min. o f collection and analyzed using HP5890A/5970B series GC-MS with SPEL-Q PLOT (Porous Layer Open Tubular) column (30 m length, 0.53 mm i.d., SUPELCO). The Tedlar bags will be heated to ca. 50 - 60C to ensure that all o f the sulfur compounds that are soluble in the condensed water vapor present in the bag are partitioned into the gas-phase. This column will capture the light compounds (<C6) that the DB-5 MS capillary column may not effectively retain during in-line gas sampling. The initial temperature will be held at 35C and 1 ml o f sample will be injected using a 1 ml gas-tight syringe. The initial temperature will be held for 1 minute and the temperature will be raised at 15C/min up to 245C. The final temperature will be held for 5 minutes. All o f reactor/transfer line systems including pyroprobe chamber and sample insert probes used in the Phase IE analyses will be appropriately packaged and stored for the future analysis. 002127 4 Figure 3. Experimental setup for heated blank sample analysis and collection. Dimensions of the reactor and transfer lines are also shown in lower drawing. 4. Combustion Tests o f Seven Selected Compounds Combustion tests for the seven selected compounds will be performed after the heated blank analysis. Similar to the heated blank analysis, the sample combustion tests will be conducted for the reactor temperature o f 600 and 900C, and the sample collection will be performed twice for 5 002128 each temperature (one for PUF sample collection and one for the Tedlar bag sample collection). The same analytical tests will be conducted as for the heated blank analyses. After the gas phase analysis and collection, the reactor will be cut in half and extraction of condensed phase products will be performed using the method previously outlined in Section 2 and 3. Figure 4 shows the schematic diagram of the experimental setup to conduct effluent in-line GC/MS analysis and PUF sample collection for the combustion test o f the selected compounds. For off-line GC-MS analysis, the PUF cartridges in Figure 3 will be replaced by a Tedlar bag. A ir and methane (if necessary) will be introduced into the pyroprobe chamber and the reactor to simulate incineration o f the samples. The flow rate o f He and air will be controlled by a flow controller (Porter Flow Instruments, DFC1400) and methane will be introduced using a calibrated syringe pump (KDS101, kdScientific). Because the methane flow rate is very low, it is necessary to use syringe pump to obtain accurate flow rates. The solid and liquid phase samples will be gasified using a pyroprobe (Chemical Data Systems, Model 120) and mixed with air and methane (if necessary) in the pyroprobe chamber. The temperature and the duration time o f ignition will range from 1000 to 1250C and 20 to 40 seconds, respectively, depending on the actual sample being gasified. The gasified mixture will be mixed with the air stream and undergo incineration in the fused silica reactor. A portion o f the effluent (1 ml/min) will be delivered to the GC-MS for product analysis and rest of effluent will be passed through two PUF cartridges for detection of PFOS using LC/MS analysis at 3M environmental laboratories. Further details are provided below. Ventilation Figure 4. Experimental setup for the combustion tests. 6 002129 1. Stoichiometric Reaction Mechanisms o f Seven Samples Based on the elemental formula o f the seven samples provided by 3M, four o f which are normalized by carbon, stoichiometric equations were developed and the amount of necessary oxygen was calculated. The results are tabulated in Table 1. In the development o f the stoichiometric equations, it is assumed that C is converted to CO2, F is converted to HF, N is converted to N2, and S is converted to SO2. Phosphorous and potassium were excluded from the equation since the contribution o f these elements is very small and their effects on the overall stoichiometry are small enough to be safely ignored. Methane is also introduced for hydrogen deficient samples to supply hydrogen to convert F to HF. In that case, additional oxygen was supplied to convert C in methane to CO2. Table 1. Coefficients o f Stoichiometric Combustion o f Selected Samples Atomic Contents o f Samples Sample C H F N O P Stoichiometric Gas Products S K o? CH4 COj H20 HF so2 Nj FC-1395 1 1.01 1.21 0.11 0.26 0 0.06 0 0.98 0.05 1.05 0 1.21 0.06 0.055 FC-807A 1 0.985 1.408 0.14 0.36 0.05 0.08 0 0.968 0.106 1.068 0 1.258 0.08 0.07 PFOS 8 0 17 0 3 0 1 1 11.5 4 12 0 16 10 From the table above, stoichiometric equations can be derived for all o f the samples. 2. Calculation of Necessary Amount of Sample (Equivalent Amount of Fluorine in PFOS) The amount of sample that will be incinerated was calculated to conserve the same amount of fluorine for each sample and is tabulated in Table 2. All samples have the equivalent amount of fluorine that is contained in 0.50 mg o f PFOS. To facilitate calculations, we define a "pseudomolecular weight" to be the sum o f the masses o f the elements in the empirical formulation of each product as given in Table 1. The amount o f air necessary for stoichiometric incineration for each sample was also calculated and is included in Table 2. 002130 7 Table 2. Amount of Sample That Contains Equivalent Amount of Fluorine in ____________________________ 0.5 mg o f PFOS____________________________ Sample Name FC -1395a (Pseudo) Molecular Weight (g) 43.62 Fluorine Fraction by weight 0.527 Mass o f Sample to be incinerated (mg) 0.57(2.19) Amount o f Air for Stoichiometric Incineration (ml) 1.50 FC-807Ab 51.567 0.519 0.58 (2.63) 1.37 PFOS 538 0.600 0.50 1.38 a,b Values in parenthesis will be used for the actual combustion test. See sample amount adjustments. For example, the amount of FC-1395 that contains equivalent amount of fluorine in 0.5 mg of PFOS can be calculated as: 0.5 (mg) x 0.600/527 = 0.57 mg and the amount of air for stoichiometric incineration can be calculated as: 0.57 (mg) x 0.001 (g/mg) / 43.62 (g/mol) x 0.98 (stoichiometric O2) x 0.0821 (atm L/(mol K) x 298 (K) /1 (atm) x 1000 (ml/L) / 0.209 (O2 fraction in air) = 1.50 ml The necessary amount of sample and air for other six compounds can be calculated in a similar manner. 3. Sample Amount Adjustments Since FC-1395 and FC-807A were provided in aqueous solution (water contents o f 74 and 78 % by weight, respectively), the amount of sample to be loaded will be 2.19 and 2.63 mg, respectively. 4. Sample Loading Method FC-1395 and FC-807A, both of which are in aqueous solution, will be placed into a slightly larger sample probe ( 2 x 4 mm (i.d. x o.d.) x 1.5 cm length) and dried with He and moderate heat (less than 100C) before being mounted into the pyroprobe. (The slightly larger sample probe will be used to enhance the drying process.) This process will aid the gasification process by requiring less energy to gasify the active ingredients o f the sample. Thermal gravimetric analysis show that significant amounts of mass are lost for both of these samples at temperatures o f ca. 150 to 160C (see Figure 5 and 6). The ratio o f the mass at ca. 160C to the original mass is an indication o f the mass lost due to water evaporation. The mass o f FC-1395 and 807A before and after this drying process will be measured to confirm that the active ingredients o f the sample are not vaporized prior to insertion in the pyroprobe. CgFi7S03'K+, which is a solid powder, will be placed into the sample probe ( 1 x 2 mm (i.d. x o.d.) x 2 cm length) with small amount o f quartz wool support (0.5 cm in length) in the bottom o f the sample probe. The quartz wool is necessary to hold the materials in place prior to the combustion test. 002131 8 FC-1395 Figure 5. Thermal Gravimetric Analysis (TGA) of FC-1395 FC-807A Figure 6 . Thermal Gravimetric Analysis (TGA) of FC-807A 5. Experimental Flow Rate Setting and Calculations Table 3 and 4 summarize the experimental flow settings at temperatures of 600 and 900C, respectively. The flow rates for He and Air can be controlled within 10 %, and the methane flow rate can be controlled within 5 %. Each compound will be incinerated under high excess air condition ranging from ca. 100 to 450 % excess air. The concentration profile of the gasified sample is not measured directly and assumed to be an average value in the excess air calculations described above. Oxygen and methane-deficient conditions may occur in the reactor during the gasification process for some o f the samples while 002132 9 the pyroprobe is heated to high temperatures (1000 to 1250C) and the volume o f the gas expands by a factor of up to 2.5. In other words, during the gasification process, the flow rate o f the gasified sample to the reactor may be faster than the calculation shown in Tables 3 and 4. The calculations shown in Table 3 and 4 are described below with FC-807A as