Final Report - Laboratory- Scale Thermal Degradation of Per?uoro-Octanyl Sulfonate and Related Precursors May 2003 BUSINESS PROPRIE AR DISTRIBUTION LIMITED WITHOUT WRITTEN CONSENT OF SPONSOR Final Report Laboratory-Scale Thermal Degradation of Per?uoro-Octanyl Sulfonate and Related Precursors This report coyers the efforts performed by the University of Dayton Research Institute (UDRI), Environmental Science and Engineering Group, Dayton, OH 45469- 0132, 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, and the Project Monitor was Eric A. Reiner and Dan C. Hakes. The UDRI Program Monitors were Philip Taylor and Tak Yamada. Ms we sea/a3 MM Dr. Philip Taylor Date Dr. Tak Yamada Date . 513391? TABLE OF CONTENTS Executive Summary Background Phase 1: Objectives and Test Protocol Phase 11: Method Development Phase Revised Test Protocol Experimental Results 5.1 5.2 5.3 5.4 Transfer Ef?ciency Test Laboratory Spike Analysis for PFOS Heated Blank Combustion Analysis 5.3.1 5.3.2 5.3.3 In-line Analysis Off-line Analysis Reactor/Transfer Line Extraction and LC-MS Analysis Combustion Tests 5.4.1 5.4.2 5.4.3 PFOS Combustion Tests 5.4.1.1 In-line Analysis 5.4.1.2 Off-line Analysis 5.4.1.3 Analysis of Extracts 5.4.1.4 LC-MS Analysis of PUF Cartridges FC-1395 Combustion Test In?line Analysis 5.4.2.2 Off?line Analysis 5.4.2.3. Analysis of Extracts 5.4.2.4. Analysis of PUF FC-807A Combustion Test 5.4.3.1. In-line Analysis 5.4.3.2. Off-line Analysis 5.4.3.3. Analysis of Extracts 5.4.3.4. LC-MS Analysis PAGE TABLE OF CONTENTS (continued) 5.5 2nd Heated Blank Combustion Analysis 5.5.1. In-line Analysis 5.5.2. Off-line Analysis 5.5.3. Analysis of PUF Cartridges 5.6 Transport Ef?ciency Tests for PFOS 5.6.1 1St Transport Ef?ciency Test 5.6.2 2ml Transfer Ef?ciency Test 5.6.3 3rd Transfer Ef?ciency Test 5.7 Sulfur Recovery Rate as S02, SOFZ, and S02F2 5.8 Extracted Ion Analysis Discussion Conclusions References APPENDICES ii PAGE FIGURE 2.1. 5.3.1. 5.3.2. 5.3.3. 5.3.4. 5.4.1.1. 5.4.1.2. 5.4.1.3. 5.4.1.4. 5.4.2.1. 5.4.2.2. 5.4.2.3. 5.4.2.4. 5.4.3.1. 5.4.3.2. 5.4.3.3. 5.4.3.4. 5.5.1. 5.5.2. 5.5.3. LIST OF FIGURES Schematic of the System for Thermal Diagnostic Studies In-line Ion Chromatogram for Heated Blank at In-line Ion Chromatogram for Heated Blank at Off-line Ion Chromatogram for Heated Blank at Off-line Ion Chromatogram for Heated Blank at In-line Ion Chromatogram for PFOS at In-line Ion Chromatogram for PFOS at Off-line Ion Chromatogram for PFOS at Off-line Ion Chromatogram for PFOS at In-line Ion Chromatogram for FC-1395 at In-line Ion Chromatogram for FC-1395 at Off?line Ion Chromatogram for at Off-line Ion Chromatogram for FC-1395 at In-line Ion Chromatogram for FC-807A at In-line Ion Chromatogram for FC-807A at Off-line Ion Chmmatogram for FC-807A at Off-line Ion Chromatogram for at In-line Ion Chromatogram for Heated Blank at In-line Ion Chromatogram for Heated Blank at Off-line Ion Chromatogram for Heated Blank at PAGE 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 Ion Chromatogram for Heated Blank at Calibration Curve (Molar Number vs. Peak Area) Total Ion Chromatogram and Corresponding HFID Signal for Combustion of PFXS at (off-line sample) Extracted Ions SOP-67, CF3-69, CF2CF2H-101, and C2F5-119) and Corresponding HFID Signal for Combustion of PFXS at (off-line sample) HFID Signal for PFOS Combustion at (off-line sample) HFID Signal for PFOS at (off-line sample) PAGE 28 33 35 36 37 37 TABLE 3. 1 . 3.2. 5.2.1. 5.2.2. 5.3.1. 5.3.2. 5.3.3. 5.3.4. 5.4.1.1. 5.4.1.2. 5.4.1.3. 5.4.1.4. 5.4.1.5. 5.4.2.1. 5.4.2.2. 5.4.2.3. 5.4.2.4. 5.4.2.5. LIST OF TABLES Linear Fit Equations and Detection Limits Transport Ef?ciency Transport Ef?ciency Test Results Net Amount of Sample Loaded PFOS Laboratory Spike Analysis Flow Rate Pro?le for Heated Blank Analysis at Flow Rate Pro?le for Heated Blank Analysis at Methanol Extraction Results for Heated Blank Analysis at PUF Extraction Results for Heated Blank Analysis Net Amount of Gasi?ed Sample for PFOS Combustion Test Flow Rate Pro?le for PFOS Combustion Test at Flow Rate Pro?le for PFOS Combustion Test at Methanol Extraction Results for PFOS Combustion Test PUF Extraction Results for PFOS Combustion Test Net Amount of Gasi?ed Sample for Combustion Test Flow Rate Pro?le for FC-1395 Combustion Test at Flow Rate Pro?le for FC-1395 Combustion Test at Methanol Extraction Results for Combustion Test PUF Extraction Results fer Combustion Test PAGE TABLE 5.4.3.1. 5.4.3.2. 5.4.3.3. 5.4.3.4. 5.4.3.5. 5.4.3.6. 5.5.1. 5.5.2. 5.5.3. 5.6.1.1. 5.6.1.2. 5.6.1.3. 5.6.2.1. 5.6.2.2. 5.6.2.3. 5.6.2.4. 5.6.3.1. 5.6.3.2. 5.6.3.3. 5.6.3.4. 5.6.3.5. LIST OF TABLES (continued) Net Amount of Gasi?ed Sample for FC-807A Combustion Test Flow Rate Pro?le for FC-807A Combustion Test at Flow Rate Pro?le for FC-807A Combustion Test at Flow Rate Pro?le for Blank Analysis between 600 and Methanol Extraction Results for Combustion Test PUF Extraction Results for FC-807A Combustion Test Flow Rate Pro?le for Heated Blank Analysis at Flow Rate Pro?le for Heated Blank Analysis at PUF Extraction Results for Heated Blank Analysis Net Amount of Gasi?ed Sample for 1St Transfer Ef?ciency Test Flow Rate Pro?le for 1St Transfer Ef?ciency Test PUF Extraction Results for 1st Transfer Ef?ciency Test Net Amount of Gasi?ed Sample for 2nd Transfer Ef?ciency Test Flow Rate Pro?le for 2nd Transfer Ef?ciency Test Methanol Extraction Results for 2nd Transfer Ef?ciency Test PUF Extraction Results for 2"?1 Transfer Ef?ciency Test Net Amount of Gasi?ed Sample for PUF Collection Flow Rate Pro?le for PUF Collection (PFOS Gasi?cation with Air) Flow Rate Pro?le for PUF Collection (PFOS Gasi?cation with He) Reactor/Valve Transfer Line Extraction Results PUF Extraction Results vi PAGE TABLE 5.7.1. 5.7.2. 5.7.3. 5.8.3. 5.8.4. LIST OF TABLES (continued) 802 Calibration Results Using PLOT Column Standard 802 Transfer Ef?ciency Sulfur Recovery Rate as Integrated HFID Peak Area of PFXS and PFOS at Integrated HF ID Peak Area of PFOS at vii PAGE 32 33 34 37 37 EXECUTIVE SUMMARY 3M requested that the Environmental Sciences and Engineering Group at UDRI evaluate the incineration of (PFOS) and two Cg per?uorosulfonamides and potential sources of PFOS to the environment upon incineration. The overall goal of this study was to determine if incineration is a potential source of per?uoroalkyl sulfonates, per?uoro- octanyl sulfonates (PFOS), which has been found in a number of 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. to gasify the materials with more severe high-temperature (600 oxidative conditions representing a secondary combustion zone. TGAs of the active ingredient indicated that higher temperatures (ca. were necessary to gasify this material. The sponsor also requested that the experiment be designed to detect low-levels of PFOS in the exhaust gases. These factors necessitated the use of large amounts of material (milligram quantities) and high-temperature, long duration exposures (ca. 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. 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 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 analyses, reactor ef?uent 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 by analysis were conducted to investigate the following: 1) the extent of conversion of the active ingredients, 2) the formation of ?uorinated organic incomplete combustion byproducts, and 3) the extent of conversion of the sul?lr to sulfur oxides. The data presented herein clearly show that incineration of and does not release PFOS to the environment. This conclusion is based mainly on the 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 quite good, 100125%. The dominant sink for sulfur was $02. analysis of per?uorinated alkyl sulfonate precursors indicated that such precursors were not present in the reactor ef?uent. This ?nding is consistent with the measurements, and strongly suggests that the C-S bond was completely destroyed (and did not reform) in the combustion tests. High levels of conversion of the PFOS were observed from the incineration tests. This conclusion was based on measurements of the reactor ef?uent 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 $02. analysis of per?uorinated alkyl sulfonate precursors indicated that such precursors were not present in the reactor ef?uent. This ?nding is consistent with the 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 ef?uent. These compounds were limited to ?uorobenzene (FC-1395 and FC-807A only), C1 or C2 ?uoroalkanes (likely products are either CHF3, CF4, or C2F6), (PFOS only), and (FC- 1395 only). Higher molecular weight ?uorinated aromatic hydrocarbons were not observed. The data from this laboratory-scale incineration study indicates that properly operating full-scale incineration systems can adequately dispose of PFOS and the C3 per?uorosulfonamides. Incineration of these ?uorinated compounds is not likely to be a signi?cant source of PFOS into the environment. With the exception of stable C1 and C2 ?uorocarbons, ?uorinated organic intermediates are also unlikely to be emitted from these facilities during the incineration of these materials. ix 5/31/2003 Laboratory?Scale Thermal Degradation of Per?uoro?Octanyl Sulfonate and Related Precursors Final Report Prepared by: Takahiro Yamada and Philip H. Taylor Environmental Sciences and Engineering Group University of 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, US-MNSPOZ, PO. Box 33331 St. Paul, MN 55133-3331 1. Background The destruction ef?ciency (DB) 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 of incinerators (Dellinger, et al., 1991). Numerous calculations and experiments have shown that emissions of undestroyed, residual POHCs are kinetically, not thermodynamically controlled (Tsang and Shaub, 1982; Trenholm, et al., 1984; Dellinger, et al. 1991). As a result, accurate assessment of 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-?ame zones of incinerators control the relative emissions of most POHCS (Clark, et al., 1984; Dellinger, et al., 1986; Dellinger, et al. 1991). This is because all molecules entering the ?ame zone of an incinerator are destroyed completely to thermodynamic endproducts and only the minute fraction escaping the ?ame zone is actually emitted from the facility. Once in the post-?ame zone, gas-phase thermal decomposition reactivity in the presence of the major gas-phase constituents of this zone control the rate of POHC destruction and formation and destruction of products of incomplete combustion (PICS). If all POHCs in a given waste stream are volatilized at approximately the same rate, they will experience the same post-?ame 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 of POHCs (as determined under a standardized set of conditions) may be used to predict their relative incinerability. The temperature for 99% destruction at 2.0 seconds gas?phase residence time, has been used previously to rank the thermal stability of 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 signi?cant variable in determining relative stability (Graham, et al., 1986; Taylor and Dellinger, 1988; Taylor, et al., 1991). Experimental and theoretical considerations suggest that various ?ame 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 of POHC relative incinerability. The UDRI thermal stability-based incinerability ranking was initially published in 1990 with further development published in1991 (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 full-scale as a basis for determining POHC incinerability. Pilot?scale studies (Carroll, et al., 1992) of 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 ratio than the baseline set of conditions) both produced statistically signi?cant correlations between product emission concentrations and their gas-phase thermal stability rankings. For the thermal failure tests, correlations above the 99% con?dence interval were observed. Full-scale studies (Dellinger, et a1., 1993) of a seven- component hazardous waste mixture indicated that thermal failure and waste/air mixing failures also produced statistically signi?cant correlations. Based on median destruction and removal ef?ciencies (DREs), the data indicated that both the mixing and thermal failure modes produced statistically signi?cant 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 of the following ?uorocarbon-based compounds: FC-807A and FC 1395 (C3 per?uoroalkyl sulfonamides), and (PFOS). The overall goal of this study was to determine if incineration is a potential source of per?uorooctanyl sulfonates (PFOS), which has been found in a number of wildlife tissue samples (Giesy, et al., 2001; Kannan, et al., 2001). This report describes the experimental studies of PFOS, and This report is broken into eight sections. The ?rst 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 the revised test protocol. Sections ?ve 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 of the phase I, phase II, and phase studies and the actual dates of the combustion tests, 2) Sample descriptions and Certi?cate of Analysis (C of A) for PFOS sample, 3) the phase 11 ?nal report and raw data, 4) the phase test protocol and addendum, 5) the 3M analytical report and 6) a spreadsheet linking the UDRI combustion tests with the 3M Analytical results. 2. Phase 1: Objectives and Test Protocol The objectives of this program were the following: 1. Determine if C3 per?uorosulfonamides form combustion products that either are per?uoro? octanyl sulfonate (PFOS) or precursors of per?uoro-octanyl sulfonate. 2. Determine the extent of conversion of PFOS under conditions representative of hazardous or municipal waste incineration, 3. Identify the major ?uorinated combustion products, 4. Determine if the sulfur present in the PFOS is quantitatively converted to sulfur dioxide and/or thionyl ?uoride (SOFZ) and sulfuryl ?uoride (SOze) at high temperature, fuel-lean combustion conditions. The development of the test protocol was based on the use of batch-charged continuous ?ow reactors developed at UDRI to study the thermal stability of organic materials (Rubey and Carnes, 1985, Rubey and Grant, 1988). Brie?y, these systems accept a small quantity of material (typically less than 1 mg). The sample and its decomposition products are volatilized, mixed with ?owing 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 system for analysis. Quanti?cation of parent species is based on transport and analysis of known quantities under non-destructive conditions. Typically, products are quanti?ed 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 identi?cation of stable ?uorinated organic intermediates and the quanti?cation of sulfur oxides in an attempt to recover 100% of the initial sulfur in the sample. Sulfur quanti?cation will be performed using a mass selectiVe detector (MSD). Consideration was also given to the use of a sulfur-speci?c detector that responds only to sulfur atoms. However, due to the universal nature of the MSD, its ability to detect both sulfur and ?uorinated organic compounds, it was decided that the MSD would be satisfactory for these experiments. Every sample presents its own unique set of challenges. In the case of PFOS, the unknowns in establishing the test protocol centered around the issue of transportability. Speci?cally, 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 of sample feed and product transport and analysis. The ?rst 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. When 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 of relatively simple tests was performed to determine if the gasification products could be transported under nominal ?ow reactor conditions. While the sample inlet systems of the UDRI reactors can be routinely heated to (with transient heating as high as the sample transport lines to and from the reactors are typically limited to 250-3 Experience has shown that under these conditions most organic compounds of interest can be tranSported without inducing thermal reactions thereby preserving the ?delity of the samples ?owing from the inlet system to the reactor and the product stream ?owing 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 gasi?cation 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 of 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 of 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 of hazardous materials allowing prior knowledge of the risks associated with burning a given waste. 9 Syslarn for Thermal Dlagnostlc Studles (STDS) Pll??ll MI) ?ns FUJI am rinan momma tumult lumen? In TEST CELLS Ilnll?i?llml new (105C) mum? tumult: mama mum? imuum cc mu 0! FECKEO 5m GE l?ll?fSlS (10" D) PLUS 4-8528' 3 so Figure 2.1. Schematic of the System for Thermal Diagnostic Studies Initially, the Advanced Thermal Photolytic Reactor System (ATPRS) was selected for this study. To satisfy the analytical requirements for PFOS detection by analysis at 3M Environmental Laboratory, we determined that relatively large amounts of sample, 0.5 to several mg, had to be gasifled in the actual experiments. This amount of sample was much larger than initially estimated (ca. 10 to 100 lag) and could not be gasi?ed with the inlet available with the ATPRS. Preliminary experiments also demonstrated that higher gasiflcation temperatures were necessary to rapidly gasify the ?uorocarbon-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 n-octane). Subsequently, it was determined that a substitute was necessary because the liquid hydrocarbon fuel originally proposed required a much larger amount of 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 de?cient and requires hydrogen source to convert 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 Preliminary combustion tests with several samples indicated that many combustion byproducts were formed at but those combustion byproducts were not observed at higher temperature (750 and and the total ion chromatograms for these higher temperatures were very similar. Therefore it was decided that two temperatures are suf?cient to analyze the combustion phenomena of the selected samples (600 and 3. Phase 11: Method Development The following method development tests were performed in phase II: 1. Verify that PFOS can be gasi?ed and transported through the UDRI thermal instrumentation system. 2. Establish recovery ef?ciencies and detection limits for stable sulfur compounds and PFOS precursors. The sulfur compounds would include but not be limited to $02, SOFZ, and SOng. PFOS precursors would include but not be limited to per?uoro?octane sulfonyl ?uoride (POSF). Establish recovery ef?ciencies and detection limits for volatile C1-C4 ?uorocarbons. 4. Develop a quantitative method of sampling the reactor ef?uent. ORBO PUF cartridges (Supelco, Inc.) will be used for sampling PFOS and its precursors from the reactor ef?uent. This section summarizes the results. Calibration curves and detection limits for 802, $02132, POSF and C3F6 (hexa?uoropropene have been established. The transport ef?ciency for each compound through the STDS was also examined. Veri?cation that the C8 per?uoroalkyl sulfonates can be gasi?ed and transported through the system was performed following the completion of the combustion tests. This decision was made based on the potential contamination of the system had the transport tests been done prior to the combustion study. PUF cartridge sampling of the reactor ef?uent was established as part of the revised phase protocol. HFP was selected as the surrogate volatile ?uorocarbon due to the lack of availability of CF4 and CF3H from gas suppliers. The linear ?t equations for each sample, their linear correlation coef?cients (R) and detection limits are tabulated in Table 3.1. Further details regarding these calibration curves are available in the Phase 11 report. Table 3.1. Linear Fit Equations and Detection Limits Sample Name Linear Fit Detection Limit (Y: peak area, X: concentration (ppm)) (ppm) 802 3.8541E5 0.9971 78.5 SOFZ - 7.0267E4 0. 99941 30.3 SOze 1.8273E6 0.99708 20.1 POSF 8.4043E5 1.0 14.1 HFP - 2.8253E6 0.9997 3.9 The transport ef?ciency of each standard was estimated by comparing the measured sample peak area obtained when the sample was injected into injection port in and passed through combustion reactor and transfer line (system transport) with that obtained when the sample was injected directly into the injection port of GC2 (direct injection). Table 3.2. Trans ort Efficiengy System Transport Direct Injection Ef?ciency Peak Area Peak Area Sample 15T 2nd AVG (1) 15t 2?a AVG (2) S02 9130332 8980717 9055525 11952302 11762267 11857285 76.4 25244352 25203780 25224066 24862639 24773683 24818161 101.6 802% 86850304 85572809 86211557 84435720 79738316 82087018 105.0 POSF 1280370 1228718 1254544 1064431 1067947 1066189 117.7 HFP 148679354 145606343 147142849 148372504 142271896 145322200 101.3 As illustrated in Table 3.2, the transport ef?ciencies for SOFZ, SOng, and HFP were within analytical error. An uncertainty of i10% is reasonable for this type of analysis. That for POSF was higher, but is nonetheless acceptable. That for was around 76%. The S02 standard was analyzed as a two-component mixture with SOFZ. Since the transport ef?ciency for was nearly 100%, the results indicate some sample losses for through the reactor and transfer lines. Because $02 is expected to be one of the major combustion byproducts, we will repeat the ef?ciency test at the onset of the actual combustion tests (see section 5.1: Transfer Ef?ciency Test). We will estimate a correction factor based on ef?ciency test results to compensate for its measured concentration during the Phase study. Further details of the initial calibration and transport ef?ciency tests can be found in the Phase II report provided in the Appendix. 4. Phase Revised Test Protocol The combustion tests consisted of 8 separate tests as listed below: $02 Transfer Ef?ciency Tests, Laboratory Spike Analysis for PFOS, Heated Blank Combustion Test, Combustion Tests for PFOS and two Cg per?uorosulfonamides, Heated Blank Combustion Test (repeat), Transfer Ef?ciency Test for PFOS, Sulfur Recovery Analysis as $02, Extracted Ion Analysis. Specific attention was being given to the sampling of PFOS during incineration. In-line and off? line analysis, PUF (polyurethane foam) collection of the reactor ef?uent and chemical extraction of 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 Prior to the sample combustion analysis, the transfer ef?ciency for was re-examined and the laboratory spike analysis for PF OS 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 ef?ciency 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 was re-analyzed using off-line analytical results. Further details are provided in the Phase test protocol and addendum that are given in an appendix to this report. The 3M analytical report (LIMS Nos. E02-0820, E02-0822, E02-0840, E02-0867, E02-0895, E02-0896, E02-0898, E02-0899, E02-0916, E02- 0917, E02-0926, E02-0968, E02-0970, and E02-097l) 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 of these compounds and ca. 90% with 10 ug addition of these compounds. 5. Experimental Results 5.1. Transfer Ef?ciency Test The S02 transfer ef?ciency tests conducted in Phase II was repeated in Phase to con?rm the Phase 11 results. The results are shown in Table 5.1.1. The 302 standard was analyzed as a two- component mixture with S02 transport ef?ciency was 83.7%, higher than previous results, 76.4%, which gives average value of 80.1%. The tranSport ef?ciency for was again nearly 100%. Table 5.1.1. Ef?ciency Test Results System TranSport Directiljection Ef?ciency Peak Area Peak Area Sample 2"d_ Average (1) 1St 2nd? Average (2) 8300590 8433620 8367105 10134575 9995499 10065037 83.7 21346398 20309703 20828051 19612747 20444301 20028524 101.9 5.2. Laboratory Spike Malysis for PFOS PFOS was dissolved with 10 ml methanol (Aldrich, HPLC grade) and 1 p1 of solution was placed into a reactor (4 mm (id) 6 mm 7 cm length) and dried by blowing high purity nitrogen. The amount of 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. Table 5.2.1. Net Amount of Sample Loaded Sample Net Weight Solvent Amount Amount Injected Net Amount of Sample (mg) (ml) (pl) Loaded (pg) PFOS 10.02 10 1.0 1.0 Table 5.2.2 shows the extraction results for PFOS laboratory spike analysis, respectively. The combined ?rst and second extracts recovered 149% of the PFOS. Table 5.2.2. PFOS Laboratory Spike Analysis Sample Extracts PFOS (pg/pl) PFOS (pg) PFOS 1St Extracts 232 1.6 PFOS 2?d Extracts 40.5 0.23 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 of PFOS) for the reactor temperature at 600 and prior to series of combustion tests. Four analyses, in-line analysis, PUF collected off-gas sample analysis, off-line analysis using Tedlar bag, and reactor/transfer line 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 was mainly used to analyze compounds equal to or heavier than C6 compounds and off-line was used for lighter compounds including S02. PUF sample and methanol extracts were analyzed for PFOS detection. The experimental setup, reactor/transfer-line con?guration, and experimental procedure followed the Phase test protocol. The Phase 111 test protocol and addendum can be found in the appendix to this report. 5.3.1. In?line Analysis Table 5.3.1 and 5.3.2 show the ?ow pro?le and carrier flow volume used for the heated blank analysis at 600 and reSpectively. 0f the total gas ?ow, 1 ml/min was introduced to the in?line 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 ?ow splitter. Air was ?owed 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 analysis. A 5970B series with a MS capillary column (30 length, 0.25 mm id, Agilent Technologies, Inc.) was used for the in?line analyses. The in-line was Operated at constant pressure (10 psi). The MS was auto-tuned with per?uorotributylamine (PFTBA) and operated at an electron multiplier setting of 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 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 signi?cant amounts of condensed phase combustion byproducts. This expectation was con?rmed and is consistent with the large amounts of ?uorochemicals that were injected into the combustion system. Table 5.3.1. Flow Rate Pro?le for Heated Blank Analysis at Time Period Reactor Flow Pyroprobe Flow Total Flow Rate Total Sampled (sec) Rate (ml/min) Rate (ml/min) (ml/min) Volume Volumed (ml) (m1) 0 120 10.5 0.80 11.30 22.60 20.60 120 130 10.5 0.80 -) 4.63a 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 13.56 4.52 4.19 Total Volume (ml) 31.80 29.13 3 Linear increase (approximate). Switched to helium for sweep. Sampled volume for PUF and Tedlar bag collection. 10 Table 5.3.2. Flow Rate Pro?le for Heated Blank Analysis at Time Period Reactor Flow Pyroprobe Flow Total Flow Rate Total Sampled (sec) Rate (ml/min) Rate (ml/min) (ml/min) Volume Volumed (ml) (ml) 0 150 7.60 0.70 8.30 20.75 18.25 150 160 7.60 0.70 -) 4.63a 8.30 9 12.23 1.71 1.54 160 170 7.60 4.63 12.23 2.04 1.87 170 190 6.54 (He)b 4.53 11.07 3.69 3.36 Total Volume (ml) 28.19 25.02 3 Linear increase (approximate). b?c Switched to helium for sweep. Sampled volume for PUF and Tedlar bag collection. +cru 4 TIC: HEI1-EOO.D 5.00 10.00 15.00 25.013 130.00 35.00 Figure 5.3.1. In-line Ion Chromatogram for Heated Blank at l-X if) c! I1 TIC: 3500- 5000- 55004 50009 4500; 3500 3000 2500. 2000? ll I: 1' ll 1 5.00 1.1.111 10.00 1 Figure 5.3.2. In-line Ion Chromatogram for Heated Blank at 2Qbo 25 5.3.2. Off?line Analysis A 0.5 Tedlar bag (SKC, Inc.) was used to collect the off-gas. The samples were analyzed within 15 minutes after collection. The ?ow pro?le was identical to the in-line analysis and PUF collection except the last time period, which was not necessary for Tedlar bag analysis. series with SPEL-Q PLOT (Porous Layer Open Tubular) column (30 length, 0.53 mm Supelco, Inc.) was used for the analyses. The off-line was operated in the constant flow mode with 28 ml/min split ?ow. The MS was auto-tuned with per?uorotributylamine (PFTBA) and operated at an electron multiplier setting of 1600 in the 11 scanning mode sweeping a mass range from 35 to 550 m/z. The Tedlar bags were moderately heated to ca. 50 with a heat gun to minimize condensation on the bag surfaces. 1 ml sample volumes were injected using a gas-tight syringe (Hamilton Figure 5.3.3 and 5.3.4 show total ion chromatograms for the heated blank at 600 and 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 of any measurable contamination. 140000 130000 120000 1 Duo!) - 100000 90000 - 60000 700003 00000 50000 40000 i 30000 20000 10000 I 1 . 0 . I 2.00 47:30 0.00 0.00 10.00 12:00 14.00 10100 10100 Figure 5.3.3. Off-line Ion Chromatogram for Heated Blank at [\kAL?ritlaur1cznk 140000 '1 30000 - 120000- 110000 100000- 90000 30000 70000. 1 60000 I 50000 i 40000 30000 20000 I 1 0000 Cl21x) -&00 OJI) (100 ?100 101x: ?000 Figure 5.3.4. Off-line Ion Chromatogram for Heated Blank at 5.3.3 Reactor/Transfer Line Extraction and LC-MS Analysis Following PUF sample collection and in? and off-line analysis at extraction of the reactor/transfer line tubing was performed. The reactor was cut in half prior to the extraction. The second half of 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 test protocol. The extractions were performed twice using 5.5 m1 of 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 of PFOS, 0.08 pg, was found in the reactor/transfer line extract in the ?rst heated blank combustion test. The amount found was 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 of the ?uorochemical 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 PFOS (rig) 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 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 PF OS and two C3 per?uorosulfonamides, FC-1395 and FC-807A. 5.4.1. PFOS Combustion Tests Combustion product analyses were performed at reactor temperatures of 600 and Four distinct analyses were conducted for each test. Two analyses were conducted at UDRI: in-line analysis and off-line analysis using Tedlar bags. The chemical extractions of the reactor transfer lines were performed at UDRJ. The PUF cartridges were extracted at the 3M Environmental Lab. The experimental setup, reactor/transfer-line con?guration, and experimental procedure followed the Phase 111 test protocol. The 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 ?rst 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 of sample gasi?ed for PFOS combustion tests. The sample probe was weighed before and after the combustion tests. 13 Table 5.4.1.1. Net Amount of Gasi?ed Sample for PFOS Combustion Test Temperature Usage Loaded Remaining Net Amount Mass (mg) of Gasi?ed (mg) Sample (ms) 600 0.47 0.02 0.45 0.48 0.10 0.38 900 PUF 0.50 0.00 0.50 TB 0. 50 0.00 0. 50 In-line analysis and off-gas collection using PUF. Off-line analysis using Tedlar Bag. Tables 5.4.1.2 and 5.4.1.3 show ?ow rate pro?les used for PFOS combustion tests at 600 and respectively. Table 5.4.1.2. Flow Rate Pro?le for PFOS Combustion Test at Time Period Reactor Flow Perprobe Flow Rate Total Flow Rate Volume (sec) Rate (ml/min) (ml/min) (ml/min) (ml9.86 0.85 0.21 10.92 10.92 60 85a 0.00 0.00 0.00 0.00 0.00 85 157 9.86 0.85 0.21 10.92 13.10 157 167 9.86 0.85 -) 4.63b 0.21 10.92 9 14.70 2.14 167 - 177 9.86 4.63 0.21 14.70 2.45 177 -197 8.61 (He)c 4.53 0.00 13.14 4.38 Total volume passed through reactor (ml) 32.993 Total volume passed through PUF (ml) 30.12f Total volume used for off-line S02 (Entitative analysis (ml) 22.07?5 a System opened due to sample insertion. Assuming no outlet ?ow. 1? Linear increase (approximate). ?1 Switched to helium for sweep. Total carrier ?ow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. ?5 Volume used to calculate total amount of $02 recovered using off-line system. Table 5.4.1.3. Flow Rate Profile for PFOS Combustion Test at Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (sec) Rate (ml/min) (ml/min) (ml/min) (ml) Air Air CH4 0 60 7.12 0.65 0.16 7.93 7.93 60 85a 0.00 0.00 0.00 0.00 0.00 85 179 7.12 0.65 0.16 7.93 12.42 179 189 7.12 0.65 9 4.63b 0.16 7.93 9 11.91 1.65 189?199 7.12 4.63 0.16 11.91 1.99 199 219 6.15 4.53 (116)d 0 10.68 3.56 Total volume passed through reactor (ml) 27.5 5? Total volume passed through PUF (ml) 24.32f Total volume used for off-line quantitative analysis (ml) 19.62g aSystem opened due to sample insertion. Assuming no outlet ?ow. Linear increase (approximate). Switched to helium for sweep. Total carrier ?ow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. 