an example. The calculation can be conducted in a similar manner for the other two compounds. The numbers in Table 3 and 4 are calculated using a spreadsheet program and the numbers are rounded to the appropriate number o f significant digits. Therefore, the calculation may not exactly reproduce the numbers shown in Table 3 and 4. In Table 3, the necessary amount o f CH4 for FC-807A can be calculated as: 0.58 (mg) x 0.001 (g/mg) / 51.6 (g/mol) x 0.106 (stoichiometric CH4 requirement, see Table 1) x 0.0821 (atm L / (mol K) x 298 (K) /1 (atm) x 1000 (ml/L) = 0.03 ml The necessary amount o f CH4 was then doubled to provide an excess o f hydrogen atoms to scavenge fluorine atoms as HF. The CH4 flow rate and sweeping time through the pyroprobe were calculated as shown below: 0.06 (ml) /1.00 (min) = 0.06 (ml/min) The air flow rate to pyroprobe was added to sweep the sample out o f the volume in 1 min. The volume o f pyroprobe is 1.5 ml (0.352 x3.14 (cm2) x 4.5 cm - 0.2 (cm3). The necessary flow rate to sweep the sample out o f the volume at 260C is: 1.5 (ml) /1 (min) x 298 (K) / (260 + 273) (K) = 0.84 ml/min Since 0.06 ml/min o f 0.84 ml/min is provided by CH4, the air flow rate will be 0.84 - 0.06 = 0.78 ml/min. The necessary air flow rate to the reactor for sample combustion can be calculated by the stoichiometric amount o f air for sample and sweeping time: 1.37 (ml) /1 (min) = 1.37 ml/min The stoichiometric combustion ratio o f methane to air is 1:9.57. Therefore the air flow rate to reactor for CH4 combustion can be calculated as: 0.06 ml/min x 9.57 = 0.57 ml/min With the additional air flow rate shown in Table 3, the total gas flow rate is calculated as 10.28 ml/min. The residence time for 0.4 cm i.d. x 8 cm effective length quartz tubing at 600C is calculated as: 002133 10 0.22 x 3.14 x 8 (ml) / [10.28 (ml/min) / 60 (s/min) x (600 + 273) (K) / 298 (K) = 2.00 s. The excess air ratio is the ratio o f additional air to stoichiometric air. For FC-807A, 7.5 ml/min additional air flow will be introduced while 1.94 ml/min is the air flow rate for stoichiometric combustion (sample + CH4). The excess air ratio is calculated as: 7.5 (ml/min) /1 .9 4 (ml/min) x 100 = 387 % 6. Effective Length of Reactor The effective length of the reactor was determined based on measured temperature profiles at 600 and 900C. The temperatures of reactor wall (outside) were measured by thermocouples (Chromel-Alumel Type K, 304 SS Sheath, OMEGA) wrapped with quartz tape to prevent radiation effects from the heater. For the reactor temperature of 600C, the temperature was set at 613C. The effective length o f 8 cm was obtained by allowing a deviation from the desired temperature (600C) by 20C, which is 3.3 % o f desired temperature. The measured temperatures at the center o f the reactor and at a distance o f 1 , 2 , 3 , 4 , and 5 cm from the center are shown in Figure 7. For the reactor temperature o f 900C, temperature was set at 928C. The 8 cm effective length was obtained by allowing a deviation from the desired temperature (900C) by 30C, which is also 3.3 % o f desired temperature. The measured temperatures at the center o f the reactor and at a distance o f 1 , 2 , 3 , 4 , and 5 cm from the center are also shown in Figure 7. e-- 600 C Tit-- 900 C Reactor Temperature Profile Figure 7. Reactor Temperature Profile for 600 and 900C. The profiles are roughly symmetrical about the center of the reactor. 11 0 0 2 1 3 4 7. F.xnerimental Procedure (Gas Phase Sample Analysis and Collection) Helium will be used initially to purge both air and methane lines to the pyroprobe and reactor/transfer line. The experiments start with setting the flow rate o f air and methane and the temperatures of GC1 (260C), furnace (600 or 900C), and the GC2 (-60C). After the temperature is appropriately set, air and methane, if necessary, will be introduced into the pyroprobe, and air will be introduced into the reactor. The exhaust gas will be vented without pressurization by setting the switching valve 1 to (2) position. The pyroprobe will not be mounted initially in the system, instead the top of pyroprobe chamber will be capped. The sample will be carefully loaded into capillary quartz tubing, 1mm (i.d.) x 2mm (o.d.) x 2.0 cm (length) or 2mm (i.d.) x 4mm (o.d.) x 1.5 cm (length), the net weight o f sample measured, and the tubing carefully inserted into the pyroprobe. After the flow rate and temperature are properly set and sample preparation is completed, the system will be held for 1 minutes to allow the flow to stabilize. The cap for the pyroprobe chamber will then be removed and the pyroprobe quickly inserted into its chamber. Immediately afterwards, the pyroprobe will be ignited to gasify the sample. After the appropriate amount o f time to sweep the gasified sample from the pyroprobe chamber (1.2 times o f sweeping time shown in Table 3 and 4), the air flow for the pyroprobe will be maximized (5 ml/min at room temperature, 8.9 ml/min at 260C) and held for 10 s. The switching valve for both the pyroprobe and reactor will then be switched to helium. After approximately 20 sec, switching valve 1 will be turned to (1) position to pressurize the GC column. As soon as the column pressurization is started, GC temperature programming and MS analysis will be started. The temperature programming will be identical to that described in Section 3 (Heated Blank Combustion Test). The PUF cartridges will be also removed from the system. The PUF cartridges will be secured, labeled, and appropriately packaged for next business day delivery to 3M Environmental Laboratory with one blank PUF. The same experiment will be repeated for the sample collection using a Tedlar bag. The sampling method and off-line GC-MS analysis will be identical to the heated blank analysis described in Section 3. Since the same reactor will be repeatedly used for two combustion temperatures, the blank analysis will be performed between each analysis to examine any carryover from the previous analysis. The exhaust gas will be vented to a laboratory hood following each test (as shown in Figure 5) to minimize any cross contamination during Phase III study. 8. Experimental Procedure (Condensed Phase Sample Extraction! After gas-phase and PUF sample collection and analysis are completed, condensed phase sample extraction will be performed. This process will be identical to Section 2 - Laboratory Spike Analysis, as illustrated in Figure 2. The collected samples will be secured, labeled, and appropriately packaged for next business day delivery to 3M Environmental Laboratory with one blank vial (40 ml) containing 5.5 ml methanol. The sample probe (capillary quarts tubing) used for sample loading will be weighed after the combustion test to determine the net amount of sample gasified. 002135 12 5. Transfer E fficiency Test for C8F17 S 0 3`K+ Figure 8 shows schematic diagram o f transfer efficiency test for CgFnSCVK*. The starting materials will be collected using two PUF cartridges in the same manner as described earlier for the combustion tests, however, in these tests, the furnace temperature will be held at 260C. The helium flow rate will be set as 20 ml/min and the temperature in the GC oven will be set as 260C. The sample preparation and loading processes are the same as the combustion off-gas collection. The switching valve, which is originally set to (2) position in Figure 8, will be switched to (1) position just before the pyroprobe/sample insertion. The sample will be collected for two minutes after gasification begins. The collected samples will be secured, labeled, and appropriately packaged for next business day delivery to 3M Environmental Laboratory with one blank PUF. Ventilation Figure 8. Transfer Efficiency Test for CgFnSOa'K4. 6 . Cross Contamination Prevention and Examination Extensive precautions will be applied to minimize any PFOS cross-contamination due to the release of these environmentally persistent materials into the immediate laboratory environment 002136 13 following each combustion test. The effluent exhaust line has been connected to a laboratory hood in KL 112 following the results o f the phase II study to mitigate the release o f PFOS into the immediate laboratory environment associated with the off-line PUF sample collection. Prior to Phase IE study, the laboratory tabletop and STDS combustion apparatus will be completely cleaned using reagent grade methanol and acetone and only the cleaned tabletop will be used for sample preparation and system assembly and disassembly. After the first cleanup o f the desktop, the surface will be wiped using 3M Scotch-Brite High Performance Cloths with HPLC grade methanol that is used for sample extraction. The cloth will be soaked with methanol and squeezed before each wipe test. The wiping methods will follow 3M 's instruction given at previous laboratory wipe test. The wiped cloth will be stored in the I-CHEM 40 ml vial provided by 3M. The vial will be stored outside o f the KL 112 where the Phase E l study will be conducted. The cleaning and wipe tests will be conducted following the completion o f each subsection task and between each sample if the section involved multiple sample analysis. 