3 Volume used to calculate total amount of recovered using off-line system. 14 Identical combustion conditions were repeated for PUF collection with in?line analysis and off-line MS analysis for each temperature. The ?rst total volume (3rd row from the bottom) is the summation of all ?ow steps. A ?ow of 1 ml/min was always supplied to the in- line system. Therefore, the volume passed through the PUF cartridge can be calculated by subtraction of the volume to the in-line 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 mi 1 ml/min. (197 85) sec. [60 sec/min] 30.12 m1 To calculate the total amount of recovered using the off-line system, the volume supplied to the in?line 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 ?rst 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 ?rst time step volume (10.92 m1) from total volume (32.99 ml). At the onset of the experiment, the methane/air mixture was ?owed through the entire system for 1 minute prior to samPle gasi?cation. Methane was introduced to supply hydrogen to consume excess ?uorine 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 ?ow through the system. The sample was then gasi?ed for 40 seconds at During and following this gasi?cation, methane/air ?ow swept the gasi?ed products from the pyroprobe to the reactor. For the combustion test, for example, the methane/air ?ow rate was 1.06 mL/min at for 1 min. 12 sec. At the temperature of 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 to gasify the sample during this ?ow period would have also forced approximately 1.9 pyroprobe volumes of gas from the pyroprobe to the reactor. During cooling from to following gasi?cation, there was likely also a temporary back ?ow of air into the pyroprobe as the gas pressure inside it I dropped. To purge the pyroprobe/transfer line, ?ow 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 combustion test, for example, the air flow rate was 4.63 mL/min at and the He flow was 4.53 mllmin. The total volume of the purging methane, air, and helium was 2.78 ml at which corresponds to 5.0 m1 at Since the effective volume of the pyroprobe chamber with the sample probe inserted is 1.5 cm3 (bottom of page 10 in Phase protocol), this volume completely ?ushes the pyroprobe chamber 3.3 times. This purging procedure was applied for the combustion test at and the blank between 600 and For in-line analysis, the head of the GC column was held at the temperature of during the entire combustion period to concentrate ef?uent gas that was introduced at 1 ml/min ?ow rate. The temperature programming was started after the ?nal helium purge. 5.4.1.1. In-line Analysis Figures 5.4.1.1 and 5.4.1.2 show total ion chromatograms for PFOS combustion at 600 and respectively. A single sulfur dioxide peak was the only identi?able peak for both combustion tests. Tetra?uorosilane, a common intermediate in the other combustion tests, was 15 not observed for the PFOS combustion tests. It is not clear why the total ion chromatograms for PFOS combustion at 600 and differ so dramatically from the other results. The MSD source might have suffered from a loss of 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 of the testing. Tic: .D 40000 33000 36000 1 32000 7 30?00 250005 ZBODO- 1 24000 - 22000- 20000 4 18?00 16000 i 1400C) I 12000 5 10000 I 3000 6000 4?00 1 I c. 1 . 5.00 . 10.00 15.00 20.00 25.00 30.00 35.00 Figure 5.4.1.1. In-line Ion Chromatogram for PFOS at A 0 r1 0 r1 (ins: TIC: .D 65000 1} 60000 55000 50000 45000 40000? 35000: 30000 25000 I 20000 15000 ?1 0?00 '1 5000 I 10100 0500 2000 25:00 30100 $500 o. i n" t? Figure 5.4.1.2. In-line Ion Chromatogram for PFOS at 5.4.1.2. Off?line Analysis Figure 5.4.1.3 shows the total ion chromatogram for off-line analyses for PFOS combustion at The largest peak at the beginning is associated with air. The second peak at 1.0 min. was identi?ed as The peak at 3.0 min. was identi?ed as sul?lr dioxide. Figure 5.4.1.4 shows the total ion chromatogram for off?line analyses for PFOS 16 combustion at 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. tr: a..1 r1 IN L) rm r1 'nc:Fc?4un?D 4000004 390000: 3130000 - 340000~ 320000- 300000, 230000 2600005 240000? 220000? 2000001 130000? 100000? 1400003 120000 1000004 40000- i 20000~ 'L000 21?) 400 61x: 000 1000 121K) 1400 101K) 1000 Figure 5.4.1.3. Off-line Ion Chromatogram for PFOS at "34.13 400000 3300001 300000 340000" 320000? 300000: 230000: 240000- 220000? 200000- 130000? 100000? 1400009 120000: 00000 30000; 60000; 40000 i - 20000? 1 xm?mw Hw000 :00 .400 000 000 1000 1200 1400 1300 1300 Figure 5.4.1.4. Off-line Ion Chromatogram for PFOS at 5.4.1.3. LC-MS Analysis of Extracts Table 5.4.1.4 shows the analytical results of the reactor/ transfer line extraction samples. Extracts of reactor/transfer line tubing after the test summed to only about 0.04% of the PFOS added. Table 5.4.1.4. Methanol Extraction Results for PFOS Combustion Test Extraction PFOS (pg/pl) PFOS (pg) 1St 15.4 0.1 1 2"d 8.61 0.059 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 less than 0.4 of the PFOS added at Only about 0.05% was captured by the PUFs at Surprisingly, somewhat larger amounts of PFOS were extracted from the second PUF in a two-PUF series at both and This suggests that some PFOS could have passed completely through the system, but in the third transfer ef?ciency tests, much larger amounts of PFOS were captured in the ?rst PUF in the series showing that the ?rst PUF typically collects more. An amount of carryover equivalent to 0.026% of PFOS added in the preceding tests was extracted from the PUF in the PFOS interim blank. Table 5.4.1.5. PUF Extraction Results for PFOS Combustion Test Temp Extraction PFOS PFOS (pg/141) (as) 600 PUF 25.1 0.62 PUF 64.0 1.6 900 PUF (15? 4.31 0.11 PUF (2n 9.01 0.22 5.4.2. FC-1395 Combustion Test Table 5.4.2.1 shows net amount of sample gasi?ed for FC-1395 combustion tests. The sample probe was weighed before and after the combustion tests. Table 5.4.2.1. Net Amount of Gasi?ed Sample for FC-1395 Combustion Test Temperature Usage Loaded Dried Remaining Net Amount of Mass (mg) Mass? (mg) Gasi?ed (mg) Sample (ms) 600 2.14 0.56 0.04 0.52 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 a In-line analysis and off?gas collection using PUF. Off-line analysis using Tedlar Bag. Calculated based on the water contents Table 5.4.2.2 and 5.4.2.3 shows ?ow rate pro?les used for FC-1395 combustion tests at 600 and respectively. The detailed explanation for each value can be found in section 5.4.1. 18 Table 5.4.2.2. Flow Rate Pro?le for FC-1395 Combustion Test at Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (sec) Rate (ml/min) (ml/min) (ml/min) (ml) Air Air CH4 0 60 9.53 0.85 0.16 10.54 10.54 60 85a 0.00 0.00 0.00 0.00 0.00 85 u? 157 9.53 0.85 0.16 10.54 12.65 157 - 167 9.53 0.35 4.63b 0.16 10.54 -) 14.32 2.07 167 - 177 9.53 4.63 0.16 14.32 2.39 177 - 197 8.20 (He)c 4.53 (He)d 0 12.73 4.24 Total volume passed through reactor (ml) 31.89a Total volume passed through PUF (m1) 29.02f Total volume used for off?line S02 quantitative analysis (ml) 21.35g System opened due to sample insertion. Assuming no outlet ?ow. Linear increase (approximate). Switched to helium for sweep. Total carrier flow volume that passed through the reactor. Total carrier ?ow volume that passed through PUFs. 3 Volume used to calculate total amount of recovered using off-line system. Table 5.4.2.3. Flow Rate Pro?le for Combustion Test at Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (sec) Rate (ml/min) (ml/min) (ml/min) (ml) Air Air CH4 0?60 7.14 0.63 0.12 7.89 7.89 60 853 0.00 0.00 0.00 0.00 0.00 85 179 7.14 0.63 0.12 7.89 12.36 179 139 7.14 0.63 4.63b 0.12 7.39 11.39 1.65 189-? 199 7.14 4.63 0.12 11.89 1.98 199 - 219 6.14 (He)c 4.53 (He)d 0 10.67 3.56 Total volume passed through reactor (ml) 27.445 Total volume passed through PUF (ml) 24.20f Total volume used for off-line S02 quantitative analysis (ml) 19.55g System opened due to sample insertion. Assuming no outlet ?ow. Linear increase (approximate). r?Switched to helium for sweep. Total carrier flow volume that passed through the reactor. Total carrier ?ow volume that passed through PUFs. 3 Volume used to calculate total amount of $02 recovered using off-line system. 5.4.2.1. In-line Analysis Figure 5.4.2.1 shows the total ion chromatogram for 01395 combustion at The ?rst peak at 0.4 to 1.0 min. was not clearly identi?ed. The second peak at 1.7 to 2.4 corresponds to sulfur dioxide. The peak at 7.1 min. was identi?ed as carbon disul?de and the largest peak at 10 minutes was identi?ed as benzene followed by ?uorobenzene at 11.1 min. The wide peak appeared at 10 to 13 minutes corresponds to tetra?uorosilane. The peaks after tetra?uorosilane include benzonitrile at 17.7 min. and naphthalene at 21.1 min. Figure 5.4.2.2 shows the total ion chromatograrn for FC-1395 combustion at The ?rst peak at 2.2 min. was identi?ed as sulfur dioxide and the peak at 11 min. was identi?ed as benzene. The sharp peak at 14.2 minutes and the subsequent wide peak both show a strong 85 signal that is attributed to tetra?uorosilane. 19 2000000 1800000_ 1000000 14000005 1200000? 1000000 800000T 400000~ ?hi? 200000 5.00 10.00 15.00 20.00 25.00 30.00 35.00 Figure 5.4.2.1. In-line Ion Chromatogram for FC-1395 at (-5, I:an an r] tun-5 TIC: .D 000000 550000 500000? 450000 4 400000 350000 300000 - 200000; 50000 a 1 00000 50000 XJ KM . In? 0 rmm_ 101x) 15km: 20in) 252x: aokn) r?s?mc Figure 5.4.2.2. In-line Ion Chromatogram for FC-1395 at 5.4.2.2. Off-line Analysis Figure 5.4.2.3 shows the total ion ehromatogram for off-line analyses for combustion at The large peak at the beginning is associated with air. The next peak at 0.9 min. was identi?ed as followed by sulfur dioxide at 3 min., at 4.8 benzene at 9.9 min. and ?uorobenzene at 10.1 min. also is likely produced during the gasi?cation process. Figure 5.4.2.4 shows the total ion chromatogram for off-line analyses for FC-1395 combustion at The largest peak is associated with air. Sulfur dioxide at 3 min. was the only identi?able product. 20 (.3 (It r! 1.1-: 400000- 330000 300000i 340000? 320000- 300000~ 230000 2000004 2400004 220000? 200000; 100000? I 100000? #40000- 120000? 100000' I 300004 00000: 40000 - 20000 A 0 . - 000 200 .100 000 000 1000 1200 1400 ?100 1&00 Figure 5.4.2.3. Off-line Ion Chromatogram for FC-1395 at AKA-J K.I rs 12.542? Tic: .0 . 400000- 3000001 3000004 340000- 320000 300000 200000v 200000 I 2400003 I 220000? I 200000 i 100000? i 100000- I 4400004 120000? 100000 30000 000004 I 400003 1 de?0.00 2.00 4.00 ELOO 3.00 10.00 12.00 14 '15.!30 13.00 A. . . ?r I. Figure 5.4.2.4. Off-line Ion Chromatogram for FC-1395 at 5.4.2.3. LC-MS Analysis of Extracts Table 5.4.2.4 shows the analytical results of the reactor/ transfer line extractions. N0 detectable amount of PFOS was found. Table 5.4.2.4. Methanol Extraction Results for FC-1395 Combustion Test Extraction PFOS(pg/ui) 1st <5.00 <0.035 <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. 21 Table 5.4.2.5. PUF Extraction Results for FC-1395 Combustion Test Temp Media PFOS PFOS (98/111) (148) 600 PUF <5.00 <0.12 PUF <5.00 <0.12 900 PUF <5.00 <0.12 PUF <5.00 <0.12 5.4.3. FC-807A Combustion Test Table 5.4.3.1 shows net amount of sample gasi?ed for combustion tests. The sample probe was weighed before and after the combustion tests. Table 5.4.3.1. Net Amount of Gasi?ed Sample for FC-807A Combustion Test Temperature Usage Loaded Dried Remaining Net Amount of Mass Massc (mg) Gasi?ed 0119 (ma) Sample (mg) 600 2.68 0.59 0.00 0.59 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 aIn-line analysis and off-gas collection using PUF. Off-line analysis using Tedlar Bag. Calculated based on the water contents Tables 5.4.3.2, 5.4.3.3, and 5.4.3.4 show the ?ow rate pro?les used for FC-807A combustion tests at 600 and and the blank test between 600 and 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 test runs. The unheated valve/transfer line tubing of the reactor/transfer line tubing was also extracted after the combustion test at The purpose of these analyses was to measure the carryover between the tests on a single ?uorocarbon product done at 600 and Table 5.4.3.2. Flow Rate Pro?le for FC-807A Combustion Test at Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (secL Rate (ml/min) (ml/min) (ml/min) (ml) Air Air CH4 0 60 9.70 0.84 0.15 10.69 10.69 60 85a 0.00 0.00 0.00 0.00 0.00 85 157 9.70 0.84 0.15 10.69 12.83 157 167 9.70 0.84 4.63b 0.15 10.69 -) 14.48 2.10 167 177 9.70 4.63 0.15 14.48 2.41 177 - 197 8.89 (H6)c 4.53 0 13.42 4.47 Total volume passed through reactor (m1) 32.50e Total volume passed through PUF (m1) 29.64f Total volume used for off-line quantitative analysis (ml) 21 .81g 3 System opened due to sample insertion. Assuming no outlet ?ow. Linear increase (approximate). ?1 Switched to helium for sweep. a Total carrier ?ow volume that passed through the reactor. Total carrier ?ow volume that passed through PUFs. 3 Volume used to calculate total amount of recovered using off?line system. 22 Table 5.4.3.3. Flow Rate Pro?le for FC-807A Combustion Test at Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (sec) Rate (ml/min) (ml/min) (ml/min) (ml) Air Air CH4 0 60 7.25 0.66 0.12 8.03 8.03 60 84El 0.00 0.00 0.00 0.00 0.00 84 - 178 7.25 0.66 0.12 8.03 12.58 178 188 7.25 0.66 -) 4.63b 0.12 8.03 12.00 1.67 188 - 198 7.25 4.63 0.12 12.00 2.00 198 - 218 6.27 (He)c 4.53 0 10.80 3.60 Total volume passed through reactor (ml) 27.886 Total volume passed through PUF (ml) 24.65f Total volume used for off-line quantitative analysis (ml) 19.858 a System opened due to sample insertion. Assuming no outlet ?ow. 1? Linear increase (approximate). Switched to helium for sweep. Total carrier flow volume that passed through the reactor. Total carrier ?ow volume that passed through PUFs. ?5 Volume used to calculate total amount of recovered using off-line MS system. Table 5.4.3.4. Flow Rate Pro?le for Blank Analysis between 600 and Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (sec) Rate (ml/min) (ml/min) (ml/min) (ml) Air Air CH4 0 120 9.70 0.84 0.00 10.54 21.08 120 130 9.70 0.84 -) 4.63a 0.00 10.54 -) 14.33 2.07 130 140 9.70 4.63 0.00 14.33 2.39 140 - 160 8.89 (He)b 4.53 (He)c 0.00 13.42 4.47 Total Volume (ml) 30.01 3 Linear increase (approximate). 1? Switched to helium for sweep 5.4.3.1. In-line Analysis Figure 5.4.3.1 shows the total ion chromatogram for FC-807A combustion at The ?rst peak at 0.6 to 1.3 min. was not clearly identi?ed. The second peak at 1.9 to 2.4 min. was identi?ed as sulfur dioxide. The peak at 7.1 min. was identi?ed as carbon disul?de. The peak at 8.1 min. which shows strong spectra at m/z 69 and 51 was not clearly identi?ed. Peaks at 10.3 and 11.1 min. were identi?ed as benzene and ?uorobenzene, respectively. The wide peak that appeared at 11.2 to 12.6 min and the subsequent background correspond to tetra?uorosilane. The two major peaks after tetra?uorosilane were not clearly identi?ed. Figure 5.4.3.2 shows the total ion chromatogram for FC-807A combustion at The ?rst 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 tetra?uorosilane. 23 TICZ50000 - a i. ?Mi: Lit-r Li UM. I 5.00 10.00 15.00 20.00 25.00 30.00 3:.00 Figure 5.4.3.1. Ion Chromatogram for FC-807A at A 0 r1 Ge TIC: 800000 4 700000 600000 1 500000 400000 "ii: 300000 200000 i 1 00000 i I 5.00 I 10:00 I 15:00 I 20:00 I 25100 30.00 35100 2? Figure 5.4.3.2. In?line Ion Chromatogram for FC-807A at 5.4.3.2. Off-line Analysis Figure 5.4.3.3 shows the total ion chromatogram for off-line analyses for FC-807A combustion at 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 identi?ed as sulfur dioxide and respectively. There were no further identi?able peaks. Figure 5.4.3.4 shows the total ion chromatograrn for off-line analyses for combustion at 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 respectively. 24 A a: r? (.11 If: TIE: ll 1.. ll Ilium Figure 5.4.3.3. Off-line GCIMS Ion Chromatogram for FC-807A at A 1.21 ?3 4000004 3300001 360030 1 320000! I 3330001 2500004 260000 220000 200000 30000 '1 40000 1200001 30300 ADUOO 1 1000000.00 2.00 4,00 (5.00 10.00 12.00 14.00 15.30 13.00 Figure 5.4.3.4. Off-line Ion Chromatogram for at 5.4.3.3. Analysis of Extracts Table 5.4.3.5 Shows the analytical results of 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 (ag) 15t <5.00 <0.035 2"d <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. 25 Table 5.4.3.6. PUF Extraction Results for FC-807A Combustion Test Temp Media PFOS PFOS (pg/111) (11g) 600 PUF <5.00 <0.12 PUF <5.00 <0.12 900 PUF <5.00 <0.12 PUF <5.00 <0.12 5.5. 2'?d Heated 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 In- line analysis, off-line analysis using Tedlar bags, and PUF cartridge sampling were conducted. The same process used for the ?rst 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 analysis. 5.5.1. In-line Analysis Tables 5.5.1 and 5.5.2 show ?ow rate pro?les and carrier ?ow volumes used for heated blank analysis at 600 and respectively. Figures 5.5.1 and 5.5.2 show total ion chromatograms for reactor temperatures at 600 and respectively. The chromatograms Show only background noise and no contamination was found for either temperature. Table 5.5.1. Flow Rate Pro?le for Heated Blank Analysis at Time Period Reactor Flow Pyroprobe Total Flow Rate Total Sampled (sec) Rate (ml/min) Flow Rate (ml/min) Volume Volurnecl (ml/min) (m1) (m1) 0? 120 10.0 0.81 10.81 21.62 19.62 120? 130 10.0 0.81 -) 4.63al 10.81 -) 14.63 2.12 1.95 130 140 10.0 4.63 14.63 2.44 2.27 140 160 8.83 (He)b 4.53 13.36 4.45 4.12 Total Volume (ml) 30.63 27.97 3 Linear increase (approximate). Switched to helium for sweep. Sampled volume for PUF and Tedlar bag collection. Table 5.5.2. Flow Rate Pro?le for Heated Blank Analysis at Time Period Reactor Flow Pyroprobe Total Flow Rate Total Sampled (sec) Rate (ml/min) Flow Rate (ml/min) Volume Volumed (mi/min) (ml) (m1) 0? 150 7.11 0.62 7.73 19.33 16.83 150 160 7.11 0.62 -) 4.63a 7.73 9 11.74 1.62 1.46 160 a 170 7.11 4.63 11.74 1.96 1.79 170 a 190 6.16 (He)b 4.53 10.69 3.56 3.23 Total Volume (m1) 26.47 23.30 aLinear increase (approximate). Switched to helium for sweep. Sampled volume for PUF and Tedlar bag collection. 26 Jh.l::i - 1 1-1 ?ma-11mm ?i'tc; . . - 1- 5 ch05 15.00 25.nch 36.09 Figure 5.5.1. In-line Ion Chromatogram for Heated Blank at I It'y'! qr." Tic: 1900c: 1 700:: -- 14sec":- 1 etc-ac: - 14cc": 1 soon 1 1 can cacao Taco noon 1590c: 400? - 350C) - 1:300 - c, 10:09 zaloo 25 ac} apt-loo salon Figure 5.5.2. In?line Ion Chromatogram for Heated Blank at 5.5.2. Off-dine Analysis Figures 5.5.3 and 5.5.4 show total ion chromatograms for the heated blank at 600 and respectively. The large peaks at the beginning are associated with air. No other peaks were observed. A11: LJ r1cj e: an 110000- 100000? soc-DoT 600001 700001 50000- 50000? 40000 - 300005 . 7 10000} l; *wuhiww2.00 4.00 6.00 3.00 10.00 12.00 14.00 16.00 13.00 5 HI Juv- Figure 5.5.3. Off-line Ion Chromatogram for Heated Blank at 27 AbLn-Iclann?m TIC: 240000 220000 200000 - 150000 - 160000 - 140000 . 120000 1 00000 - - ?50000 400001 . . . 0.00 2.00 4.00 6.00 3.00 10.00 12.00 14-00 13.00 10.00 20000 Figure 5.5.4. Off-line Ion Chromatogram for Heated Blank at 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/til) PFOS (pg) 600 <10.0 <0.25 900 <10.0 <0.25 5.6. Transport Ef?ciency Tests for PFOS Sample transfer ef?ciency tests were conducted to investigate how ef?ciently PFOS would be transferred through reactor/transfer line system. Three types of tests were conducted as described in the Phase protocol and its addendum. 5.6.1. 1st Transport Ef?ciency Test In the ?rst transfer ef?ciency test, PFOS was volatilization in the pyroprobe chamber and the reactor and transfer lines were heated to PUF cartridge sampling of the off-gases was performed. This test examines the transfer ef?ciency of samples gasi?ed in the pyroprobe and transported through reactor. Table 5.6.1.1 shows the net amount of gasi?ed sample for the 1St transfer ef?ciency test. Table 5.6.1.2 shows the flow pro?les. Table 5.6.1.1. Net Amount of Gasifled Sample for lSit Transfer Ef?ciency Test Sample Loaded Remained after Net Amount of Mass (mg) Gasi?cation (mg) Gasi?ed Sample (mg) PFOS 0.53 0.05 0.48 28 Table 5.6.1.2. Flow Rate Pro?le for 13? Transfer Ef?ciency Testa Time Period Reactor Flow Pyroprobe Total Flow Rate Total Sampled (sec) Rate (ml/min) Flow Rate (ml/min) Volume Volume? 4(ml/minL (ml) (ml) 0 60 16.0 0.82 16.82 16.82 15.82 60 84 0.00 0.00 0.00 0.00 84? 156 16.0 0.82 16.82 20.18 18.98 156 166 16.0 0.32 4.53? 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 a Helium was used for all carrier ?ow. 5 Linear increase (approximate). Sampled volume 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 the sample was either thermally dissociated in the pyroprobe chamber or the gasi?ed sample was completely condensed in the pyroprobe/reactor transfer line tubing. Table 5.6.1.3. PUF Extraction Results for 1st Transfer Ef?ciency Test Sample PUF PFOS PFOS Extracts (pg/111) (11g) PFOS 1st <5.00 <0.12 2?d <5.00 <0.12 5.6.2. 2"Cl Transfer Ef?ciency 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 of the reactor. PUF sample cartridges were connected to the perprobe using the shortest possible transfer line heated to The pyroprobe and transfer line were extracted using methanol. Table 5.6.2.1 shows the net amount of gasi?ed sample for 2nd transfer ef?ciency test. Table 5.6.2.2 shows the ?ow pro?les. Table 5.6.2.1. Net Amount of Gasi?ed Sample for 2"d Transfer Ef?cieneLTest Sample Loaded Remained after Net Amount of Mass (mg) Gasi?cation (mg) Gasi?ed Sample (mg) PFOS 0.47 0.00 0.47 29 Table 5.6.2.2. Flow Rate Pro?le for 2"d Transfer Ef?ciency Testa Time Period Pyroprobe Flow Volume (sec) Rate (ml/min) (ml) 0 60 0.63 0.63 60 82 0.00 0.00 82 176 0.63 0.99 176 - 186 0.63 4.53b 0.43 186?216 4.53 2.27 Total Volume (ml) 4.32 a Helium was used for carrier ?ow. Linear 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 of PFOS survive pyrolysis conditions of the pyroprobe, and enter the heated transfer lines up to the reactor. However, none of 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 (pg/Ml) (Mg) PFOS 15t 897 21 2?(1 <10.0 <0.24 Table 5.6.2.4. PUF Extraction Results for 2"d Transfer Ef?ciency Test Sample PUF PFOS PFOS Extracts (pg/til) (ug) PFOS 15t <10.0 <0.25 2?d <10.0 <0.25 5.6.3. 3rd Transfer Efficiency Test A 3rd transfer ef?ciency 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 of the PUF cartridges. Table 5.6.3.1 shows the net amount of gasi?ed 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 of GC oven was increased to prevent the condensation of gasi?ed sample. When the GC oven temperature reached 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. 30 Table 5.6.3.1. Net Amount of Gasified Sample for PUF Collection Sample Carrier Loaded Remained after Net Amount of Gas Mass Gasi?cation Gasi?ed Sample (mg) (mg) (mg) PFOS Air 0.48 0.00 0.48 PFOS He 0.50 0.04 0.46 Tables 5.6.3.2 and 5.6.3.3 also show ?ow rate pro?les PFOS gasi?cation under oxygen-rich and oxygen-de?cient conditions. Table 5.6.3.2. Flow Rate Pro?le for PUF Collection (PFOS Gasi?cation with Air) Time Period Temperature Carrier Gas Used Total Volume Sampled Volumea (sec) Condition and Flow Rate (ml/min) (m1) (ml) 0 439 GC Oven 25 9 260 Air 10.7 78.29 7097 439 ?637 Furnace 103 -) 575 Air 10.7 35.31 32_01 637 937 GC 260, Furnace 575 Air 10.7 53.50 4850 937 997 GC 260, Furnace 575 He 8.6 8.60 760 Total (ml) 175.70 159.08 a Sampled volume for PUF collection. Table 5.6.3.3. Flow Rate Pro?le for PUF Collection (PFOS Gasi?cation with He) Time Period Temperature Carrier Gas Used Total Volume Sampled Volumea (sec) Condition and Flow Rate (ml/min) (ml) (ml) 0 410 GC Oven 30 -) 260 He 10.8 73.80 6697 410 615 Furnace 140 -) 575 He 10.8 36.90 33 .48 615 975 GC 260, Furnace 575 He 10.8 64.80 5830 Total (ml) 175.50 159.25 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 3rd transfer ef?ciency test showed quite clearly that some measurable PFOS air, 11% He) could pass from the heated reactor where it was volatilized in this test to the PUFs. Larger amounts of PFOS air, 30% He) also accumulated in the reactor/transfer lines upstream of the PUF cartridges. The majority of the PF OS accumulated in the portion of the transfer line heated to 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 Gasi?cation Location Extracts PFOS PFOS (133291) (as) Reactor 1 5? 1 908 24 Air 2?d 35.4 0.45 Valve 1st 696 2.4 pros 2nd 22.3 0.079 Reactor 13530 171 He 2"?1 150 1.9 Valve 15? 2218 7.7 2?d 102 0.35 31 Table 5.6.3.5. PUF Extraction Results Sample Carrier Cartridge PFOS PFOS Gas (pg/111) (as) PFOS He 15t 2330 <1o.0 <0.12 5.7. Sulfur Recovery Rate as 802, SOFZ, and SOZFZ Based on the in- and off-line analyses, sulfur was found mainly as $02. No SOFZ and 80ng were detected. The sulfur recovery rate as using in?line system was not quantitatively repeatable. This was due primarily to the low peak resolution using the cryogenic focusing method at with a holding time of ca. 4 min. Because the peaks using the off-line system were much sharper than peaks observed using in~line we decided to use off-line analytical results to quantitatively analyze the sulfur recovery analysis as $02. 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: 802 (M01) =[Area 494980] [1 .7997x 10?] Table 5.7.1. Calibration Results Using PLOT Column Cone. (ppm) M01. 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 32 8.010'5 4.9498e+05? 1.7997e+14x 0.99656 . I 7.0106 6.0106 5.0106 4.0105 Peak Area 3.0 106 as 1.010210?3 310'? 410''3 510'8 Mo! Figure 5.7.1. S02 Calibration Curve (Molar Number vs. Peak Area) Prior to the sulfur recovery analysis as S02, a third S02 transfer ef?ciency test was conducted using the off?line analysis approach. Table 5.7.2 shows the results. Air was ?owed through the reactor at 8.85 ml/rnin for 2 min. 30 sec. while the S02 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 for PFOS, FC-1395 and FC-807A. The last column shows the sulfur recovery rate taking into account a transfer ef?ciency rate of 75.6%. Results for the C3 per?uorosulfonamides were quite reasonable, 100i25%. Results for PFOS were not as good, with recovery rates of only 50?60%. Table 5.7.2. Standard Transfer Ef?ciency Volume (ml) Area Calculated M01. of Moi. Used Transfer Ef?ciency 22.13 10591947 83.4 22.13 8515987 1.63E-06 67.8 Average 75.6 33 Table 5.7.3. Sulfur Recovery Rate as Compound Temp. Volume Area Calculated Gasi?ed of MOI. of Recovery Recovery Rate (C) (ml) Mol. Mass Gasi?ed Rate after Ef?ciency (mg) Sam?e Correction PFOS 600 22.07 2169830 3.27E-07 0.38 7.06E-07 46.3 61.2 900 19.62 2676600 3.46E-07 0.50 37.2 49.2 FC-1395 600 21.35 4159651 5.52E-07 0.52 7.15E-07 77.2 102.1 900 19.55 3402701 0.43 5.9lE-07 71.6 94.7 600 21.81 6587251 8.58E-07 0.59 93.8 124.0 900 19.85 6354547 0.53 8.22E-07 91.9 121.5 5.8. Extracted Ion Analysis The following ions 119-C2F5, and 67-SOF) were extracted from the total ion chromatograms of the PFOS and C3 per?uorosulfonamide tests (in-line and off-line analyses) to analyze for the presence of per?uorinated and sulfonate-containing intermediates. The purpose of this analysis was to provide additional information regarding the potential formation of volatile ?uorocarbons and volatile ?uorinated oxysulfur compounds that were not identi?ed in the 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 disul?de. This analysis further indicated that 69 and 119 ions were present in most if not all of 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 ?uorocarbons were present that were not identi?ed in the analysis of the total ion chromatograms. In contrast to tests results for other ?uorocarbon 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 ?ame 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 of another compound with per?uoroalkyl moieties having less than 8 carbons, labeled as PFXS, was analyzed in addition to the HFID data for PFOS combustion products. Analysis of these HFID data showed the formation of volatile fluorocarbons. This analysis did not give quanti?able results, but due to the structural similarity of PFXS and PFOS, this analysis substantiates the potential formation of volatile ?uorocarbons from the combustion of PFOS. Figure 5.8.1 shows the total ion chromatogram and the corresponding HFID signal for PFXS off? line analysis at 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, C02) but does respond to ?uorocarbons, it is apparent that volatile ?uorocarbons are eluting from the GC column simultaneously with the air constituents. Mass spectral ions corresponding to volatile ?uorinated compounds, including 1, SOF-67, 69, 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 of 0.8 min. corresponds to a mass spectral signal that contains the following 34 ?uorocarbon ions: 51, 69, and 119. The 51 ion occurs near the tail of the HFID signal while the 69 and 1 19 ions occnr near the peak of the FID signal. Likely candidates that can be attributed to the 51 and 69 ions are tri- and tetra?uoromethane. Likely candidates for the 119 ion are penta or hexa?uoroethane. Penta?uoroethane 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 hexa?uoroethane would elute earlier than penta?uoroethane due to its lower boiling point. Thus, the most probable candidates that correspond to the HFID signal at 0.8 min. are tri- and tetra?uoromethane and/or hexa?uoroethane. -1 0000001 TIC: 900000 600000 - 700000 500000 -: 500000 400000 300000 - 200000 - 1 00000 2.00 4.00 6.00 3.00 10.00 ?12.00 14.00 16.00 18.00 Fag?a0-r. 1 A Jl 4cm?, . 1 . -- 0.0-0 2.00 4.00- 5.300 B_b? ?0.00 12:00 141?00 19:00. 15100 l'ir'r?m. .. Figure 5.8.1. Total Ion Chromatogram and Corresponding HFID Signal for Combustion of PFXS at (off?line sample) 35 A r10! 4:3 ?2.10 80000 60000 - 40000 - 20000 i r'r: Iii) A la r: (.3 (.1: as 30000 00000- 40000 20000_ Ian 51 .00 (50.70 to 51.70): PCS-60T.D . - -?50 1.5 3.00 3.50 4.00 libr?l to 0 i r'n 80000i 60000 40000 20000. (5w 300004 00000J 40000 - 20000- 0 Ar! dean": GIL-3 60000 -s 40000i 20000 0 i f\ I.) r141! an r! more 75000 05000? 50000_ 45000? 40000; 35000 30000- 25000? 20000- 15000- 10000? 5000 1 D. 30 i try (mt-u (150 2.00 2.50 3.00 3.50 :0 {51:3} 0.1) :53 '7 0 to. {535EL) .000 3050 It)? 1 to 101 1.50 2.00 Iii-30 '100 3,50 '4.00 Iron '1 '1 'l 8. Vii) to ?l ?l ?23! . 7'0} I 00 2.50 3.00 3.50 4,00 4.50 PCS-BOT. ?1 A .00 I . 1.50 2.00 2.50 3.00 3.50 4.00 4.50 Figure 5.8.2. Extracted Ions (CF2H-51, SOF-67, CF3-69, and C2F5-119) and Corresponding HFID Signal for Combustion of PFXS at (off?line sample) Figure 5.8.3 shows the HFID signal for PFOS combustion at and the integrated HFID peak areas for PFXS and PFOS are shown in Table 5.8.3. The retention time of 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 are shown in Figure 5.3.4 and Table 5.8.4. The peak is ca. 1% of the 36 response obtained at thus indicating nearly complete destruction of ?uorinated compounds under these conditions. A Ln 1 r; a) cuta- ?1 A 130000- 1 1 0000 100000; 90000 30000 1 70000 60000 - 50000R 30000: 20000 - ?i 40000 '1 0000 .Fvone (150 21x} 250 :100 :lso 41x3 .mso Figure 5.8.3. HFID Signal for PFOS Combustion at (off-line sample) Ab r1 deal FC 7-90'10.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 13.00 Figure 5.8.4. HFID Signal for PFOS at (off-line sample) Table 5.8.3. Integrated HFID Peak Area of PFXS and PFOS at Sample Peak Area Net Amount of Gasi?ed Sample (m3) PFXS 1190193 0.52 PFOS 3547614 0.38 Table 5.8.4. Integrated HFID Peak Area of PFOS at Sample Peak Area Net Amount of Gasi?ed Sample (mg) PFOS 39041 0.50 37 6. Discussion The motivation of this study was to determine the incinerability of per?uoro-octanyl sulfonate (PFOS) and if other per?uoro-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. to gasify the materials with more severe high-temperature (600 oxidative conditions applying to the secondary combustion zone. TGAs of the active ingredients indicated that higher temperatures were necessary to gasify these unique materials. The sponsor also requested that the experiment be designed to detect low-level concentrations of PFOS in the exhaust gases. These factors necessitated the use of large amounts of material (milligram quantities) and high-temperature, long duration exposures (ca. 