7. Samples to be sent to 3M The following samples will be sent to 3M Environmental Laboratory for each test shown in Figure 1 excluding test 1. Blanks for PUF, solvent, and wipe test will be included in each shipment whenever these analyses/collection are performed. Next business day delivery will be used for all shipments. Eleven total shipments are scheduled. The contents for each shipment to be delivered are as follows: Test 2 ----- Two extracts (5.5 ml) for each test compound, one solvent blank (5.5 ml), one wipe test, and one wipe test blank Test 3 ----- Two sampled PUF cartridges, one blank PUF cartridge, two extracts (5.5 ml), one solvent blank (5.5ml), two wipe test, and one wipe test blank Test 4 ----- Four sampled PUF cartridges [two for 600C (1st and 2nd collections) and two for 850C (1st and 2nd collections)], one blank PUF, two extracts (5.5 ml) (1st and 2nd), one solvent blank (5.5 ml), two wipe tests, and one wipe test blank Test 5 ----- Two sampled PUF cartridges, one blank PUF cartridge, two extracts (5.5 ml), one solvent blank (5.5ml), two wipe test, and one wipe test blank Test 6 ----- Two sampled PUF cartridges (1st and 2nd) for each test compound, one blank PUF cartridge, two wipe tests, and one wipe test blank 8 . Changes in Original Protocol Three significant changes have been made as the experimental approach has evolved after the original proposed protocol was approved by EPA. They are outlined below. 002137 14 1. Significant changes were made to the sample inlet and gasification system. To satisfy the analytical requirements for PFOS detection by LC/MS analysis by 3M, we determined that relatively large amounts o f sample, 0.5 to several mg, had to be gasified in the actual experiments. This amount o f sample is much larger than initially estimated (ca. 10 to 100 jig) and could not be gasified with the inlet available with the Advanced Thermal/Photolytic Reactor System (ATPRS). Preliminary experiments in phase II also demonstrated that higher gasification temperatures (> 400C) were necessary to rapidly gasify the fluorocarbon-based samples. As such, the System for Thermal Diagnostic Studies (STDS), equipped with a hightemperature pyroprobe that can gasify milligram quantities o f material, is proposed for the phase m combustion tests. The STDS is very similar to the ATPRS with regard to its incineration/ analytical capabilities and is a satisfactory substitute for the ATPRS. 2. In the approved protocol, we had originally planned sample combustion with hydrocarbon fuels (e.g., n-octane) for all o f samples. Subsequently, it was determined that a substitute was need because the liquid hydrocarbon fuels originally proposed require much larger amount of oxygen (air) to obtain stoichiometric oxidation and it is impossible to maintain the residence time o f 2 seconds in the reactor under stoichiometric or excess air environments. Methane has the lowest chemical oxygen demand of any hydrocarbon fuel and is a satisfactory replacement. We propose to use methane as a fuel if the sample is hydrogen deficient and requires hydrogen source to convert F to HF, otherwise fuel will not be introduced to the reactor. 3. In the approved protocol, we also proposed to conduct combustion tests at three temperatures (600,750, and 900C). Preliminary combustion tests with several samples indicates that many combustion byproducts were formed at 600C, but those combustion byproducts were not observed at higher temperature (750 and 900C) and the GC-MS total ion chromatograms for these higher temperatures were very similar. Therefore it is proposed that two temperatures are sufficient to analyze the combustion phenomena o f the selected samples (600 and 900C). 0O 2138 15 November 4,2002 Addenda for Phase III Protocol 9 2 nd Transfer E fficiency Test for C8F i7 S 0 3'K+ (PFOS) In addition to the transfer efficiency tests specified in phase HI protocol, direct transfer efficiency tests where the gasified samples are collected without passing through the combustion reactor will also be performed. Samples will be collected using two PUF cartridges. Extraction of the entire system (pyroprobe chamber and transfer tubing) will be performed using methanol as the solvent. This additional study will provide information concerning how much PFOS is transported from the pyroprobe through the transfer lines to the reactor entrance. The transfer efficiency tests in the phase III protocol address sample transport from the pyroprobe to the combustion reactor exit. Figure 9 shows a schematic diagram o f the direct transfer efficiency test for PFOS. The gasified samples will be collected using two PUF cartridges in the similar maimer as described in Section 5 o f the phase HI protocol. The PUF cartridges will be directly connected to the pyroprobe chamber by 19.5 cm long, 1/8" o.d. Silcosteel tubing (Silcosteel, Restec, Inc.). The GC oven temperature will be held at 260C through the entire analysis. The detailed flow profiles are shown in Table 3. Helium will be used as a carrier gas. The flow will be set as 0.63 ml/min and held for one minute before the sample is inserted and gasified. After the sample is placed in the pyroprobe, the flow will remain at 0.63 ml/min for 94 seconds while the sample is gasified at 1250C for 40 seconds. The flow rate will then be maximized to 4.53 ml/min and held for 30 seconds to purge the sample from the pyroprobe chamber and transfer line. The conditions and operational procedures were determined to simulate gas-phase combustion o f PFOS at 600C. The calculated entire volume is 3.79 ml as shown the detail below: Pyroprobe chamber: (0.35)2 (cm2) x 3.14 x 8 (cm) Transfer line:_______ fO.10812 (cm2l x 3.14 x 19.5 (cm) Total: = 3.08 ml = 0.71 ml 3.79 ml The system will be extracted with methanol using five times the volume o f the pyroprobe and heated transfer lines (19.0 ml). Prior to the extraction, the sample probe and pyroprobe will be removed from the system. The collected samples will be secured, labeled, and appropriately packaged for the delivery to 3M Environmental Laboratory with a methanol solvent blank. 002139 l November 4,2002 Table 3. Flow Rate Profile for Direct Transfer Efficiency Test Time Period Pyroprobe Flow Volume (sec) Rate (ml/min) (ml) 0-60 0.63 0.63 60-85 0.00a 0.00 85 -1 7 9 0.63 0.99 179-189 189-219 0.63 4.53b 4.53 0.43 2.27 Total Volume (ml) 4.32 *No flow due to open system to insert the sample. b Linear increase (approximate) Ventilation Figure 9. Direct Transfer Efficiency Test for PFOS. 002140 2 November 4,2002 10. Additional Extraction Analysis o f Unheated Sample Transport Lines In addition to the extractions specified in the phase III protocol, the unheated sample transport lines downstream of the combustion furnace (switching valve and the transfer line between switching valve and PUF cartridge) will be extracted using methanol. This analysis will be performed for FC-807A and PFOS after the combustion tests at 600C. This analysis will determine if PFOS condensation occurs while the effluent is being collected using ambient temperature PUF sampling cartridges. The method will be similar to other extraction analysis. The measured volume o f the unheated transport line is 0.55 ml. The line will be extracted with methanol using a volume equal to 5 times the transport line volume (2.75 ml). The collected samples will be secured, labeled, and appropriately packaged for the delivery to 3M Environmental Laboratory with a methanol solvent blank. 11. Blank Combustion Analysis U sing Single PUF between 600 and 900C Combustion Test. After combustion tests of the first three samples were completed, we decided to perform another blank combustion analysis using a single PUF after the combustion test at 600C but before the combustion test at 900C for the rest o f the samples (FC-807A and PFOS). The temperature o f the GC oven and reactor will be set at 260 and 600C, respectively. Table 4 shows the flow profile that will be performed for this analysis. Table 4. Flow Rate Profile for PUF Collection (Blank Analysis between 600 and 900C) Time Period Reactor Flow Pyroprobe Flow Rate (sec) Rate (ml/min) (ml/min) Total Flow Rate (ml/min) Volume (ml) 0-120 120-130 130-140 140 - 160 A ir 9.70 9.70 9.70 8.89 (He)b A ir 0.84 0.84 4.63* 4.63 4.53 (He)c 10.54 10.54 -> 14.33 14.33 13.42 21.08 2.07 2.39 4.47 Total Volume (ml) aarL ii near increase (approxim ate). b .,Cc Sn w itcih_ edj t^ o hei _ i l*ium for sw eep 30.01 Air and helium will be used for the sample collection. The flow rate for the reactor and the pyroprobe will be same as the actual combustion test at 600C. Air will flow for 120 seconds and then increased to the maximum flow rate and held for 10 seconds. Air will be replaced by helium to purge all the air from the system for 20 seconds. The collected samples will be secured, labeled, and appropriately packaged for the delivery to 3M Environmental Laboratory with the other PUFs and methanol extractions. 