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, 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 111 test protocol is a reasonable extrapolation of a full-scale incineration study of PFOS and its potential precursors. Combustion tests for PFOS and two C3 per?uorosulfonamides, FC-1395 and FC-807A, were completed as requested by the sponsor. ln?line and off?line analyses, reactor ef?uent 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 of conversion of the active ingredients, 2) the formation of ?uorinated intermediate organic products, and 3) the extent of conversion of the sulfur to sulfur oxides. There was no indication that PFOS was generated from FC-1395 and combustion. No quanti?able amount of PFOS was detectable at a detection limit of ca. 10 ng/ml. During PFOS combustion, small amounts of PFOS were detected in the reactor/transfer line system and the PUF sample cartridges, speci?cally, 0.04% of gasi?ed sample in the reactor/transfer line system, less than 0.4% in the PUF cartridges at and 0.05% in the PUF cartridges at High levels of PF OS destruction were thus achieved at temperatures of To validate the experimental results pertaining to the sampling and analysis of PFOS where in many instances the analytical results were below the level of quantitation, a series of transfer ef?ciency tests were conducted. The goals of the transport (or transfer) ef?ciency 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 ef?ciencies and analytical detection limits. In the 1st transfer ef?ciency test where the ability of the combustion system to transport PFOS was assessed, analysis of the PUF cartridges indicated the lack of any detectable material. This result indicated that PFOS was either thermally destroyed in the pyroprobe chamber or the gasi?ed sample condensed in the pyroprobe/reactor transfer lines and never reached the PUF sample cartridge. Based on the results of 1St transfer ef?ciency test, a 2ud transfer ef?ciency test was conducted to investigate the latter possibility. In these tests, 38 substantial amounts, 3.4% of PFOS gasi?ed, were indeed found in the pyroprobe/transfer line extracts. However, once again, analysis of the PUF cartridges positioned of the pyroprobe/transfer line were negative for PFOS. The 2rld test showed that measurable amounts of PFOS survive pyrolytic conditions in the pyroprobe and the heated transfer lines. The unanswered question was how much PFOS was transferred through the reactor/transfer line tubing and sammed by PUF cartridges if this material was formed in the combustion chamber. A 3":1 transfer ef?ciency 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 of the combustion chamber and transfer line system was then heated to This is the temperature of 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 while the transfer lines remained as When the combustion chamber was heated, some of the PFOS was likely entrained into the gas stream, and a larger proportion was probably destroyed. Nevertheless, a substantial portion of the PFOS was transported through the transfer lines to the PUFs where it was detected. PFOS was also found in the transfer lines. Speci?cally, results showed that measurable PFOS air, 11% He) passed from the combustion chamber to the PUF sampling cartridges. Results also showed that larger amounts of PFOS 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 of 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 of the sulfur in the samples would be oxidized to $02, SOFZ, and SOng under high?temperature oxidative conditions. The analyses indicated that the sulfur was recovered as No or 80ze was detected. Recovery rates were variable. Nearly 100% sulfur recovery was obtained from The recovery rate obtained from FC-807A was approximately 120%. Recovery rates were 50-60% for PF OS. There are two potential sources of error in the sulfur mass balance. The most likely is the condensation of 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 of error is the lack of complete quantitative transport of the 802. Three transport efficiency tests yielded an efficiency of 78.6i4 The transport ef?ciency was accounted for in the sulfur mass balance. The high repeatability of these recovery tests suggests that this source of error is small compared to potential condensation of the active ingredients and their primary degradation products including 802 on the walls of the reactor and transfer lines. analysis of the reactor ef?uent was conducted to assess the formation of combustion intermediates, products of incomplete combustion. The most abundant combustion byproduct was benzene. Benzene was observed for the all of the samples except PFOS. Fluorobenzene was also observed from the combustion of FC-1395 and FC 807A. For PFOS, the intermediate in highest concentration at was a C1 or C2 ?uorocarbon alkane, most 39 likely tri? or tetra?uoromethane or hexa?uoroethane. At the concentration of this compound was much lower in comparison with the results. The nature of this byproduct and its thermal stability is consistent with other tests we have conducted on ?uorinated samples that Show that per?uorinated alkanes are stable intermediates and require temperatures in the secondary combustion zone in excess of for high levels of destruction (Ciba Special Chemicals Corp., 2002). Small amounts of (PFOS only) and 1,2- di?uoroethene only) were also observed at The formation of per?uoroalkanes and alkenes was not unexpected and is consistent with the molecular structure of the starting material, where a C3 saturated ?uorocarbon chain is present. There was no evidence to suggest that ?uorinated acids were signi?cant combustion products. Fluorinated acids have been observed by analysis in combustion studies of 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 of more highly ?uorinated aromatic compounds, di- through hexa?uorobenzene nor was there evidence to suggest that poly?uorinated 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 There was no evidence that these precursors formed during PFOS combustion. Further examination of the total ion chromatograms for the SOF ion also indicated the lack of formation of secondary amine precursors, alcohol during the combustion of PFOS, FC-807A, and FC-1395. A small amount of undestroyed PFOS was observed in the analyses. It is unlikely that PFOS reformed during the combustion process due to the presence of large amounts of methane as the fuel for the combustion process. The presence of excess methane fuel relative to ?uorochemical product results in signi?cant concentrations of atoms that ef?ciently scavenge atoms as HF and prevent the reformation of long per?uoroalkyl chains. The hydrocarbon fuel to ?uorochemical ratio will likely be even higher under actual incineration conditions, further limiting the reformation of per?uoroalkyl chains. Per?uorinated alkanes, necessary building blocks to the formation of precursors to PFOS, were limited to C1 and C2 compounds, further indicating that reformation of PFOS, requiring C3 per?uoroalkyl chains, did not occur in the combustion system. 40 7. Conclusions The data presented herein clearly show that incineration of and FC-807A does not release PFOS to the environment. This conclusion is based mainly on the 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, 100i25%. The dominant sink for sulfur was $02. analysis of per?uorinated alkyl sulfonate precursors indicated that such precursors were not present in the reactor ef?uent. This ?nding is consistent with the measurements, and strongly suggests that the C-S bond was completely destroyed (and did not reform) in the combustion tests. High levels of conversion of the PFOS were observed from the incineration tests. This conclusion was based on measurements of the reactor ef?uent 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 $02. analysis of per?uorinated alkyl sulfonate precursors indicated that such precursors were not present in the reactor ef?uent. This ?nding is consistent with the 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 ef?uent. These compounds were limited to ?uorobenzene (PC-1395 and FC-807A only), C1 or C2 ?uoroalkanes (likely products are either CHF3, CF4, or C2F6), and (PFOS only) and 1395 only). Higher molecular weight ?uorinated aromatic hydrocarbons were not observed. The data from this laboratory-scale incineration study indicates that properly operating full-scale incineration systems can adequately dispose of PFOS and the C3 per?uorosulfonamides. Incineration of these ?uorinated compounds is not likely to be a signi?cant source of PF OS into the environment. With the exception of stable C1 and C2 ?uorocarbons, ?uorinated organic intermediates are also unlikely to be emitted from these facilities during the incineration of these materials. 41 Tsang, W. and Shaub, W., Chemical Processes in the Incineration of Hazardous Materials, Detoxification of Hazardous Wastes, . Exner, Ed., Ann Arbor, 1982, 41. 43 31111991450 sawq pun 911113111; 1 xgpuaddv Project Time Line Phase I March 2001 - October 2001 Phase 11 February 2002 Phase 111 March 2002 September 2002 Combustion Test Schedule - 2002 Date Description 2/1, 2/4, 2/7,2/15, Standard sample calibration 2/18, 2/19, 2/24 3/19 7/29 Combustion test system and method development 7/30 PFOS extraction 8/2 Heated blank extraction before combustion test 8/8, 8/9 FC-1395 combustion test 8/19, 8/20 FC-807A combustion test 8/23, 8/26 PFOS combustion test 8/27 Heated blank extraction after combustion test 8/28 PFOS transfer ef?ciency test 8/30 PFOS transfer ef?ciency test 9/3 9/5 Off-line S02 calibration 9/6 Non-heated blank extraction 9/18 9/20 PFOS transfer ef?ciency test Appendix 2 Sample descriptions and Certi?cate of Analysis (C of A) for PFOS sample) Appendix Sample descriptions and Certi?cate 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 of clear glass with black screw plastic cap Labeled as: 98-0211?3916-1 Lot 217 For 7.5 cm o.d. 13.5 cm height circular column shape with 5.2x6.0 cm i.d.xo.d.)circular top made of clear glass with metal screw cap. Labeled as: Material FC-807A 8681 BC AS Time 1 1:10 Lot No. 30177 Drum 1 Step 4 Date 12-22-2K Sampled By C. Senior For FC-1395 7.5 cm o.d. 17.5 cm height circular column shape with 1.9x2.5 cm circular top made of amber glass with black screw plastic cap. Labeled as: Name: FC-1395 Lot 90086 Date: 11/7/00 Reference Standard Descriptions: The following was retrieved from 3M Environmental Laboratory?s sample tracking systems. The original shipment to Univ of Dayton during April of '01 was the following: 20.1 PPM Per?uoro octane sulfonyl ?uoride, serial CC79754 4950 PPM Thionyl ?uoride, serial CC43285 10,049 PPM Sulfuryl ?uoride, serial FF17680 99.9+% Sulfur dioxide, lecture bottle, 3M barcode E0000002106 \Centre Analytical Laboratories. Inc. State Coilege. PA 1.6801 3048 Research Drive Phone: (814} 2316032 INTERIM CER IF I CA OF ANAL YS IS Revision 1(9/7/00) Centre Analytical Laboratories COA Reference 3M Product: PFOS, Lot 217 Reference 8 Purity: 86.9% Fax: {814) 231-1253 Or {814) 231-1580 7 Manganese Test Name Speci?cations Result 86.9% Appearance White Oystalline Powder C?oniorms identification Pogit?ve Metals 1. Calcium 1. 0.005 2. Magnesium 2. 0.00} u-?Lfm?o 3. Sodium 3. 1.439 4. Potassimn2 4. 6.849 xx-tx?MFE-?E: 5. Nickel 5. (0.001 6. Iron 6. 0.005 7. <0.001 "rm-a1 "Vo Impurity (NMR) 1,93 Total Impurity S. 4 1 wt 94: Trotai 1111pr it)? (GUM-S) None Detected Related Compounds - POAA 0 . 3 3 wt. Residual Solvents (TGA) Purity by DSC Inorganic Anions (1C) 5? Chloride Fluoride Bromide 4. Nitrate Nitrite 6. Phosphate .?Sulfato4 U: 35?" None Detected Nor 430.0 1 5 {3.5 9 <0 .040 wt .s?wt 33/0 <-0.009 <10 . 0 0 "Rut. 430.000/9: Organic Acids 3 (1C.91: 0. '30 0.28 2 PFPA 3 IAIFBA 3 4 NFPA Elemental Analysis": 1 Carbon 2 Hydrogen 3 Nitrogen - '4 Sulfur 5 Fluorine VI Theoretical 'l?hcoretical Theoretical Valuc *3 0?34: Theoretical Value 5.95% - Theoretical Value .74 3.84 54. .943 Page of 3. \Centre Analytical Laboratories. Inc 3048 Research Drive State College, PA 16801 0 Phone: (314) 231?8032 Fax: (814) 231?1253 or (814) 231?158( INTERIM CER TIFI CA TE 0F ANAL YSIS Centre Analytical Laboratories COA Reference 0233-01844. Date of Last Analysis: 0881;500 Expiration Date: 08f31i?01 Storage Conditions: Frozen Reassessment Date: 08531501 lPurity 100% (sum of metal impurities, 1.45% impurities, Fluoride, impurities, acid impurities, 0.33%) Total impurity from all tests 13.09% Purity 100% 13.09% 86.9% 3Potassium is expected in this salt form and is therefore not considered an impurity. 3Purity by DSC is generally not applicable to materials of low purity. No enclotherm was observed for this sample. iSulfur in the sample appears to be cenvettcd to 304 and hence detected using the inorganic anion method conditions. The anion result agrees well with the sulfur determination in the elemental analysis, lending con?dence to this interpretation. Based on the results, the $04 is not considered an impurity. Tri?uoroacetic acid HFBA Hepta? uorobutyric acid PA Nonofluoropentanoic acid PFPA Pentalluoropropanoic acid ?Theoretical value calculations based on the empirical formula, C31: This work was conducted. under EPA Good Laboratory Practice Standards (40 CFR 160). Pace 3 of? Went-e Analytical Laboratories. Inc 3048 Research?Drove State College, PA 16801 . Phene: (814} 231-8032 Fax: (814) 231-1253 or (814) 231-158C INTERIM CER IFI CA TE 0F ANAL YSIS Centre Analytical Laboratories COA Reference 023-018A LC.st Purity Pro?le: Impurity thwt. 0 C4 1.22 C5 1.33 C6 4.72 C7 1.14 Total 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: ,x?m Xgi??/ Das?id S. Bell Date Scien 'st, Ce ical Laboratories Reviewed By: ma ohm Flaherty Date Laboratory Manager, Centre Analytical Laboratories (.70AU23-018A Page 3 of? Appendix 3 Phase II Final Report and Raw Data August 1, 2002 3M Phase II Final Report: Laboratory-Scale Thermal Degradation of Per?uoro?octanylsulfonate and C3 Per?uoroalkyl Sulfonamides Prepared by: Environmental Sciences and Engineering Group University of Dayton Research Institute Summary Calibration curves and detection limits for 802, SOFZ, SOng, POSF, and C3F6 (hexa?uoropropene have been established. The transport ef?ciency 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 ?t equations, detection limits, and transport ef?ciency are provided in this report. Veri?cation that Cg per?uoroalkyl sulfonates can be gasi?ed and transported through the system will be performed following the completion of the phase 111 tests. This decision was made based on the potential contamination of the system had the transport tests been done prior to the phase combustion study. HFP was selected as the surrogate volatile ?uorocarbon due to the lack of availability of CF4 and CF3H from gas suppliers. Experimental Setup Six standards (802, SOze, POSF and HFP) were injected through the STDS reactor con?guration that will be used for the Phase combustion test. The same samples were also injected directly into the system and compared with the earlier tests to derive the transport ef?ciency for each material. Figure 1 shows a schematic diagram of reactor and in-line system that was used for the Phase II study. Data Acquisition Exhaust Line Switching Syringe Valve Pressure Gang Flow Reducer Injection I: (Pressure Controller) Port Furnace DB5 uartz GC Colum Remit? Split MS GC2 Figure 1. Schematic Diagram of Experimental Setup for the Phase 11 Study. August 1, 2002 The system consists of two GCs, the ?rst GC (GCI in Figure 1) was used to maintain reactor and transfer line at to transport samples ef?ciently and the second GC (GC2 in Figure 1) was used for sample analysis. The furnace in was also maintained at a temperature of Helium (He) was used as carrier ?ml/min using a differential ?ow controller (Porter Instruments). A ?ow splitter was installed between reactor and GC column to vent excess gas. A 21 ml/min ?ow rate was used to de?ne a residence time of 1 sec in the combustion reactor. The combustion reactor used in this study (and the Phase combustion test) is 4 mm 6 mm with an effective length of 5 cm. While the sample was being collected, the switching valve was opened toward exhaust line 