002141 3 November 4,2002 1 2 3 rdj ransfer E fficiency Test for PFOS (Sample in Reactor) Another transfer efficiency test where PFOS is directly placed in the reactor and gasified will also be conducted. This analysis will demonstrate the PFOS transport efficiency of the overall system downstream of the combustion reactor. It will also demonstrate how efficiently the PUFs capture the PFOS that exits the reactor in the vapor/aerosol phase. Figure 10 shows a schematic diagram o f 3rd transfer efficiency test. GC/MS in-line analysis, sample collection using PUF, off-line GC/MS analysis using Tediar bag, and reactor/transfer line, valve extraction using methanol will be performed in this study using air and helium as carrier gases. A detailed analytical procedure follows. 1. PUF collection and in-line GC/MS analysis for PFOS gasification with air. 2. Tediar Bag Collection and off-line GC/MS analysis for PFOS gasification with air. 3. Methanol extraction for PFOS gasification with air. 4. PUF collection and in-line GC/MS analysis for PFOS gasification with He. 5. Tediar Bag Collection and off-line GC/MS analysis for PFOS gasification with He. 6. Methanol extraction for PFOS gasification with He. The sample will be loaded into a sample probe and placed in the middle of the reactor. The gasification temperature will be determined based on the TGAs conducted in the development of the Phase I test protocol. The transfer lines will be heated to 260C and then the reactor will be heated to the appropriate temperature. The reactor temperature will be between 525 and 575C depending on die sample and carrier gas. The temperature will be held for 5 minutes for sample collection and in-line GC/MS analysis. The PUF collection, in-line GC/MS analysis and off-line GC/MS analysis will be performed in the similar manner as described in Section 5 o f the phase III protocol. The flow rate will be set as 10.8 ml/min to maintain the sample retention time in the reactor at approximately 2 seconds. The calculated reactor volume and measured valve/transfer line volume are 1.82 and 0.21 ml, respectively, yielding a total volume o f 2.03 ml. The reactor/transfer line, valve system will be extracted by methanol using a volume equal to 5 times the volume o f the reactor/transfer line, and valve (10.2 ml). Prior to the extraction, sample probe will be removed from the system. The collected samples will be secured, labeled, and appropriately packaged for the delivery to 3M Environmental Laboratory with a methanol solvent blank. 002142 4 November 4,2002 Figure 10. Schematic Diagram of 3rd Transfer Efficiency Test 002143 November 4,2002 13. Sulfur Recovery Analysis Sulfur recovery rate as SO2 using the in-line GC/MS system was not quantitatively repeatable. This was due primarily to the low SO2 peak resolution using the cryogenic focusing method at -60C with a holding time o f ca. 4 min. Because the SO2 peaks using the off-line GC/MS system were much sharper than those observed using in-line GC/MS, we decided to use off-line GC/MS analytical results to quantitatively analyze the sulfur recovery analysis as SO2. This section describes the overall protocol for these tests. 13.1 Calibration Curve Pure sulfur dioxide (Aldrich 99.9+ %) will be diluted to 100,400, 700, 1000 ppm using the Tedlar bag (SKC Inc., 0.5 L) to construct the calibration curve. The column and the GC/MS operating conditions will be same as used for off-line GC/MS analysis of the actual combustion tests. Each concentration will be performed twice and the average will be taken. 13.2 SO2 Transfer Efficiency Analysis Known amount o f SO2 standard will be injected into reactor and collected along with carrier gas (air) flow by 0.5 L Tedlar bag. 1 ml o f collected sample will be injected to off-line GC/MS system and recovery rate will be calculated using the calibration established above. Figure 11 shows the schematic diagram o f SO2 transfer efficiency test. The reactor/transfer line system will be heated at 260C throughout the SO2 transfer efficiency test. Dry air will be used as a carrier flow. The flow rate for the reactor and pyroprobe will be 8.0 and 0.75 ml/min, respectively. After the switching valve is turned to (1) position, 1 ml o f 4.0% concentration SO2 will be injected to the reactor. The sample will be collected for 2.5 min, then the switching valve will be turned to (2) position and the bag will be closed. The sampled bag will be brought to off line GC/MS system and 1 ml of sample will be injected. The total amount of molar number in the Tedlar bag will be calculated based on the calibration curve and the total volume collected. The recovery rate will be estimated based on the total amount o f molar number collected over the total amount o f molar number injected. The test will be conducted twice and the average will be taken. OOP-1HH" 6 November 4,2002 Figure 11. Schematic Diagram of S 0 2 Transfer Efficiency Test 002145 7 Appendix 5 The 3M Analytical Report 002146 A n a ly tica l R e p o rt Analytical Results for the University of Dayton Research Institute Study Titled "Laboratory-Scale Thermal Degradation of Perfluoro-Octanyl Sulfonate and Related Precursors" Combined Laboratory Report for E02-0820, E02-0821, E02-0840, E02-0867, E02-0895, E02-0899, E02-0916 E02-0917, E02-0926, E02-0968, E02-0969, and E02-0971 Testing Laboratory 3M Environmental Technology & Safety Services 3M Environmental Laboratory 2-3E -09 935 Bush Avenue, SL Paul, M N 55106 Laboratory Contact W illiam K. Reagen, P h .b Bldg. 2-3E -09 P .O .B o x 3331 SL Paul, M N 55133-3331 Phone: (651)778-6565 FAX: (651) 778-6176 Requester Eric A . Reiner 3M Environmental Technology & Safety Services Bldg. 2-3E -09 P .O .B o x 3331 S t Paul, MN 55133-3331 002147 Page 1 of 30 3M Environmental Laboratory University of Dayton Incineration Study 1 Introduction Solvent extracts and polyurethane foam (PUF) cartridges (Supelco, ORBOTM-1000, 22mm OD PUF Sampler) were submitted to the 3M Environmental Lab to determine at what levels PFOS was present in the samples generated at the University of Dayton Research Institute, URDI, during the study titled `Laboratory-Scale Thermal Degradation of Perfluoro-Octanyl Sulfonate and Related Precursors*. Sample results presented here were generated at 3M using LC/MS instrumentation to detect and quantitate the PFOS anion (CeF^SCV). Individual study samples and quality control samples are presented in Appendix A, which contains both the measured anion concentrations and the concentration of PFOS uncorrected for purity and the contribution of the potassium cation to the mass used allowing URDI to calculate percent recoveries. The interpretation of results is beyond the scope of this report and will be completed by URDI study personnel and the 3M requester and presented in the URDI final report 2 Sample Receipt Reported samples were received at the 3M Environmental Laboratory from URDI between August 20 and September 23,2002 and analyzed between September 13 and October 8,2002. The samples consisted of methanol extracts and PUF cartridges. All samples were stored at room temperature in sample check-in until analysis. After a sample was analyzed, the remaining extract or sample was stored in a refrigerator at approximately 4aC. Dates of receipt of all samples are documented In the raw data. Samples E02-0899-43014 and E02-0899-43012 were not located with the associated samples in sample check-in. These samples were associated with the extraction blank and first extraction for the second heated blank combustion. There are no results reported for these samples. Three sample containers, l-Chem vials, were received not labeled. It is assumed that these samples correspond to the blank, first and second extraction samples (E02-0840-42716, E020840-42714, and E02-0840-42715) for the FC-1395 incineration test, since they were received with the other FC-1395 samples. The individual l-Chem vials associated with these samples were consequently labeled as E02-0840-A, B, and C and were identified as such in the raw data and report The wipe samples that arrived with each set of samples were not analyzed but are retained for possible future analysis. All study samples collected but not analyzed will be retained until permission is provided by the requester to discard them in an appropriate manner. 3 Holding Times Holding times for analysis were not assigned prior to sample receipt Sampling dates, receipt dates and analysis dates are all documented in the raw data. It is not expected that sample storage conditions at the laboratory would contribute to analyte degradation, especially since study samples were subjected to the thermal degradation study conditions. It is also expected that the fluorochemicals measured are stable in methanol over the time period of this study. Q Q 2 3 . 4 8 Page 2 o f30 3M Environmental Laboratory University of Dayton Incineration Study 4 Methods - Analytical and Preparatory Preparatory and analytical methods were not validated for this project but are processed with quality control spikes and blanks to assess method performance. For this project, methanol extracts and polyurethane foam (PUF) cartridges were analyzed via LC/MS. Most of the methanol extracts did not require any further preparation prior to analysis. However, some extracts did require a simple dilution in methanol prior to analysis. These samples (extracts and dilutions) were aliquoted into sample vials and analyzed. The PUF samples, lab control blanks, and lab control spikes required extraction prior to analysis. In summary, the PUF was extracted by removing the large plastic endcap at the wide end of the cartridge and pushing the PUF with a dean disposable glass pipette until the top was approximately halfway down the cartridge. Then twenty milliliters of methanol was added to the PUF in the cartridge. The large plastic endcap was replaced and the cartridge was vortex mixed for at least fifteen seconds and then inverted five times to ensure proper mixing. Then the sample was allowed to sit for fifteen minutes to allow for desorption of the analytes of interest After fifteen minutes, the sample was drained and washed again with the same twenty milliliters an additional four times for a total of five washes. After the fifth wash, the methanol was collected and aliquoted into a sample vial for analysis via LC/MS. Analysis of samples was conducted based on ETS-8-155.1 "Analysis of Waste Stream, Water Extracts or Other Systems Using HPLC-Electrospray/Mass Spectrometry." This method is not written specifically for the extraction of PUF cartridges, just for the analysis of the analytes of interest via LC/MS. The method was modified (documented as deviations) to strengthen the data quality for these analyses by the following: standard curves are to be injected only prior to the samples, CCVs are injected at least every ten samples, the coefficient of determination is to be greater than 0.990, CCVs must be within 25%, the system suitability must be <5.0% relative standard deviation (RSD) for area counts and <2.5% RSD for retention times, and the standards should be within 25% (lower limit of quantitation (LLOQ) 30%) of their true value. Any deviations from this method are discussed in section 5 ofthis report. Samples were analyzed on an Agilent 1100 Series LC/MSD in the negative ion mode. Approximate instrument conditions are presented below. Actual conditions are documented in the raw data. LC CONDITIONS: Column Flow: Injection Volume: Column Temperature: Column: Column Size: 0.300 ml/min 3-5 pL 30C Betasil C18 2x50 mm, 5 p Solvent A: Solvent B: Gradient 2 mM Ammonium Acetate Methanol Time 0.00 0.50 3.00 5.50 6.00 9.00 %A %B 85 15 85 15 0 100 0 100 85 15 85 15 002149 Page 3 o f30 3M Environmental Laboratory MS CONDITIONS: Mode: SIM Polarity: Negative V Cap: 4000 V PFOS SIM Ion: 499 University of Dayton Incineration Study 5 Analysis 5.1 C alibration Calibrations curves were constructed using at least five concentrations with quadratic fitting. All coefficients of determination were greater than 0.990 and all calibration standards used in the calibration curves were within 25%, the LOQ within 30%. Calibration standards outside this range that were excluded are documented in the raw data along with technical justification for deactivation of curve points. Continuing calibration verification standards (CCVs) were analyzed after no more than 10 samples. All CCV recoveries were within 25% as specified by the method. 5.2 System S u itability Out of the ten analytical runs all system suitabilities passed for PFOS except for on 10/04/02. The system suitability was 5.2%, exceeding the 5.0% RSD criterion typically allowed. Since ail calibration curves and CCVs all passed forthis analysis, the data was accepted. 5.3 Blanks All solvent blanks were less than one half the area counts of the lower limit of quantitation with two exceptions. On 9/30/02, a methanol blank contained approximately 9.4 pg/pL of PFOS. This methanol blank was followed by E02-0895-42975 (PFOS-BLK-PUF), which had PFOS levels below the LLOQ (<5.00 pg/pL). Since the next sample following the blank was <LLOQ, this one time occurrence did not affect the data. A blank PUF cartridge was extracted with each set of samples and analyzed. This analysis showed less than one half the area counts of the lower limit of quantitation for each analyte, thus meeting the acceptance criterion for blank sample results. 5.4 Laboratory Control Spikes Laboratory Control Spikes (LCS) consisted of PUF cartridges spiked at known levels of 1 pg and 10 pg were prepared with each set of PUF samples. Each LCS was spiked by removing the large plastic endcap at the wide end of the cartridge and injecting the appropriate amount of spiking solution just below the surface of the PUF. The LCS was allowed to dry for at least 30 minutes before it was extracted as described in section 4 of the report The average PUF LCS recoveries for the 1 pg and 10 pg spikes are 82% and 92% respectively for PFOS. Sample results are not corrected for this recovery information. Summaries of each analysis of the LCSs are presented in Appendix B. 002150 Page 4 of 30 3M Environmental Laboratory University of Dayton Incineration Study 5.5 Sample Calculations Sample Calculation: Final Result(ug) = InstrumentResult (ug/L)x Dilution Factorx Extraction VoIume(L) So for E02-0968-43362 (TE3-EX-PFOS-R-3) Final Result (ug) = 270--- X50x0.0102 L = 138 ug Polyurethane Foam (PUF) Cartridge spike recoveries: __ Instrument Result (ug/L)x 0.02 L . . . Percent Recovery -------------------------- -- ------------ x 100 Spiked Amount (ug) So for 020923LCS-1 (PFOS): 38.2 -- x 0.02 L Percent Recovery = ------- Is------------ xlOO = 76% 1.00 ug 6 Data Summary Individual sample results are presented in appendix A. Each sample is identified with its respective LIMS number and the code that was associated with the sample upon arrival at 3M Environmental Laboratory. Sample results are given as pg/pL (or ng/mL or parts per billion) and in pg (if applicable) for each analyte of interest. Samples that were not detected above the lower limit of quantitation (LLOQ) are reported as less than quantities ("<*) with the numerical value being the LLOQ for the analysis of that particular sample. Laboratory Control Spikes are presented in appendix B and are reported in pg/pL and the percent recovery is given. Averages and standard deviations are only calculated for each spiking level of the Laboratory Control Spikes. Individual samples were not corrected for recovery. 7 Data / Sample Retention The final report and raw data will be retained according to 3M Environmental Lab standard operating procedures. 002151 Page 5 o f30 3M Environmental Laboratory 8 Appendices Appendix A: Individual Sample Results Appendix B: Laboratory Control Spikes Appendix C: Example Chromatograms University of Dayton Incineration Study 002152 Page 6 o f30 3M Environmental Laboratory University of Dayton Incineration Study 9 Signatures S & fa sP A * Millieu* #eofert,fi` S^2H 3 William K. Reagen, Ph.D., Technksl Manager * Date a Kent R. Lindstrom, Senior Research Chemist Date ' 0 0 2 1 .5 3 Page 7 of 30 3M Environmental Laboratory University of Dayton Incineration Study Appendix A: Individual Sam ple Results 002154 Page 8 of 30 3M Environmental Laboratory University of Dayton Incineration Study S am ple E02-0820-42500 HB1-600-1 E02-0820-42502 HB1-900-1 E02-0820-42504 HBl-BLK-PUF E02-0820-42505 HB1-1 E02-0820-42307 HB1-BLK. E02-0821-42519 PFOS1 E02-0821-42520 PFOS2 E02-0840-42708 FC1395-600-1 E02-0840-42709 FC1395-600-2 E02-0840-42710 FC1395-90O-1 E02-0840-42711 FC1395-900-2 E02-084O-427I2 FC1395-BLK-PUF E02-0840-A FC1395 EXTRACT E02-0840-B FC1395 EXTRACT E02-0840-C FC1395 EXTRACT E02-0867-42903 FC807-600-1 E02-0867-42904 FC807-600-2 E02-0867-42905 FC807-69BLK E02-0867-42906 FC807-900-1 E02-0867-42907 FC807-900-2 E02-0867-42908 FC807-BLK-PUF E02-0867-42909 FC807-0 E02-0867-42910 FC807-1 E02-0867-42911 FC807-2 E02-0867-42912 FC807-BLK E02-0895-42970 PFOS-600-1 E02-0895-42971 PFOS-600-2 E02-0895-42972 PFOS-69BLK E02-089-42973 PFOS-900-1 E02-0895-42974 PFOS-900-2 . E02-0895-42975 PFOS-BLK-PUF E02-0895-42976 PFOS-O E02-0895-42977 PFOS-1 E02-0895-42978 PFOS-2 E02-0895-42979 