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 system used in Phase II analysis was a Hewlett Packard incorporating a DB-S MS capillary column (30 length, 0.25 mm Agilent Technologies, Inc.) All samples were diluted in helium (Research Grade, Air Products, Inc.) to establish calibration curves and detection limits. The amount of sample injected was 1 ml for gas-phase samples (802, SOZF, 802F2, POSF, and HFP). Measurements were performed in duplicate for each sample and concentration. Operating Procedure Calibration 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 After sample injection, the ?ow 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 for min., heated to at 10?C/min. and held for 1 min. The GC was heated to for 10 min after each analysis to ?ush out any residual material from the column. The MS was auto-tuned with per?uoro- tributylamine (PFTBA) and operated at EMV (2000)!) in the scanning mode sweeping from 45 to 550 AMU. Direct Injection All conditions, GC oven temperature programming, total ?ow, 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. August I, 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 detection limit criteria for identifying an unknown (Method 8260B page 23 24). In our approach, the masses of 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% of the target ion. The detection limit was then speci?ed 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. i 20%. For example, Figure 19 and 20 in the Appendix illustrate the total ion chromatogram and mass spectra for $0ze (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 of 102, 83, 67, and 48 correspond to $02132, SOF, and SO, respectively and it is reasonable to choose these ions to quantify SOze. Figures 24 and 25 in the Appendix show the total ion chromato gram and mass spectra for a concentration of 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 of 4.0 ppm. The 102 ion is not present at this concentration. Therefore, the detection limit for S02F2 was determined as 20.1 ppm. Similar analysis was conducted for all of standards and the results are brie?y discussed below. Figures 2 to 7 show calibration plots for 802, 802F2, POSF, PBSF, and HF P, respectively. The linear ?t equations for each sample, their linear correlation coef?cients (R) and detection limits are tabulated in Table 1. Table 1 Linear Fit Equations and Detection Limits Sample Name Linear Fit Detection Limit (Y: peak area, X: concentration (ppm)) (ppm) 802 Y: 3.8541E5 0.9971 78.5 - 7.0267E4 0.99941 30.3 S02F2 1.8273E6 0.99708 20.1 POSF 8.4043E5 1.0 14.1 HFP - 2.8253E6 0.9997 3.9 The linear ?t for each calibration shows reasonable high correlation coef?cients. Because only 2 concentrations could be measured above the detection limit for POSF, the value is 1.0. Based on the linear ?t 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 response throughout the concentration range examined. The concentration range used to obtain the 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 August 1, 2002 for S02 (1570 ppm). The ions of 48 (SO) and 64 (S02) were chosen as target ion and major ion, respectively. The ion of 64 was not evident at a concentration of 15.7 ppm. The detection limit was thus determined as 78.5 ppm~3.8541iz+05 5381.3x 0.9971 . 1?3?1 I I I I I 200 400 600 300 1000 1200 1400 1600 Conc. (ppm) Figure 2. Calibration Plot for The concentration range used to obtain the SOFZ calibration was 3034 to 303.4 ppm. Figure 9 in the Appendix shows the mass spectra for The ion of 67 (SOF) was chosen as target ion and the ions of 86 (SOFZ) and 48 (SO) were chosen as major ions. All ions exist at a concentration of 30.3 ppm. At 6.1 ppm, there was no response to the sample. Therefore, the detection limit was determined as 30.3 ppm. August 1, 2002 SOFZ 3.0 107 -70257 3333.511 0.99041 2.5 105.010 0500 1000 1500 2000 2500 3000 3500 Cone. (ppm) Figure 3. Calibration Plot for The concentration range used to obtain 80ng calibration was 7034.3 to 100.5 ppm. The detection limit was determined as 20.1 as discussed above. 010? a 1.02?r3e +05 10331:: R: 0.99708 3 7 10? 6 10? 51o10?: - 5 0 1000 2000 3000 4000 5000 0000 7000 8000 Cone. (ppm) Figure 4. Calibration Plot for SOZFZ 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 of 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 August 1, 2002 (C3F7) were chosen as the major ions. The 100 and 13] ions were not present at a concentration of 8 (Fig.33), and the detection limit was determined as 14.1 ppm. POS ?8.4043e P05 1.0423t3+05x 1 12105 1.010a ,3 3.010 Area 0 5 10 15 20 25 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 81 (C2F3), 100, 131 (C3F5), and 150 were chosen as major ions. The ion of 81 was not present at a concentration of 1.9 (Fig. 51). The detection limit was thus determined as 3.9 ppm. HFP I -2.82 5391-06 4- 4975x R: 0.9997 area I I I I I 0 2000 4000 I I 6000 Cone. (ppm) Figure 7. Calibration Plot for HFP Transport Ef?ciency 8000 I I I 110? 1210? August 1, 2002 The transport ef?ciency of each standard was estimated by comparing the measured sample peak area obtained when the sample was injected into injection port in and passed through combustion reactor and transfer line (system transport) with that obtained when the sample was injected directly into the injection port of GC2 (direct injection). Table 2. Transport Ef?ciency System Transport Direct Injection Ef?ciency Peak Area Peak Area Sample 1st 2nd AVG (1) 15t 2"(1 AVG (2) S02 9130332 8980717 9055525 11952302 11762267 11857285 76.4 SOF2 25244352 25203780 25224066 24862639 24773683 24818161 101.6 SC)ng 86850304 85572809 86211557 84435720 79738316 82087018 105.0 POSF 12803 70 1228718 1254544 1064431 1067947 1066189 117.7 HFP 148679354 145606343 147142849 148372504 142271896 145322200 101.3 The transport ef?ciencies for SOFZ, SOze, and HFP were within analytical error. An uncertainty of i 10 is reasonable for this type of analysis. That for POSF was higher, but is nonetheless acceptable. That for S02 was around 76%. The S02 standard was analyzed as a two-component mixture with SOFZ. Since the transport ef?ciency for was nearly 100%, the results indicate some sample losses for 802 through the reactor and transfer lines. Because S02 is expected to be one of the major combustion byproducts, we will repeat the ef?ciency test August 1, 2002 as part of the Phase study. We will estimate 3 S02 correction factor based on 802 ef?ciency test results to compensate for its measured concentration during the Phase study. August 1, 2002 Appendix (Raw Data for Phase II Report) The total ion chromatograms of the 6 standards $0ng, POSF and hexa?uoropropene 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. Ala r1 at an II TIC: CLSOFSJZ) 400000 I 350000 300000 250000 I 200000 - 150000 100000 50000 1.00 1.50 2.00 2.50 3.00 3.50 Figure 8. Total Ion Chromatogram for SOF2 (3034 ppm) and (1570 ppm) Abu nuisance. Scan 39 (0.451 min): CLSOFBJD (-) (:37 220000 - 200000~ 180000? 1600005 '1 40000 100000? 80000 - 50000- 40000- 200004 }8 86 - -- . 384042444648 Figure 9. Mass Spectra for (3034 ppm) August 1 2002 At) LI :1 c3 Scan 140 (1.570 min): 43 45000 (34 40000- 1 35000? . 30000 250001 I i 20000' I 5000 ?l 0000 EST-J i 4 .5 5000 6'0 652 61?4- 65 6 7r0 72 74 miz. m? Figure 10. Mass Spectra for (1570 ppm) Abundance: 'nc;CLsoF513 300000T I 250000? 2000004 1 50000 - 1 100000? 500001 . . In.I. 0.000.400,000.801.001 .201.401 .601 .802.002 .202 .402.602_803.003.203.40 im Figure 11. Total Ion Chromatogram for (2124 ppm) and (1099 ppm) Abu r1le 100000? 1 60000 1 40000 20000 00000 30000; 1 30000 I 40000 20000? 0. ., . . 0.20 0.40 0.600.30 .00 1.20 1.40 ?1 .00 ?l 'Tunepm? Figure 12. Total Ion Chromatogram for (1214 ppm) and (628 ppm) August 1, 2002 ?(3.9.0062 TIC: CLSOF9.D 30000 - 25000? 20000; 1 5000 - I _10000- Ill; \f 1 5000 - Ax Wit?: -. .- \rr1111? . a An 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.30 2.00 2.20 2.40 2.60 2.80 3.0 Wye?nu?? Figure 13. Total Ion Chromatogram for SOF2 (303.4 ppm) and (157 ppm) Abundance 14000" 12000; 6000; I) 8000- 4000: .l I 2000- I ?h if?) . ,4 q,?l -LL may) 0-. . Ii?h?ni. . I ?h A Tuna": Figure 14. Total Ion Chromatogram for (151.7 ppm) and (78.5 ppm) Ab an c: (in- Scan 164 (1.832 min): 13004 4:8 (34 1200T 11004 10001 900m 300? 7001 600? 500T 400i 300% 200? 100? om'r'T? I I I?llr11fz?m7-?v Figure 15. Mass Spectra for $02 (78.5 ppm) August 1, 2002 ISL: r'i r) 1.1-, r' {In :In? Figure TIC: ?l .0 ZEDD 26002 2400; 22007 20009 1500? 1500- 1400; 1' 12005 1000f II 3003 600? 4001.60 2.00 2.20 2.40 2.60 16. Total Ion Chromatogram for (30.3 ppm) and (15.7 ppm) . . . . Q20 Qko Q60 aha L60 L20 rho mac (nib .l I 111 a I '1 11?. Illa" 45 3 .D [Eff 10001 9004 300 700 600 500 - 300 9'4 Figure 17. Mass Spectra for (30.3 ppm) 38 40 I mat-e Benn 1 72 (1.920 mar-II600 550- 500 45E) ADD 350 zoo - 250:33 3940 a 1 42 4:344 3'2 6'3 6'4 5'5 3'6 Figure 18. Mass Spectra for $02 (15.7 ppm) l?to 750000 700000 550000 - 550000 -- 500000 450000 400000 300000 - 250000 - 200000 '1 50000 00000 5000C) - August 1, 2002 Tl?: i m- wr . . .1, (1&0 ?140 (160 (L80 ?1 m1 .00 ?l .60 1 .80 2.00 2.50 2.r40 Figure 19. Total 1011 Chromatogram for 8021?; (10049 ppm) AmtuLlecieal1<:ue n?zm 300000- 230000? 2400003 2200001 200000; 1300007 140000{ 120000: 30000? 600005 40000? 20000: 48 Scani?3?l336rhh?:hK3L5F224uD 83 102 1 1 54(m3 1174 91 110 -uu3 152 . cur-.- 700000? 650000 600000- 550000 500000? 1 4000003 350000? 300000 - 250000 2000005 1000005 50000 01 I "7141',- 40 D. Figure 21. Total Ion Chromatogram for SOze (7034 ppm) 20 il?l? +1 . 50 6b 8b 110 120 130 140 150 Figure 20. Mass Spectra for 80ze (10049 ppm) 70 TIC: HCL5F223.D who mho 1.60 I I 050000 500000 5 50000 350000 - 300000: 250000 - 200000 50000 - 100000 50000 - August 1, 2002 TIC: 0 Ti :11 raci :53 :23 170000; '1 60000 50000 ?1 40000 1200004 1100005 1 100000; 90000L 300009 700003 50000? 400005 20000: 3 130000' Eb 0.450 100.100'200 Figure 22. Total Ion Chromatogram for SOng (4020 ppm) 0. TIC: 10000- Tunemn 5500 .5000 - 4500 - 4000 - 3500 - 3000 -- 2500 - 2000 - ?0.20 0.40 0.50 0.80 1.0 Figure 23. Total Ion Chromatogram for SOze (1005 ppm) TIC0.10 0.20 0.30 0.40 0.50 0.00 0.70 0.00 0.90 .20 Figure 24. Total 1011 Chromatogram for (20.1 ppm) 1.00 1.510 1 Ab Ll (.195: 2400 2200 2000 r-?a 280? - I: ZELDCI -- 2400 2:200 - EDDIE -- 1 1 '1 1 1 ay-v-?m .. :1 August 1, 2002 Scan 32 (0.373 min): 4 1022 . 4:2. 70 Figure 25. Mass Spectra for 80ze (20.1 ppm) TIG: I [Ivuvvmr IEI -I- for $0ze (4.0 ppm) Figure 26. Total Ion Chromatogram C). Al'.u.4rn..l.m nu. .. .. Sc-r? RB (0.32% min): (AllFigure 27. Mass Spectra for $0ze (4.0 ppm) .3 '4 A Ir.) 1.: den may: 00000? 45000- 400001 1 350001 30000~ 25000; 200003 10000? 100003 5000 - August 1 2002 TIC: in 'M*wymm?um . 00 0.00 0.00 7.00 0.00 9.00 10.00 11.00 Figure 28. Total 1011 Chromatogram for POSF (20.1 ppm) Ah? I'i t1 A21- 19000 - 19000: 17000: 10000: 15000: 140005 13000? 12000 10?00 9000 5000: 7000 - 600? - 0000? 4000; 3000 2?00 - 000 7 50-" 920 (10.214 min): GE) -1u5?v 100 I 43BID 9?0 100 1101201130 140150 150170130190 200210220 Figure 29. Mass Spectra for POSF (20.1 ppm) LI r'l dun 1'1 40000 - 35000 - 30000 25000 - 2000C) - 1 5000 - ?l 0000 5000: 1 .I . ?1.00 2,00 3. TIC: I n] nn111. .. . .. I be 4ix: 000 e100 1&00 six) 000 10kn31moo ??00 Figure 30. Total Ion Chromatogram for POSF (14.1 ppm) Abundance: 9000? 8000; 7000: 6000: 5000i 40003 30005 20004 1000 - Abu nd?nce 7000 6000 5000 4000 - 3000 - 2000 - 1000? 1 Scan 922 (10.235 min100 110 120 Figure 31. Mass Spectra for POSF (14.1 ppm) TSC: H: 1 I 1111,. . . . . August 1, 2002 i 0 . .. 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.0011.0012.00 Timev?r: Figure 32. Total Ion Chromatogram for POSF (8.0 ppm) Abur'n den net?.1- 3500 - 3000 - 2500 - 20001 '1 500 '1 1000- 500 ?2 Scan 922 (10.236 mln): 1 193 100 110 120 130 140 150 Figure 33. Mass Spectra for POSF (8.0 ppm) ?1 (5 fr) August 1, 2002 2400000 (1 TIC: 2200000 9 2000000- 1000000- 1600000 I 1400000J 12000001 10000004 4 300000? 400000 I I I. 200000" I 0, ,.r1 .17. ..Tji?Tr?fi?f..l 1.. ,rT? 'w?r Tunemw Figure 34. Total Ion Chromatogram for Hexa?uoropropene (HFP) (10,000 ppm) Abundance 1 1 900000? 69 7000004 600000- 500000; 400000: 300000? 1 200000: 100000100 110 120 n1I.?mw Figure 35. Mass Spectra for HFP (10,000 ppm) Ata- TIC: PFPS. 4 1600000 500000 1400000j 1300000- 1200000T 1100000? I 1000000 000000: 000000 700000- 000000: !h 500000? 300000 1 200000 - 4000001 1000001 i a'n 4:9 -- Figure 36. Total Ion Chromatogram for HFP (7,000 ppm) 10 August 1, 2002 Ah r'l we: TIC: 350000- 300000? 750000- 700000? 650000 . 550000~ I 500000? 4500001 400000; 350000- 300000- 2500004 200000? 150000- 100000: 50000~ 1 . I - 0.50 1.00 1.50 2.00 2.50 3.00 ELIEO Figure 37. Total Ion Chromatogram for HFP (4,200 ppm) irn us; TIC: 2000003 100000- 150000? I 170000? 160000 150000 I 140000- 130000- 120000? 110000: 100000T 00000- 60000; 70000? 50000? 50000- 40000 - 30000 4 20000? 10000Yw.m 020:140:100umbo L00 Figure 38. Total Ion Chromatogram for HF (1,050 ppm) h't'mh-m 2- LI f1 r1 (zen TIC: .D 8000 -: 7500 - 7000? f! 6500- 0000j 5500{ 50001 4500f 40004 3500! 3000: I 1' 2 000 1 500 [?ll IR . 1 DOD HEW. fa, A #3 0.20 0.40 0.00 0..00 Figure 39. Total Ion Chromatogram for HFP (3.9 ppm) 2500} Irnm-m?- 11 A bund uncu- m/z 3500 - .3000 25005 2000 -- 1500- 1000? 500 '3 August 1, 2002 48 (0.552 min): J2) 13:95150165110115150155130155 Figure 40. Mass Spectra for HFP (3.9 ppm) AIL: I'i Li a: Irv-:42? 5200? 3000: 25004 2500_ 2400? 2200- 20004 1500? 1500? 1400? 1200; 1000 5: Boo; 500i 400% 200 ?l?l rrua?1300 1200 ?1 1 oc- -- 1500 goo 300 - 500 .400 - 30? - zoo 1055 5'5 7'0 7'5 5'0 5'5 9'5 9'5 16016511019512'0155150155 I r' '1 TIC: A . . . Figure 41. Total Ion Chromatogram for HF (1.9 ppm) - I I Sedan (0.580 min): 9. 5 '15; (J C.) Figure 42. Mass Spectra for HFP (1.9 ppm) 12 umpuappV pun 1000101d 1891 111 aseqd 17 xgpueddv July 30, 2002 Phase Protocol: Laboratory-Scale Thermal Degradation of Perfluoro-octanylsulfonate and C3 Perfluoroalkyl Sulfonamides Prepared by: Environmental Sciences and Engineering Group University of Dayton Research Institute Summary The phase study will consist of 6 separate tests as shown in Figure 1. The main objective of this study is the simulation of the incineration of seven ?uorocarbon-based samples provided by 3M. Speci?c attention is being given to the potential formation of PFOS during the incineration of these materials. In?line and off-line 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 PF OS by Prior to the sample combustion analysis, the transfer ef?ciency for 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 ef?ciency tests for will be performed at the conclusion of the phase study. 1. SO: Transfer Ef?ciency Tests 2. Laboratory Spike Analysis for PFOS 3. Heated Blank Combustion Test iv 4. Combustion Tests for FC-1395, FC-807A, and 5. Heated Blank Combustion Test (repeat) 6. Transfer Ef?ciency Test for Figure 1. Chronological summary of tests to be conducted during Phase 1. 802 Transfer Ef?ciency Tests In the phase II transfer ef?ciency test, sulfur dioxide (802) showed recovery ef?ciency of 76.4 The standard was analyzed as a two-component mixture with SOF2 (thionyl ?uoride) and the SOF2 recovery rate was nearly 100%. Therefore, it is quite conceivable that was absorbed on the surface of reactor and transfer line. We will conduct another analysis to con?rm this result and to estimate the recovery coef?cient for the calculation of $02 concentration from the combustion tests. 2. Laboratory Spike Analysis for PFOS A 1 ug sample will be used for the PFOS spike analysis. This is the amount of PFOS that would be formed if 0.1% of the per?uoroalkyl portion of the ?uorochemical products used in this study were converted to PFOS in the reactor. Analysis of the extracts from these spiked reactor/transport systems will show if this amount of PFOS can be extracted and detected accurately. 