PFOS-BLK E02-0899-43007 602-0899-43009 HB2-600-1 HB2-900-1 E02-0899-430H HB2-BLK-PUF E02-0916-43085 PFOS-TE-1 E02-0916-43086 PFOS-TE-2 E02-0916-43087 TE-BLK E02-0917-43094 PFOS-TE2-I E02-0917-43095 PFOS-TE2-2 E02-0917-43096 TE2-BLK E02-0917-43106 PF0S-TE2X-1 E02-0917-43107 PFOS-TE2X-2 E02-0917-43108 PFOS-TE2X-BLK E02-0926-43141 NHB-1 E02-0926-43142 NHB-2 E02-0926-43143 E02-0968-43360 NHB-BLK PFOS-HE-TE3-1 E02-0968-43361 PFOS-HE-TE3-2 E02-0968-43362 TE3-EX-PFOS-R-3 E02-0968-43363 TE3-EX-PFOS-R-4 E02-0968-43364 TE3-EX-PFOS-V-3 E02-0968-43365 TE3-EX-PFOS-V-4 PFOS* (P*ML) <10.0 <10.0 <10.0 14.9 <10.0 232 401 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 <5.00 25.1 64.0 612 411 9.01 <5.00 25.5 15.4 8.61 6.06 <10.0 <10.0 <10.0 <5.00 <5.00 <5.00 <10.0 <10.0 <10.0 897 <10.0 <10.0 <5.00 <5.00 <5.00 2330 44.0 13530 150 2218 102 PFOS* ( 0 <010 <010 <010 0.082 <015 1.3 012 <0.10 <0.10 <0.10 <0.10 <0.10 <0.028 <0.028 <0.028 <0.10 <0.10 <0.10 <0.10 <0.10 <0.10 <0.014 <0.028 <0.028 <0.028 010 11 0.13 0.086 0.18 <0.10 0.070 0.08S 0.047 0.033 <010 0 .2 0 <010 <0.10 0 .1 0 0 .1 0 010 010 020 17 0 .1 9 0 .1 9 0 .0 2 8 0 .0 2 8 0 .0 2 8 47 0.88 138 11 62 029 pros C o rrected * * ( t) 015 015 015 0.10 0 .6 8 v 1.6 028 0 .1 2 0 .1 2 0 .1 2 0 .1 2 0 .1 2 0 .0 3 5 0 .0 3 5 0 .0 3 5 0 .1 2 0 .1 2 0 .1 2 0 .1 2 0 .1 2 0 .1 2 0 .0 1 7 0 .0 3 5 0 .0 3 5 0 .0 3 5 0.62 1.6 0.16 0.11 012 0 .1 2 0.09 0.11 0.059 0.041 015 015 0 .2 5 0 .1 2 0 .1 2 0 .1 2 015 015 0 .2 5 21 0 .2 4 014 0 .0 3 5 0 .0 3 5 0 .0 3 5 58 1.1 171 1.9 7.7 0.35 002155 Page 9 o f30 3M Environmental Laboratory University of Dayton Incineration Study Sam ple E02-0968-43366 TE3-EX-BLK-2 E02-0968-43370 PFOS-BLK-TE3 E02-0969-43371 PFOS-AIR-TE3-1 E02-0969-43372 PFOS-AIR-TE3-2 E02-0969-43373 TE3-EX-PFOS-R-1 E02-0969-43374 TE3-EX-PFOS-R-2 E02-0969-43375 TE3-EX-PFOS-V-1 E02-0969-43376 TE-EX-PFOS-V-2 E02-0971-43393 TE3-EX-BLK-1 PFOS* (paM L) <10.0 <10.0 997 <10.0 1908 3S.4 696 22.8 <10.0 PFOS* (U) ** <0.20 20 <0.10 19 0.36 1.9 0.064 pros C o rrected * * (n ) * <0.23 23 <0.12 24 0.43 2.4 0.079 PFOS result! a n presented u collected for parity as the anion. ** PFOS is pretested uncorrected for purity and u the potauium sa lt The cocrcctiooi used w n 0.8060 (0.869 purity x 0.9273 correction for poturium ). ** T b ae u m plet i n ju it blanks o f the methanol uied m the study. There ij oo aaodated volume to calculate ug for these nm ples. 002156 Page 10 of 30 3M Environmental Laboratory University of Dayton Incineration Study Appendix B: Laboratory Control Spikes 002157 Page 11 of 30 3M Environmental Laboratory University of Dayton Incineration Study Table 1; 1 ng Laboratory Control Spike Sample PFOS percent (pg/nL) recovery RPD 020913LCS-1 020913LCS-2 020913LCS-1 43.4 87% 4.9% 43.6 91% 45.6 91% 4.0% 020913LCS-2 020923LCS-1 020923LCS-2 020923LCS-1 020923LCS-2 47.4 95% 38.2 76% 14% 44.0 88% 37.1 74% 19% 44.8 90% 020930LCS-1 020930LCS-2 35.3 71% 3.3% 36.5 73% 021001LCS-1 021001LCS-2 34.7 69% 10% 38.4 77% 020927LCS-1 020927LCS-2 Average Standard Deviation RSD 41.5 42.3 41.0 4.27 10% 83% 85% 82% 8.5% 2.0% The true vnhie o fPFOS in the LCS samples it 50.0 pg/uL (1.00 ug) RPEWRelative Percent Difference Table 2:10 ug Laboratory Control Spikes Sample Q20913LCS-3 020913LCS-4 020913LCS-3 020913LCS-4 020923LCS-3 020923LCS-4 020923LCS-3 020923LCS-4 020923LCS-3 020923LCS-4 020923LCS-3 020923LCS-4 Average Standard Deviation RSD PFOS percent (pg/uL) recovery RPD 464 93% 6.8% 497 99% 489 98% 5.9% 519 104% 414 83% 4.6% 433 87% 434 87% 4.3% 453 91% 425 85% 4.6% 445 89% 458 92% 3.7% 476 95% 459 92% 31.6 6.3% 7% The true value o f PFOS in the LCS temples ii 500.0 pg/nL (10.0 ng) 002158 Page 12 of 30 3M Environmental Laboratory University of Dayton Incineration Study Appendix C: Example Chromatograms 002159 Page 13 of 30 3M Environmental Laboratory D ata F i l a i \ \ E t a t a r g e t \ t a r g e t \ c b a a \ i t c h y . i \ I 021004.b\ITCHY0 2 2 .D Pag* 1 R e p o rt D a te : 2 1 -May-2 00 2 0 9 :0 1 3M Environmental L aboratory Data f i l e Lab Bn? I d In j Data O p erato r S ip XaCo M ac Into \ \ E t e t a x g e t \ t a x g e t \ c h e n \ i t c h y . i \ I 021004 .b\ITCBY022 -C 02 001- 07-2 04-OCT-2 0 0 2 1 4 :4 0 c h ria In a t ID: ltd q r .l 50 pg/uL c a lib r a tio n atandard Method i \ \ I t a t a r g o t \ t a r g e t \ c h e e \ i t c h y . i \ I 021004.b \I 021004.a Math D ata : 2 1 -May-a003 0 9 :0 1 i t c h y . 1 Quant Type: EtTD Cal D ata : U4 -OCT-2 002 1 4 :4 0 Cal F i l e : IT 0R 0 2 2 .D Xla b o ttle : 4 C alibration Staple, Level: 4 D ll F acto r: 1.00000 In te g ra to r: Falcon Compound S o b lla t: PFOS.aub Target V eraiun: 4.12 Proceaaing Boat: 919559 c o iO -K - c University of Dayton Incineration Study Page 14 of 30 3M Environmental Laboratory University of Dayton Incineration Study Page 15 o f 30 3M Environmental Laboratory Dae* *11! \\R c * r.a rg n r.\r.a rg R rA c h \ii;c fa y .i\i0 2 0 * 2 (.b \l'n 3 o jy .u v*g 1 RuiiutL O a to i 2 X-Mty-2001 0 i 37 3M E nvironm ental T.ebon*tnry DmUa 11 \ \ B t t * r 9 e t \ t * r g a t \ c b \ l t c b y . l \ X 0202C.b\ITCHY0 39.I> Lab to p I d s MeOR b la n k Znj Data 26- sef-2002 a iia a O perator s k je I n a t IDs itc h y , i Bap I n to i TM-A-4 52 0 Mise In fo t Comment < Method > \ \ B t e t * r g * t \ ta r g e t \ c h e m \ l t e h y .l \ X 02092f . b \ I 0209? 6 .m Math D ate i 2 1 -May>2003 0B t36 a lc h Quant Type KID Cal D ata i 28 -B8F-2 00 2 1 8 :4 5 C al P l i a i ITCW0 2 3 .D A la b o t t l e 82 D ll F acto r: 1.00000 In teg rato rs Falcon Compound O u b li t> PPOO.aub T eruel Vmreioa; 4 .12 P ro c a a a ln g Boats 1V1 PS50 I Ml HIM .M .*1 !.( Mil aiM.V* SIMM QC F lag begaod M - Coopound reapoaae m anually in ta g ra ta d . oc to k -ffh to University of Dayton Incineration Study Page 16 o f 30 3M Environmental Laboratory D ata P i l o t \ \ E t a t a x g o t \ t a r s o t \ c h c a \ i t c h y . l \ I 031004.b\lTCHf0 3 3 .D Pag* 1 Report D atei ll-N ay-2003 o f i U 3N SnvircmaauiLel L aboratory D ata f i l e i \ \ B t a t a x g e t \ t a r g e t \ o h e e \ i t o b y . i \ I 03l 0 0 4 .b\ITtaiY0 3 3 .D Lab S ip I d i KaOH B lank I n j D ata 0 4 -OCT-3 0 0 2 1 4:2 3 O perator t ch rla In a t ID: itch y , i Bap In fo i m -A -4530 Mlec In fo t P n -- >aiwt | Method i \\B ts ta r g e t\ta r g e t\c h a * \itc h y . i \ 1021004.b \I 021004 . a Ma th D ate s 2 1 'K*y>2003 09 i21 i t c h y . i Quant Types BSTD C el D ate t 04 OCT- 2002 1 4 x40 C elF i l e t XTCBT0 2 2 .D A le b o t t l e i 93 D ll F actors 1.00000 In teg rato rs Falcon Compound S u b lie ts PFOS.oub T arget Versions 4.12 P ro c e s s in g Boats W19SS9 SMB(9) 4M 1* .MB Mil Ml IIU.M I1M0S QC F lag Legend M - Cospound response sem uslly in te g ra te d . C . w cao University of Dayton Incineration Study h* VlUUyt a* ^,IMWMt,tMilHlHlt Mr * Page 17 o f 30 3M Environmental Laboratory Dt P i l e : \\K te ta rg e t\te rg e t\n h w n \1 t r J t y . i \ i t m 0Q4 .b\iTCHY0S7 .D Pag Report D ate: 21 Nay 2003 09:32 3N Xnvironnental Laboratory Data f i l e i \\B te ta rg et\ta x g e t\c b ee \itC b y .l\X 0 2 1 0 0 4 .b\XTCBY057.D Lab Bep I d i 020930 BLR In j D sts 04-OCT-2002 20:40 Operator ebria Inst IDi itchy.1 Sap In fo BLANK PUF Mise In fo Coanent Method \\B ts ta rg e e \ta x g o t\c h e n \itc h y .1M0210M .b\loaioo .a Math d a te 31-May-2003 O f|J1 i t c h y .i Quant Typai MXD Cal Data 04-arr-3002 lCtCO Cal F ilo : ITQROaa.D Ala b o t t l e i Cl D ll F a c to rt 1.00000 In teg ra to ri Falcon Coavound S u b itati PPOS.sub Target Version: 4.13 Prnnaaslng Boati W19SS9 WT BP n M.Vtr *.UI .M l M i l QC Plag Legend M Compound reaponee Manually in te g ra te d . M.n iMM o o > -tY University o f Dayton Incineration Study 9m i Page 18 o f 30 3M Environmental Laboratory Data P ilo t \\B tatar9O t\tar9Q t\ohaa\itcby.i\I021002.b\lTC H Y 050.D Pag 1 K tport Date: 21-May-2003 10:04 IN Environmental la b o ra to ry Date f i l e \\B te ta rg e t\ta x g a t\c h e m \itc h y . i\X021002 . b\ITCHT050 .D Lab sap Id i 102-00*7*42903 I n j Date i 03-OCT-2002 0 0 t20 Operator j kje Znet IDt Itchy, i Sap In to i FC007-SQO-1 Miee Info i Co--on t t Method t \ \B t s t a r g e t \ ta r 9 e t\c h em \ltch y . i\I021002. b\I021002. a Meth Date t 21~Nay-2a0309t42 e ic h Quant Types BS1D Cal Date 1 02-OCT-2002 1947 CalP ilc iITCBT024.D Ale b o ttle s IS D il P acto n 1.00000 In teg ra to r: Falcon Compound Bubliats PPOO.eub Target Veraloo: 4.12 Proceeaing Boat* V19S59 9mn kid m .w> <it i.k i QC Flag Legend M - Compound reeponoe manually In te g ra te d . mv tan. iim m C o N H a VL University o f Dayton Incineration Study i ma<*> Page 19 o f 30 3M Environmental Laboratory Data F ila i \\S tatargat\tarpet\cheni\ltchy.l\I021003.b\nC K T 0i2.D Paga 1 Report Datai 21-May-2003 10i04 3M Environment a l la b o ra to ry Data f i l a i \ \R ta tn r g e t\ta r g e t\c h a a \itc b y .i\I021002. b\lTCUY0S2.D la b