10 mg of PFOS will be dissolved with 10 m1 methanol (Aldrich, HPLC grade) and 1 ul of solution (containing lug of PFOS) will be placed into a reactor (4 mm (id) 6 mm 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 of methanol used to dissolve the samples. The total volume of 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 m1: as calculated (0.2 cm 0.2 cm 3.14 7 cm) Total 1.1 ml The concentration of PFOS in the spike that is extracted with ?ve 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 PF OS (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 of PFOS subsequent to the high-temperature combustion stage would be indicative of likely PFOS release to the environment from actual incineration systems. Thus, the extraction procedure will focus on the high-temperature reactor of the highest temperature point) and the reaction product transfer lines between the reactor and the various sample collection systems. The following paragraph describes the analytical extraction procedure. The end of a 1/16? tee will be capped prior to extraction. The total amount of methanol used will be 5.5 ml, ?ve times the volume of the reactor/transfer line. The methanol will be stored in 40 ml vials (Wheaton CLEAN-PAK, clear certi?ed with pre-cleaned lined cap) and the vials will be connected to the end of 1/ 16? tubing using 1/ 16? stainless tubing. The other end of reactor will be connected to another 40 ml vial (Wheaten CLEAN-PAK, clear certi?ed 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 ?ow (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 collection and will be used for con?rming that all of 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 0 Flow controller ent th 1 Reieggir 1/16 Tubing 1/8 Tubing Reactor (4 6mm 7cm) 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 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 the sample collection using Tedlar sampling bags (0.5L, SKC Inc.). Two 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 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 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 ?ow 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 respectively. The residence time in the reactor (4 mm id. 6 mm o.d. 14 cm length with 8 cm effective length) will be ca. 2.0 s. The determination of the effective length of the reactor is discussed in Section 4. The ?ow rate will be controlled within $10 error. A majority of the ef?uent will pass through the PUF cartridge for sample collection and mlfmin will be directed into the GC column for in~line analysis. In-Zine GC-MSAnalvsis: A series with MS capillary column (30 length, 0.25 mm id, Agilent Technologies, Inc.) will be used for the phase study. The initial temperature of GC2 will be held at and sample will be concentrated at the head of the column for 2 and 2.5 min for reactor temperature of 600 and respectively. During this time period, PUF combustion ef?uent 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 of GC2 will be started. The initial temperature will be held for 1 minute and the temperature will be raised at 10?C/min up to The ?nal 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. of collection and analyzed using series GC-MS with SPEL-Q PLOT (Porous Layer Open Tubular) column (30 length, 0.53 mm id, SUPELCO). The Tedlar bags will be heated to ca. 50 to ensure that all of 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 that the MS capillary column may not effectively retain during in?line gas sampling. The initial temperature will be held at and 1 ml of 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 15?C/min up to The ?nal temperature will be held for 5 mmutes. All of reactorltransfer line systems including perprobe chamber and sample insert probes used in the Phase analyses will be appropriately packaged and stored for the future analysis. Ventilation Air System Data Acquisition Flow Controll Jill. . . Pressure valvcl Cartridges 2 Pyropmbe Flow Reducer Chamber (Pressure Controller) Furnace nos _eactor GC 0 Split Flow Controller MS GC2 GCI Pyroprobe Chamber 22 cm (7 9.5mm 8cm) 1/16 Tubing 1/8 Tubing Reactor 8 8 cm (4 6mm 14cm) aim 1/16 Tee 2cm 1/8 Tee 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 of 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 of 600 and and the sample collection will be performed twice for 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 ef?uent in?line analysis and PUF sample collection for the combustion test of the selected compounds. For off-line GC-MS analysis, the PUF cartridges in Figure 3 will be replaced by a Tedlar bag. Air and methane (if necessary) will be introduced into the pyroprobe chamber and the reactor to simulate incineration of the samples. The ?ow rate of He and air will be controlled by a ?ow controller (Porter Flow Instruments, and methane will be introduced using a calibrated syringe pump decienti?c). Because the methane ?ow rate is very low, it is necessary to use syringe pump to obtain accurate ?ow rates. The solid and liquid phase samples will be gasi?ed 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 of ignition will range from 1000 to and 20 to 40 seconds, respectively, depending on the actual sample being gasi?ed. The gasi?ed mixture will be mixed with the air stream and undergo incineration in the fused silica reactor. A portion of the ef?uent (1 ml/min) will be delivered to the GC-MS for product analysis and rest of ef?uent will be passed through two PUF cartridges for detection of PF OS using analysis at 3M environmental laboratories. Further details are provided below. Ventilation System A He Switching Valve 2 Switching High Voltage DC Power Supply Air Data Acquisition (1) "7 (2) and Analysis Switching Pressure Valve 1 Injection Flow Reducer :0 (Pressure Controller) (2) Syringe Pump Furnace yroprobe DB5 "art: and sample GC Column Reactor I Split Flow Controller MS GC2 GCI Figure 4. Experimental setup for the combustion tests. 1. Stoichiometric Reaction Mechanisms of Seven Samples Based on the elemental formula of the seven samples provided by 3M, four of 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 deveIOpment of the stoichiometric equations, it is assumed that is converted to C02, is converted to HF, is converted to N2, and is converted to $02. Phosphorous and potassium were excluded from the equation since the contribution of 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 de?cient samples to supply hydrogen to convert to HP. In that case, additional oxygen was supplied to convert in methane to C02. Table 1. Coefficients of Stoichiometric Combustion of Selected Samples Stoichiometric Atomic Contents of Samples Gas Products Sample 0; CH4 C02 H20 HF N2 FC-1395 1 1.01 1.21 0.110.26 0 0.06 0 0.98 0.05 1.05 0 1.21 0.06 0.055 FC-SOTA 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 11From the table above, stoichiometric equations can be derived for all of the samples. 2. Calculation of Necessarv Amount of Sample (Equivalent Amount of Fluorine in The amount of sample that will be incinerated was calculated to conserve the same amount of ?uorine for each sample and is tabulated in Table 2. All samples have the equivalent amount of ?uorine that is contained in 0.50 mg of PFOS. To facilitate calculations, we de?ne a "pseudo- molecular weight" to be the sum of the masses of the elements in the empirical formulation of each product as given in Table 1. The amount of air necessary for stoichiometric incineration for each sample was also calculated and is included in Table 2. Table 2. Amount of Sample That Contains Equivalent Amount of Fluorine in 0.5 mg of PFOS (Pseudo) Fluorine Mass of Sample to Amount of Air for Molecular Fraction by be incinerated Stoichiometric Sample Name Weight weight (mg) Incineration (ml) FC-l395?3l 43.62 0.527 0.57 (2.19) 1.50 51.567 0.519 0.58 (2.63) 1.37 PFOS 538 0.600 0.50 1.38 Values in parenthesis will be used for the actual combustion test. See sample amount adjustments. For example, the amount of that contains equivalent amount of ?uorine in 0.5 mg of PFOS can be calculated as: 0.5 (mg) 0.600/527 0.57 mg and the amount of air for stoichiometric incineration can be calculated as: 0.57 (mg) 0.001 (g/mg) /43.62 (g/mol) 0.98 (stoichiometric 02) 0.0821 (atm L/(mol K) 298 1 (atm) 1000 (ml/L) 0.209 (02 fraction in air) 3 1.50 ml The necessary amount of sample and air for other six compounds can be calculated in a similar manner. 3. Sample Amount Adiustments Since FC-1395 and FC-807A were provided in aqueous solution (water contents of 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 larger sample probe (2 4 mm (id. 1.5 cm length) and dried with He and moderate heat (less than before being mounted into the pyr0probe. (The larger sample probe will be used to enhance the drying process.) This process will aid the gasi?cation process by requiring less energy to gasify the active ingredients of the sample. Thermal gravimetric analysis show that signi?cant amounts of mass are lost for both of these samples at temperatures of ca. 150 to (see Figure 5 and 6). The ratio of the mass at ca. to the original mass is an indication of the mass lost due to water evaporation. The mass of FC-1395 and 807A before and after this drying process will be measured to con?rm that the active ingredients of the sample are not vaporized prior to insertion in the pyroprobe. which is a solid powder, will be placed into the sample probe (1 2 mm (id 2 cm length) with small amount of quartz wool support (0.5 cm in length) in the bottom of the sample probe. The quartz wool is necessary to hold the materials in place prior to the combustion test. FC-1395 100 - - ?"100 200 300 400 500 500 Temperature, Figure 5. Thermal Gravimetric Analysis (TGA) of FC-BOTA 1oo has? so? 60? La Weight Remaining 0 100 200 300 400 500 600 Temperature. 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 respectively. The ?ow rates for He and Air can be controlled within 10 and the methane ?ow rate can be controlled within i 5 Each compound will be incinerated under high excess air condition ranging from ca. 100 to 450 excess air. The concentration pro?le of the gasi?ed sample is not measured directly and assumed to be an average value in the excess air calculations described above. Oxygen and methane-de?cient conditions may occur in the reactor during the gasi?cation process for some of the samples while the pyroprobe is heated to high temperatures (1000 to and the volume of the gas expands by a factor of up to 2.5. In other words, during the gasi?cation process, the ?ow rate of the gasi?ed 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 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 of signi?cant digits. Therefore, the calculation may not exactly reproduce the numbers shown in Table 3 and 4. In Table 3, the necessary amount of CH4 for FC-807A can be calculated as: 0.58 (mg) 0.001 (g/mg) 51.6 (g/mol) 0.106 (stoichiometric requirement, see Table 1) 0.0821 (atm (mol K) 298 (K) 1 (atm) 1000 (ml/L) 0.03 ml The necessary amount of was then doubled to provide an excess of hydrogen atoms to scavenge ?uorine atoms as HF. The CH4 ?ow rate and sweeping time through the pyroprobe were calculated as shown below: 0.06 (ml) 1.00 (min) 0.06 (ml/min) The air ?ow rate to pyroprobe was added to sweep the sample out of the volume in 1 min. The volume of pyroprobe is 1.5 ml (0.352 x3.14 (cmz) 4.5 cm 0.2 (cm3). The necessary ?ow rate to sweep the sample out of the volume at is: 1.5 (ml) 1 (min) 293 (K) (260 273) (K) 0.84 ml/min Since 0.06 ml/min of 0.84 ml/min is provided by CH4, the air ?ow rate will be 0.84 0.06 0.78 ml/min. The necessary air ?ow rate to the reactor for sample combustion can be calculated by the stoichiometric amount of air for samme and sweeping time: 1.37 (ml) 1 (min) 1.37 ml/min The stoichiometric combustion ratio of methane to air is 1:9.57. Therefore the air ?ow rate to reactor for CH4 combustion can be calculated as: 0.06 ml/min 9.57 0.57 ml/min With the additional air flow rate shown in Table 3, the total gas ?ow rate is calculated as 10.28 ml/min. The residence time for 0.4 cm i.d. 8 cm effective length quartz tubing at is calculated as: 10 0.22 3.14 8 (ml) [10.28 (ml/min) 60 (S/min) (600 273) (K) I 298 (K) 2.00 s. The excess air ratio is the ratio of additional air to stoichiometric air. For FC-807A, 7.5 nil/min additional air flow will be introduced while 1.94 ml/min is the air ?ow rate for stoichiometric combustion (samme CH4). The excess air ratio is calculated as: 7.5 (ml/min)/ 1.94 (ml/min) 100 387 6. Effective Length of Reactor The effective length of the reactor was determined based on measured temperature pro?les at 600 and 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 the temperature was set at The effective length of 8 cm was obtained by allowing a deviation from the desired temperature by i which is i 3.3 of desired temperature. The measured temperatures at the center of the reactor and at a distance from the center are shown in Figure 7. For the reactor temperature of temperature was set at The 8 cm effective length was obtained by allowing a deviation from the desired temperature by i which is also i 3.3 of desired temperature. The measured temperatures at the center of the reactor and at a distance from the center are also shown in Figure 7. 600 900 Reactor Temperature Pro?le 1000 . . . . . . . . . . . . . .. . . . . . . . . 80.Temperature (Distance from Center (cm) Figure 7. Reactor Temperature Pro?le for 600 and The profiles are roughly symmetrical about the center of the reactor. 11 7. Experimental 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 ?ow rate of air and methane and the temperatures of furnace (600 or and the GC2 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 (id) 2mm 2.0 cm (length) or 2mm 4mm 1.5 cm (length), the net weight of sample measured, and the tubing carefully inserted into the pyroprobe. After the ?ow rate and temperature are properly set and sample preparation is completed, the system will be held for 1 minutes to allow the ?ow to stabilize. The cap for the pyroprobe chamber will then be removed and the perprobe quickly inserted into its chamber. Immediately afterwards, the perprobe will be ignited to gasify the sample. After the appropriate amount of time to sweep the gasi?ed sample from the pyroprobe chamber (1.2 times of sweeping time shown in Table 3 and 4), the air ?ow for the pyroprobe will be maximized (5 ml/min at room temperature, 8.9 ml/min at 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 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 gasi?ed. 12 5. Transfer Efficiency Test for Figure 8 shows schematic diagram of transfer ef?ciency test for 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 The helium ?ow rate will be set as 20 nil/min and the temperature in the GC oven will be set as 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 gasi?cation 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 System He High Voltage DC Power Supply Flow Controller I: PUF Switching I a Pyroprobc and Sample I Cartr'di Furnace I uartz Reactor l?I: Figure 8. Transfer Ef?ciency Test for 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 13 1. Signi?cant changes were made to the sample inlet and gasi?cation system. To satisfy the analytical requirements for PFOS detection by analysis by 3M, we determined that relatively large amounts of sample, 0.5 to several mg, had to be gasi?ed in the actual experiments. This amount of sample is much larger than initially estimated (ca. 10 to 100 ug) and could not be gasi?ed with the inlet available with the Advanced Thermal/Photolytic Reactor System (ATPRS). Preliminary experiments in phase II also demonstrated that higher gasi?cation temperatures were necessary to rapidly gasify the ?uorocarbon-based samples. As such, the System for Thermal Diagnostic Studies (STDS), equipped with a high- temperature pyroprobe that can gasify milligram quantities of material, is proposed for the phase 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 n-octane) for all of 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 of 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 de?cient and requires hydrogen source to convert 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 Preliminary combustion tests with several samples indicates that many combustion byproducts were formed at but those combustion byproducts were not observed at higher temperature (750 and and the GC-MS total ion chromatograms for these higher temperatures were very similar. Therefore it is proposed that two temperatures are suf?cient to analyze the combustion phenomena of the selected samples (600 and 15 November 4, 2002 Addenda for Phase Protocol 9. 