Bop Id i B02-0940*42711 I n ) Data I 03-OCT-2002 02t27 Operator i kja In e t IDi Itc h y .1 Sap In fo FC1395-900-2 Miao In fo Comaant : Method I \\K C s ta rg a t\ta rg a t\c h a a \ltc h y .l\I0 2 1002.b\I021002.m Hath Data i 21 May 200309i42 Oicb Quant Typai KID Cal Date I 02-OCT-2002 1947 CalF ila ilTOnTO24.D M a b o t tl a i 42 D ll F aeton 1.00000 In teg rato ri Falcon Compound s u b ita ti PPUS.aub Target Versioni 4.12 Processing Hoati N19bb9 I m a (IH IH I.UI i .u i aia QC Flag Legend M - Compound raaponaa manually In te g ra te d . M l MI.O 1MHM cc to O University of Dayton Incineration Study i pm<> Page 20 o f 30 3M Environmental Laboratory Data P ilo t \\B ta ta ig o t\ta rg c t\a h e ia \itc h y .i\X021002 .b\ITCKYO<l.D Pago 1 fteport Datoi 21-May-2001 I0t04 3M Snyiroonental U b o n t o r y Otba 11 t \ \ 8 U t* n t\C X M t\cb B \ltctay . l\X 0a i 002 .to\I1CHT0C3 ,D Lab f i n Ids B02-0M0-42710 In l Oat 03-OCT-2002 02t37 Operator Xnat ID: Itchy, i tap Info 1385-800-1 Mlac In fo Oooocnc Method \\Btataxgat\taxgttt\vfciu*\ituliy.i\X 021002 .b \i021002 .n Nath Data 21-May-2003 08t42 aioh Quutt Typai I8TD c a l Data 02 OCT 2002 15i47 Cal Pile* ITCHT024.D Ala b o ttle s 43 D ll PicfcOTi 1.00000 Intag rato ri Palcon Coapouad B ubliatt PPOB.oub Target Veraion: 4.12 Procaaaing Boat: *15559 v mu >.Qt .11 OC Flag legend M - coapouad reeponee Manually integxatad. nau> tm to * cc University o f Dayton Incineration Study 4t 14; Page 21 o f 30 3M Environmental Laboratory Data F ile ; \\if te ta x g e t\ta rg a t\c h e \d u d e jr. i\D020924 bNPODBOOlO.D Faga 1 Report Data* 2l*Niy*200J 0 9 14$ 1M Environmental L aboratory Data f i l a t \\Btatarget\terget\che*\dudejr.l\D020924.b\D UD80030.D Lab 8ap Id* B02-09M-43360 In j Data I 24-8BF-2002 19i50 Operator t kja Jnat IDi d u d a jr.l Sap In fo i PFOS-HB-TE3~l 50DF Nlae In fo i Coanaat i Method i \\B ta ta z g e t\ta rg e t\c h e \d u d e jr. 1\D020924.b\t>020924. Math Data i 21-May-2003 09i47 a ic h Quant Types B8TD Cal Date i 24-SKP-2002 iv is s Cal F ile t DODB0024.D Ala b o ttle ; 2 1 Dll Factori 1.00000 In teg rato r; Falcon Compound B ubliati PFOS.eub Target Veralont 4 .1 2 Proceaeing Boat; N19559 i not ion .MS i .m MU .Ml ri.MN W.OI C O 05 00 University of Dayton Incineration Study Page 22 o f 30 3M Environmental Laboratory Data F i l e : \\B ta ta r g e t\ta r g e t\c h m \ltc h y .l\I 0 2 0 9 2 f .b\XTC9Y027.D Paga 1 Report Dotot 21-Hay-2003 0i37 3N Rnv1roowonto1 L aboratory Dato f i lo < \\ltat*rget\target\che\ltchy.i\l02092fi.b\IT O IY 027.1 Lob Sop IdI B02-0S95-42979 Xnj Doto t 2C-MP-2002 19*27 Operator * kje loot 10 itafay.i Sop In fo s PrOS-BLK Mioc In fo t r o o f nr j Method 1 \\B te tm rg e t\targ e t\c h em \lto h y .i\I0 2 0 2 .b \I0 2 0 2 6 . Math Data i 21-May-200309ilC a ie h Quant Typet HID Cal Data i 2C-OP-2002 I I I CalF ila iITCW023.D Ala b o t tl a i 21 Dii F aeton 1.00000 In teg rato rI Falcon Goapound S u b ita ti PFOS.aub Targai. Varalo: 4.12 Procaaaing Boati W19559 University of Dayton Incineration Study mu n u t s> me** > i .m mum.imidiwpa Page 23 o f 30 3M Environmental Laboratory Data F il e : \\B te ta rg e t\ta rg a t\c h o a \ltc h y .i\I0 2 0 9 2 (-b \[T C lft0 4 7 .D Pag* 1 Report D atai 21-May-2003 09:17 IN Bnrlronmantal Laboratory Data f i l e \\K ta ta r g e t\ta r g e t\c h e \ltc h y . 1\I020924. b\ITCHT047.D Lab Sap Id : B02-00C7-43912 la ) Date t 2-atP-3002 2 2 isa Operator kja In s t ID: Itchy. 1 s i p in fo yCBOy-Hm Hiao in fo HaUacxl \\B L H L aruaL \L axgaL \dw aiM tuhy.l\I020926.b\102092S .ai Nath Data 2 1 -Hay-lOOl 09i3C a lc b Quant Type: KID Cal Data 24-0BF-2Q02 10:45 Cal F il e : XTOH023.D Ala D ll b o ttle : Factori 317.00000 In teg rato ri Falcon Ooopound B ubliat: PFOS.aub Target Voreloni 4.12 Frocasalng Hoati N195S9 1 PMM(Wj ir 4.llt 4.A1 QC Flag Lagand M - Compound raapona* manually iata g ra c o d . MMI 1MSI mi.M atMM cc 10 o University o f Dayton Incineration Study Page 24 o f 30 3M Environmental Laboratory DC* M ie i \\R tatarg et\targ et\ch ea\d u d eJr.i\D 0 2 0 2 5 A .b \D (n o o a9 .D Paga 1 Report Datai 21-May-2003 O lisi 3N Environmental Laboratory Data f i la i \\Btatargat\target\ahen\cludejr.i\D02092&A.b\DUDB0029.D Lab 8af> Id i B02-0968-43364 in i Data i 2b-6-20 0 2 14tJb Operator t kja Znat IO: d u d a jr.l San Info i TR3-RX-PF08-V-3 SODF Miao Info i Method \\Etetarget\target\chM \dudejr.i\D020925A.b\D020925a.m Nath Data 21-May-2003 09i9 e ic h Quant Typai B8TD Cal Data 25-80-2002 13iM Cal F il t DUDB0025.D Ala b o ttle . 3_1_ D ll Factors 1.00000 In teg rato r: Falcon Compound Oublit i PFOS.aub Targot Varaloni 9.12 Proccaalng Hoot: W.9SS9 *t.m1M .MS uh Co -4- M* Ftloi University o f Dayton Incineration Study llll.lf lllll.l Page 25 o f 30 3M Environmental Laboratory Data F ila t \\Etstarget\taxget\chea\dudejr.l\D020925A.b\DUDB0039.D mar. 1 Report D atei 21-May-2003 0 ) :53 1 M Rnv1ronmental Laboratory Data f i l e Lab Sap Id InJ Date operator Sip Info Mlac Info \\Btataiget\target\cheB\diida1r.l\D020925A.b\DDDB0019.D E02-09C9-433C2 25-8BP-2002 l i 07 Xnet iDi d u d e jr.l TB3-KX-PFOS-R-3 SODF Method \\Etetargat\targat\ehae\dudaJr.l\D020925A.b\D 020925a.a Math Data -May-2003 09:49 e lc h Quant Type: BSTD Cal Date Ale b o ttle Dll Factor 23105.0-0S0B0I0-2002 13:5 Cal V ile: EUX0025.D In teg rato r Faloon Coapound S u b lia t: FFOB.eub Target Veraion: 4.12 Froceealng Boat: M19559 m i.aaa .as* i . m immct an C O P a University o f Dayton Incineration Study ira wi Page 26 o f 30 3M Environmental Laboratoiy Unta P li a i \\B tatarg at\taru et\ch eii\itch y .i\II> 2 0 9 2 * .b \IC H 7 0 2 e.D Faga 1 Ruport D atct 21-May-2901 09:37 JH Rnvironuanhal ta b o ra to ry DaLa f i l a \\B ta ta x g a t\ta rg a t\c h a a \lte b y .l\l0 2 0 9 2 0 .b \IT a ix 0 2 a .l la b Sap ld i 802-0993-42979 Inj Date oparator 2MSa-SBP-2002 19>39 In at ID: itc h y .i 8^> In fo PFOS-2 Mlac la fo Ooanant Hathod i \\B tatar9ut\taxgat\cham \ltchy.i\i02092C .b\I02092C .a Meth Data : 21-May-2003 0 9 ilc a ic b Quant Typoi BtlD Cal Data I 24-HKP-2002 19i5 Cal F ile : ITCHT023.D Ma b o ttla i 22 DU F aet n 1.00000 Xntagrator: Palean Coapound p u b li tt PPOS.aub Targat Vara loin 4.12 Proceaaing Hoatt N19SS9 University o f Dayton Incineration Study Page 27 o f 30 3M Environmental Laboratory Oat F il e : \\B totxgat\targat\cbe*\ltcby.l\X 020a26.b\IT C IiX 049.U Page l JLeport D atai 21-May-2003 0937 3M Bnviroomental L aboratory Data f i l a : \\B ta ta rg a t\ta rg a t\c h a a \ltc h y .l\X 0 2 0 9 2 6 b\!TCHY049.D Lab 8ap Id* B02-0I67-42910 In j Dato i 26-819-2002 2 3 :1 9 O parator i Jeja Xnot XDi itc b y .i d a p Zafo i PCS07-1 Mioc In fo i donnant : Mathod i \\B tetaraat\targ at\ch aM \itcA y .l\I0 2 0 9 2 .t> \I0 2 0 9 3 .n Math Data r21-Hay-20030 ) t ) ( lch Quant Typai OTO Cal Unta i 2S-BKP-20021* i4S Cal F ila i ITOEY023 .D Ala b o t tl a i 39 ol raet o n 1.00000 In tag rato n ralen Coagnund 6u b lia ti PPOG.aub Targat Varaioo: 4.12 Procaaaing HOati M195S9 1 M I MIM m l.M .M I . ! QC Plag Legand M - Coapound raaponaa Manually in ta g ra ta d . M tn IM .M NMM University o f Dayton Incineration Study sw rktot v a u f i r i r iix^ j w ii^ M iw u M iq u MM t Page 28 o f 30 3M Environmental Laboratory Data M ia i \\KLnr.aTgnt\targat\che\dudejr.l\D020924.b\SQDS0037.D Paga 1 PepOrL DuLOl 21 Huy 2003 OOlSC 3M I n v l z u a u t i l la b o ra to ry Data I lio I W ststa ig o t M argot\chon\dudejr.i\D020924.b\DUDK0037.D Lab Sap Idi >02-0909-43373 Inj Data i 24-SBP-2002 2 0il2 Operator kja In st IDi d u d sjr.l s ip In fo : rK3-BX-PF08-R-l 50DF Mise In to I Coaaaant i Method I \\S ts ta rg a t\ta x g e t\c h a a \d u d a j r . i\D020924 .b\D020924. a Hath Data i 21-Nay-2003 09147 e lc h Quant Typei s tio Cal Date : 24-SSP-2002 17:55 Cal F ile t DUES0024.D Ala b o t tl e I at u i l PaotorI i.ooooo Integratori Falcon Compound S u b ite ti PPOS.sub Target Versioni 4.12 Processing HoeLi W19S59 MM Is/MI ImMI 4.Ml MS HUH NISI Ml University o f Dayton Incineration Study Page 29 o f 30 3M Environmental Laboratory D a F il a i \\B tB tax g at\tax g et\ch aa\d u d o lr.i\D 0 3 0 9 2 4 ,b\DUDB0030.D Page 1 Report Datai 21-Hay-300] 09.56 IN Buvironwantal Laboratory Data Clio I \\Btataxgat\target\chaai\dudejr.l\DO20924.b\DODIOOie.D Lab Sap Id i 02-09(9-4117 In} Data 24-SSP-2002 20.23 Operator i I n a t IDt d u d ijr . 1 Sap In fo i t-EI-PPOS-V-2 Mise In to i Co-- ant i Mathod i . i\D020924 .UD020924. m Nath Data i 21-May-a03 09:47 loh Quant Typai HID Cal Data 24-6BP-2002 17:55 Cal F ila : DUH0024.D Ala b o ttin i Dll Faeton 217.00000 In teg rato ri Falcon Compound S u b llo ti PPOB.oub Targat Varalon: 4.12 Procaaalng Hoad W19SS9 cc N K o University o f Dayton Incineration Study at* n u t SMttrtwp >\trta r J HIMl.l> ,! Page30of30 Appendix 6 Spreadsheet Linking the UDRI Combustion Tests with the 3M Analytical Results 00^177 Spreadsheet linking UDRI Thermal Testing and 3M Analytical Results 3M Sample Number E02-0821-42516 E02-0821-42517 E02-0821-42518 E02-0821-42519 E02-0821-42520 E02-0821-42523 E02-0821-42524 E02-0821-42525 E02-0820-42500 E02-0820-42501 E02-0820-42502 E02-0820-42503 E02-0820-42504 E02-0820-42505 E02-0820-42506 E02-0820-42507 E02-0820-42508 E02-0820-42509 E02-0820-42510 E02-0840-42708 E02-0840-42709 E02-0840-42710 E02-0840-42711 E02-0840-42712 E02-0840-42714 E02-0840-42715 E02-0840-427I6 E02-0840-42717 E02-0840-42718 E02-0840-42719 E02-0867-42903 E02-0867-42904 E02-0867-42905 E02-0867-42906 E02-0867-42907 E02-0867-42908 E02-0867-42909 MS-0867-42910 -0867-42911 to Date Sampled 7/30/2002 7/30/2002 7/30/2002 7/30/2002 7/30/2002 7/30/2002 7/30/2002 7/30/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/9/2002 8/9/2002 8/9/2002 8/9/2002 8/9/2002 8/9/2002 8/9/2002 8/9/2002 8/9/2002 8/9/2002 8/9/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 UDRI Sample Description WT-DT-1 WT-BT-1 WT-BLK.-1 PFOS 1 PFOS 2 PFS - BLK WT-BT-2 WT-BLK-2 HB1-600-1 HB1-600-2 HB1-900-1 HB 1-900-2 HB1-BLK-PUF HB1-1 HB1-2 HB1-BLK. WT-BT-3 WT-DT-3 WT-BLK-3 FC1395-600-1 FC1395-600-2 FC1395-900-1 FC1395-900-2 FC1395-BLK-PUF FC1395-1 FC 1395-2 FC1395-BLK WT-BT-4-3 WT-DT-4-3 WT-BLK.-4-3 FC807-600-1 FC807-600-2 FC807-69BLK FC807-900-1 FC807-900-2 FC807-BLK-PUF FC807-0 FC807-1 FC807-2 Test* 5.2 5.2 5.2 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.4.2 5.4.2 5.4.2 5.4.2 5.4.2 5.4.2 5.4.2 5.4.2 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 Detailed Sample Description Desktop wipe test before Test 2 Bench top wipe test before Test 2 Wipe test blank for before Test 2 1st extraction of PFOS spike 2nd extraction of PFOS spike Solvent Blank for PFOS and PFBS extractions Bench top wipe test after Test 2 Wipe test blank for after Test 2 1st PUF for heated blank Combustion at 600C 2nd PUF for heated blank Combustion at 600C 1st PUF for heated blank Combustion at 900C 2nd PUF for heated blank Combustion at 900C PUF blank for heated blank Combustion 1st extraction for heated blank Combustion 2nd extraction for heated blank Combustion Extraction blank for heated blank Combustion Wipe test for bench top after heated blank Combustion Wipe test for desktop after heated blank Combustion Wipe test blank after heated blank Combustion 1st PUF for FC-1395 Combustion at 600C 2nd PUF for FC-1395 Combustion at 600C 1st PUF for FC-1395 Combustion at 900C 2nd PUF for FC-1395 Combustion at 900C PUF blank for FC-1395 Combustion 1st extraction for FC-1395 Combustion 2nd extraction for FC-1395 Combustion Extraction blank for FC-1395 Combustion Wipe test for bench top after FC-1395 Combustion Wipe test for desktop after FC-1395 Combustion Wipe test blank after FC-1395 Combustion 1st PUF for FC-807 Combustion at 600C 2nd PUF for FC-807 Combustion at 600C Blank Combustion between 600 and 900C 1st PUF for FC-807 Combustion at 900C 2nd PUF for FC-807 Combustion at 900C PUF blank for FC-807 Combustion Valve and Extended Tubing Extraction after 600C FC-807 Combustion 1st extraction for FC-807 Combustion 2nd extraction for FC-807 Combustion 05 Spreadsheet linking UDRI Thermal Testing and 3M Analytical Results E02-0867-42912 E02-0867-42913 E02-0867-42914 E02-0867-42915 E02-0895-42970 E02-0895-42971 E02-0895-42972 E02-0895-42973 E02-0895-42974 E02-0895-42975 E02-0895-42976 E02-0895-42977 E02-0895-42978 E02-0895-42979 E02-0895-42980 E02-0895-42981 E02-0895-42982 E02-0899-43007 E02-0899-43008 E02-0899-43009 E02-0899-43010 E02-0899-43011 E02-0899-43012 E02-0899-43013 E02-0899-43014 E02-0899-43015 E02-0899-43016 E02-0899-43017 E02-0916-43085 E02-0916-43086 E02-0916-43087 E02-0916-43088 E02-0916-43089 E02-0917-43094 E02-0917-43095 E02-0917-43096 E02-0917-43097 E02-0917-43098 E02-0917-43099 E02-0917-43106 E02-0917-43107 E02-0917-43108 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/26/2002 8/26/2002 8/26/2002 8/26/2002 8/26/2002 8/26/2002 8/26/2002 8/26/2002 8/26/2002 8/26/2002 8/26/2002 8/26/2002 8/26/2002 8/27/2002 8/27/2002 8/27/2002 8/27/2002 8/27/2002 8/27/2002 8/27/2002 8/27/2002 8/27/2002 8/27/2002 8/27/2002 8/28/2002 8/28/2002 8/28/2002 8/28/2002 8/28/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 FC807-BLK WT-BT-4-4 WT-DT-4-4 WT-BLK.-4-4 PFOS-600-1 PFOS-600-2 PFOS-69BLK. PFOS-900-1 PFOS-900-2 PFOS-BLK-PUF PFOS-O PFOS-1 PFOS-2 PFOS-BLK WT-BT-4-7 WT-DT-4-7 WT-BLK-4-7 HB2-600-1 HB2-600-2 HB2-900-1 HB2-900-2 HB2-BLK.-PUF HB2-1 HB2-2 HB2-BLK WT-BT-HB2 WT-DT-HB2 WT-BLK-HB2 PFOS-TE-1 PFOS-TE-2 TE-BLK WT-DT-6 WT-BLK-6 PFOS-TE2-1 PFOS-TE2-2 TE2-BLK. WT-BT-TE2 WT-DT-TE2 WT-BLK.-TE2 PFOS-TE2X-1 PFOS-TE2X-2 PFOS-TE2X-BLK 5.4.3 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.6.1 5.6.1 5.6.1 5.6.1 5.6.1 5.6.2 5.6.2 5.6.2 5.6.2 5.6.2 5.6.2 5.6.2 5.6.2 5.6.2 Extraction blank for FC-807 Combustion Wipe test for bench top after FC-807 Combustion Wipe test for desktop after FC-807 Combustion Wipe test blank after FC-807 Combustion 1st PUF for PFOS Combustion at 600C 2nd PUF for PFOS Combustion at 600C Blank Combustion between 600 and 900C 1st PUF for PFOS Combustion at 900C 2nd PUF for PFOS Combustion at 900C PUF blank for PFOS Combustion Valve and Extended Tubing Extraction after 600C PFOS Combustion 1st extraction for PFOS Combustion 2nd extraction for PFOS Combustion Extraction blank for PFOS Combustion Wipe test for bench top after PFOS Combustion Wipe test for desktop after PFOS Combustion Wipe test blank after PFOS Combustion 1st PUF for 2nd heated blank Combustion at 600C 2nd PUF for 2nd heated blank Combustion at 600C 1st PUF for 2nd heated blank Combustion at 900C 2nd PUF for 2nd heated blank Combustion at 900C PUF blank for 2nd heated blank Combustion 1st extraction for 2nd heated blank Combustion 2nd extraction for 2nd heated blank Combustion Extraction blank for 2nd heated blank Combustion Wipe test for bench top after 2nd heated blank Combustion Wipe test for desktop after 2nd heated blank Combustion Wipe test blank after 2nd heated blank Combustion 1st PUF PFOS 1st Transfer Efficiency 2nd PUF PFOS 1st Transfer Efficiency PUF Blank for 1st Transfer Efficiency Wipe Test Desktop 1st Transfer Efficiency Wipe Test Blank 1st Transfer Efficiency 1st PUF PFOS 2nd Transfer Efficiency 2nd PUF PFOS 2nd Transfer Efficiency PUF Blank for 2nd Transfer Efficiency Wipe Test Bench top 2nd Transfer Efficiency Wipe Test Desktop 2nd Transfer Efficiency Wipe Test Blank 2nd Transfer Efficiency 1st extraction PFOS 2nd Transfer Efficiency 2nd extraction PFOS 2nd Transfer Efficiency Blank extraction PFOS 2nd Transfer Efficiency 6 /,T?:on Spreadsheet linking UDRI Thermal Testing and 3M Analytical Results E02-0926-4314I E02-0926-43142 E02-0926-43143 E02-0926-43144 E02-0926-43145 E02-0971-43393 E02-0969-43371 E02-0969-43372 E02-0969-43373 E02-0969-43374 E02-0969-43375 E02-0969-43376 E02-0968-43360 E02-0968-43361 E02-0968-43362 E02-0968-43363 E02-0968-43364 E02-0968-43365 E02-0968-43366 E02-0968-43367 E02-0968-43368 E02-0968-43369 E02-0968-43370 9/6/2002 9/6/2002 9/6/2002 9/6/2002 9/6/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 NHB-1 NHB-2 NHB-BUC. WT-BT-NHB WT-BLK.-NHB TE3-EX-BLK-1 PFOS-AIR-TE3-1 PFOS-AIR-TE3-2 TE3-EX-PFOS-R-1 TE3-EX-PFOS-R-2 TE3-EX-PFOS-V-1 TE3-EX-PFOS-V-2 PFOS-HE-TE3-1 PFOS-HE-TE3-2 TE3-EX-PFOS-R-3 TE3-EX-PFOS-R-4 TE3-EX-PFOS-V-3 TE3-EX-PFOS-V-4 TE3-EX-BLK.-2 WT-BT-TE3-PFOS WT-DT-TE3-PFOS WT-BLK-TE3-PFOS PFOS-BLK-TE3 * corresponds to section number in final report. 1st extraction for non-heated blank 2nd extraction for non-beated blank Extraction blank for non-heated blank Wipe test on bench top after non-heated blank Wipe test blank after non-heated blank 5.6.3 1st Blank extraction for 3rd Transfer Efficiency 5.6.3 1st PUF for PFOS in air 3rd Transfer Efficiency 5.6.3 2nd PUF for PFOS in air 3rd Transfer Efficiency 5.6.3 1st Extraction of Reactor and Transfer line for 3rd Transfer Efficiency of PFOS in air 5.6.3 2nd Extraction of Reactor and Transfer line for 3rd Transfer Efficiency of PFOS in air 5.6.3 1st Extraction of Valve & Short Transfer line for 3rd Transfer Efficiency of PFOS in air 5.6.3 2nd Extraction of Valve & Short Transfer line for 3rd Transfer Efficiency of PFOS in air 5.6.3 1st PUF for PFOS in He 3rd Transfer Efficiency 5.6.3 2nd PUF for PFOS in He 3rd Transfer Efficiency 5.6.3 1st Extraction of Reactor and Transfer line for 3rd Transfer Efficiency o f PFOS in He 5.6.3 2nd Extraction of Reactor and Transfer line for 3rd Transfer Efficiency of PFOS in He 5.6.3 1st Extraction of Valve & Short Transfer line for 3rd Transfer Efficiency o f PFOS in He 5.6.3 2nd Extraction of Valve & Short Transfer line for 3rd Transfer Efficiency of PFOS in He 5.6.3 2nd Blank extraction for 3rd Transfer Efficiency Wipe Test Bench top PFOS 3rd Transfer Efficiency Wipe Test Desktop PFOS 3rd Transfer Efficiency Wipe Test Blank PFOS 3rd Transfer Efficiency 5.6.3 PUF Blank for PFOS in air 3rd Transfer Efficiency c c r: 0: C