2ncl Transfer Ef?ciency Test for (PFOS) In addition to the transfer ef?ciency tests speci?ed in phase protocol, direct transfer ef?ciency tests where the gasi?ed 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 ef?ciency tests in the phase protocol address sample transport from the pyroprobe to the combustion reactor exit. Figure 9 shows a schematic diagram of the direct transfer ef?ciency test for PF OS. The gasi?ed samples will be collected using two PUF cartridges in the similar manner as described in Section 5 of the phase 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 through the entire analysis. The detailed ?ow pro?les 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 gasi?ed. After the sample is placed in the pyroprobe, the ?ow will remain at 0.63 ml/min for 94 seconds while the sample is gasi?ed at for 40 seconds. The ?ow 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 of PFOS at The calculated entire volume is 3.79 ml as shown the detail below: Pyroprobe chamber: (0.35)2 (cmz) 3.14 8 (em) 3.08 ml Transfer line: (0.108)2 (cmz) 3.14 19.5 (cm) 0.71 ml Total: 3.79 ml The system will be extracted with methanol using ?ve times the volume of 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. November 4, 2002 Table 3. Flow Rate Pro?le for Direct Transfer Ef?ciency Test Time Period Pyroprobe Flow Volume (sec) Rate (ml/min) (m1) 0 60 0.63 0.63 60 85 0.00El 0.00 85 179 0.63 0.99 179 189 0.63 4.53b 0.43 189 219 4.53 2.27 Total Volume (ml) 4.32 a No ?ow due to open system to insert the sample. Linear inerease (approximate) Ventilation :m He High Voltage DC Power Supply Flow Controll DO PUF Cartridges Pyroprobe and Sample Cartridge Figure 9. Direct Transfer Ef?ciency Test for PFOS. November 4, 2002 10. Additional Extraction Analysis of Unheated Sample Transport Lines In addition to the extractions speci?ed in the phase protocol, the unheated sample transport lines 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 This analysis will determine if PFOS condensation occurs while the ef?uent is being collected using ambient temperature PUF sampling cartridges. The method will be similar to other extraction analysis. The measured volume of 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 Using Single PUF between 600 and Combustion Test. After combustion tests of the ?rst three samples were completed, we decided to perform another blank combustion analysis using a single PUF after the combustion test at but before the combustion test at for the rest of the samples (FC-807A and PFOS). The temperature of the GC oven and reactor will be set at 260 and respectively. Table 4 shows the ?ow pro?le that will be performed for this analysis. Table 4. Flow Rate Pro?le for PUF Collection (Blank Analysis between 600 and Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (sec) Rate (ml/min) (ml/min) (ml/min) (ml) Air Air 0 120 9.70 0.84 10.54 21.08 120 130 9.70 0.84 -) 4.633 10.54 9 14.33 2.07 130 140 9.70 4.63 14.33 2.39 140 - 160 8.89 (He)b 4.53 13.42 4.47 Total Volume (ml) 30.01 a Linear increase (approximate). Switched to helium for sweep Air and helium will be used for the sample collection. The ?ow rate for the reactor and the perprobe will be same as the actual combustion test at Air will ?ow for 120 seconds and then increased to the maximum ?ow 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. November 4, 2002 12. 3rd Transfer Ef?ciency Test for PFOS (Sample in Reactor) Another transfer ef?ciency test where PFOS is directly placed in the reactor and gasi?ed will also be conducted. This analysis will demonstrate the PFOS transport ef?ciency of the overall system of the combustion reactor. It will also demonstrate how ef?ciently the PUFs capture the PF OS that exits the reactor in the vapor/aerosol phase. Figure 10 shows a schematic diagram of 3rd transfer ef?ciency test. in-line analysis, sample collection using PUF, off-line analysis using Tedlar 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 analysis for PFOS gasi?cation with air. 2. Tedlar Bag Collection and off-line analysis for PFOS gasi?cation with air. 3. Methanol extraction for PF OS gasi?cation with air. 4. PUF collection and in-line analysis for. PFOS gasi?cation with He. 5. Tedlar Bag Collection and off-line analysis for PFOS gasi?cation with He. 6. Methanol extraction for PF OS gasi?cation with He. The sample will be loaded into a sample probe and placed in the middle of the reactor. The gasi?cation 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 and then the reactor will be heated to the appropriate temperature. The reactor temperature will be between 525 and depending on the sample and carrier gas. The temperature will be held for 5 minutes for sample collection and in-line analysis. The PUF collection, in-line analysis and off-line analysis will be performed in the similar manner as described in Section 5 of the phase protocol. The ?ow 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 of 2.03 ml. The reactor/transfer line, valve system will be extracted by methanol using a volume equal to 5 times the volume of 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. November 4, 2002 Ventilation Switching System Valve 2 Air He ?7(2 . . Flow 0 PUF Controller Cartridges Valvel (nu? Furnace uartz Reactor Split Sample Probe Figure 10. Schematic Diagram of 3Ird Transfer Ef?ciency Test November 4, 2002 13. Sulfur Recovery Analysis Sulfur recovery rate as using the in?line system was not quantitatively repeatable. This was due primarily to the low peak resolution using the cryogenic focusing method at with a holding time of ca. 4 min. Because the peaks using the off-line system were much sharper than those observed using in?line we decided to use off-line analytical results to quantitatively analyze the sulfur recovery analysis as 802. 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 using the Tedlar bag (SKC Inc., 0.5 L) to construct the calibration curve. The column and the operating conditions will be same as used for off-line analysis of the actual combustion tests. Each concentration will be performed twice and the average will be taken. 13.2 Transfer Ef?ciency Analysis Known amount of standard will be injected into reactor and collected along with carrier gas (air) ?ow by 0.5 Tedlar bag. 1 ml of collected sample will be injected to off-line system and recovery rate will be calculated using the calibration established above. Figure 11 shows the schematic diagram of transfer ef?ciency test. The reactor/transfer line system will be heated at throughout the transfer ef?ciency test. Dry air will be used as a carrier ?ow. The ?ow 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 of 4.0% concentration 802 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 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 of molar number collected over the total amount of molar number injected. The test will be conducted twice and the average will be taken. Analytical Report Analytical Results for the University of Dayton Research Institute Study Titled ?Laboratory-Scale Thermal Degradation of Perfluoro-Octanyl Sulfonate and Related Precursors? Comblned Laboratory Report for 502-0320, E02-0821. EOZ-OBBT, 502-0395. E02-0899, [502-0916 E02-0917. E02-0926, Elm-0968, Elm-0969, and Testing Laboratory 3M Environmental Technology Safety Services 3M Environmental Laboratory 2-3E-09 935 Bush Avenue, St. Paul, MN 55106 Laboratory Contact William K. Reagan, Bldg. 2-3309 PO. Box 3331 St. Paul. MN 55133-3331 Phone: (651 778-6565 FAX: (651) 778-6176 Requester Eric A. Rainer 3M Environmental Technology Safety Services Bldg. 2-3E-09 P.0. Box 3331 St. Paul, MN 55133-3331 Page of 30 3M Environmental Laboratory University of Dayton Incineration Study 1 I Introduction Solvent extracts and polyurethane foam (PUF) cartridges (Supelco, cancer-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 Per?uoro-Octanyl Sulfonate and Related Precursors?. Sample results presented here were generated at 3M using LCIMS instrumentation to detect and quantitate the PFOS anion 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 ?nal report. "saapr?'n?cerpr 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 Dates of receipt of all samples are documented in the raw data. Samples and E02-0899-43012 were not located with the associated samples in sample check-in. These samples were associated with the extraction blank and ?rst 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, ?rst and second extraction samples (Em-084042716, E02- 0840-42714, 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 B. and and were identi?ed 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 analer degradation. especially since study samples were subjected to the thermal degradation study conditions. It is also expected that the ?uorochemicals measured are stable in methanol over the time period of this study. Page 2 of 30 3M Environmental Laboratory University of Dayton Incineration Study 4' Methods - Arraiytical and-I'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 LCIMS. 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 clean 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 ?fteen seconds and then inverted ?ve times to ensure proper mixing. Then the sample was allowed to sit for ?fteen minutes to allow for desorption of the analytes of interest. After ?fteen minutes. the sample was drained and washed again with the same twenty milliliters an additional four times for a total of ?ve washes. After the ?fth wash. the methanol was collected and aliquoted into a sample vial for analysis via Analysis of samples was conducted based on ETS-8-155.1 ?Analysis of Waste Stream. Water Extracts or Other Systems Using HPLC-ElectrosprayiMass Spectrometry.? This method is not written speci?cally for the extraction of PUF cartridges. just for the analysis of the analytes of interest via LCIMS. The method was modi?ed (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 coef?cient of determination is to be greater than 0.990. CCVs must be within 125%. the system suitability must be relative standard deviation (RSD) for area counts and RSD for retention times. and the standards should be within 125% (lower limit of quantitation (LLOQ) i30%) of their true value. Any deviations from this method are discussed in section 5 of this report. Samples were analyzed on an Agilent 1100 Series in the negative ion mode. Approximate conditions are presented below. Actual conditions are documented in the raw data. LC CONDITIONS: Column Flow: 0.300 ml/mln Solvent A: 2 mM Ammonium Acetate Injection Volume: 3-5 pL Solvent B: Methanol Column Temperature: Gradient: Column: Betasil C18 Time %8 Column Size: 2x50 mm. 5 0.00 85 15 0.50 85 15 3.00 0 100 5.50 0 100 6.00 85 15 9.00 85 15 Page 3 of 30 3M Environmental Laboratory University of Dayton Incineration Study MS CONDITIONS: Mode: SIM PFOS SIM Ion: 499 Polarity: Negative Cap: 4000 5 Analysis 5.1 Calibration Calibrations curves were constructed using at least ?ve concentrations with quadratic ?tting. All coef?cients of determination were greater than 0.990 and all calibration standards used in the calibration curves were within the LOO within 130%. Calibration standards outside this range that were excluded are documented in the raw data along with technical justi?tion for deactivation of curve points. Continuing calibration veri?cation standards (CCVs) were analyzed after no more than 10 samples. All CCV recoveries were within 125% as speci?ed by the method. 5.2 System Suitability Out of the ten analytical runs ail system suitabi?ties passed for PFOS except for on 10104102. The system suitability was exceeding the 5.0% RSD criterion typically allowed. Since all calibration curves and CCVs all passed for this 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 of PFOS. This methanol blank was followed by which had PFOS levels below the LLOQ (<5.00 Since the next sample following the blank was 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. Page 4 of 30 3M Environmental Laboratory University of Dayton incineration Study 5.5 Sample Calculations Sample Calculation: Final Result (ug) Instrument Result (Hg/L)XDilution Factorx Extraction Volume (L) So fcrE02-0968-43362 (TE3-EX-PFOS-R-3) Final Result (ug) 27035?x50x03102 138 ug Polyurethane Foam (PU F) Cartridge spike recoveries: instrument Result (cg/L) 0.02 Spiked Amount (11 g) x100 Percent Recovery 80 for (PFOS): 33.23?g?xonzL Percent Recovery 100 76% . ug re Baa-smea- Individual sample results are presented in appendix A. Each sample is identi?ed 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 (or ng/rnL or parts per billion) and in pg (if applicable) for each analyte of interest. Samples that were not detected above the lower limit of quantitaticn (LLOQ) are reported as less than quanti?es with the numerical value being the LLOQ for the analysis of that particular sample. Laboratory Control Spikes are presented in appendix and are reported in pgluL and the percent recovery is given. Averages and standard deviations are only calcuiated for each Spiking level of the Laboratory Spikes. Individual samples were not corrected for recovery. 7 Da ta Sample Retention The ?nal report and raw data will be retained according to 3M Environmentai Lab standard operating procedures. Page 5 of30 3M Environmental Laboratory Appendix A: Individual Sample Results Appendix 8: Laboratory Control Spikes Appendix C: Example Chromatograms University of Dayton Incineration Study Page 6 of 30 3M Environmental Laboratory University of Dayton Incineration Study 9 3mm; William K. Reagen, Techni Manager Da'te KW 9/21/02; Quality Assurdwce Representative Da'te 05/22 /03 Kent R. Senior Research Chemist Date Page 7 of 30 3M Environmental Laboratory University of Dayton Incineration Study Appendix A: Individual Sample Results Page 8 of 30 3M Environmental Laboratory Sample [102-082042500 1302082042502 11201-9001 0202-0820-4250! 1302-0820?42505 11131-1 1302-0820-4250? PFOS 1 502082142520 2 1502-0840-4303 15024184042709 FC1395-600-2 302-0811042710 FC1395-900-1 1302-0840-4271 1 FC 1395-900-2 1302-0840-4232 FC1395-BLK-PUF 1102-0841014 F01395 EXTRACT E02-0840-B FC1395 EXTRACT 1502?08404: 1031395 EXTRACT 1302-0867-4290! FC807-600-2 1302-0867-42905 302-0361429015 FC807-900-1 1302-0867?4290? 1302086742908 FC807-BLK-PUF 1302-0867-0909 FC807-0 EDI-086742910 1502-0867-4291 FC802-2 [502?0315742912 1302089542970 PFOS-600-1 802-0895429111 PFOS-600-2 1502-0895-4291! 302489542973 10108-90041 802-0895429114 1302-0895-4296 PFOS-BLK-FUF 1302089542926 PFOS-O 1302-0895-4297? 002-0895425178 PFOS-2 1302039542979 PFOS-BLK 1502089943007 11132-6001 13024139943009 11132-9001 50208994301 1 302-0910430116 PFOS-TE-Z E020916-43087 TE-BLK 1502-0917-6094 502-0917430115 PFOS-TEZ-Z 1302091743096 TEZ-BLK 802-0917431116 PFOS-TEZX-2 13024191743103 PFOS-TEZX-BLK 1302-0926-4314! EDI-092643142 NHB-Z Roz-092643143 NHB-BLK Bum-35343360 PFOS-HE-TE3-1 1302-0968-4336! PFOS-HE-TEJ-Z 802-0913843362 TE3-EX-PF08-R-3 1302-0968-6363 TES-BX-PFOS-R-4 13024196343365 (Willa) 10.0 4.10.0 <10.0 14.9 (10.0 232 40.5 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 6.00 25 . 1 64.0 6.32 4.31 9.01 6.00 25.5 15.4 8.61 6.06 10.0 (10.0 (10.0 6.00 6.00 6.00 <10.0 <10.0 60.0 89? (10.0 <10.0 6.00 6.00 6.00 2330 44.0 13 530 150 2218 102 6.20 <0.20 410.20 0.082 6.55 1.3 0.22 10 10 <10. 10 <0.10 <10. 1 0 40.028 6.028 <0.028 10 10 (0.10 [0 10 41.10 (0.014 (0.023 <0.028 <0.028 0.50 1.3 0.13 0.086 0.18 6.10 0.070 0.085 0.047 0.033 ?0.20 ?0.20 <0.20 [0 10 10 6.20 6.20 ?0.20 1? <0.19 1 9 <0.028 <0.028 41.023 4? 0.88 138 1.5 6.2 0.29 PFOS Corrected" (0.25 40.25 6.25 0.10 <0.63 . 1.6 0.28 12 <0.12 <0.12 12 <0.12 <0.035 <0.035 <0.035 12 12 <30. 12 12 12 <0.12 <0.017 <0.035 <0.035 (0.035 0.62 1.6 0. 16 0.1 1 0.22 12 0.09 1 0.059 0.041 ?0.25 <0.25 <0.25 <0.12 [2 <0.12 (0.25 <0.25 <0.25 21 <0.24 <0.24 <0.035 <0.035 40.035 53 1.1 1'11 1 .9 7.7 0.35 University of Dayton Incineration Study Page 9 of 30 3M Environmental Laboratory Bin-096343366 TE3-EX-BLK-2 ISM-096843370 PFOS-BIX-TBS E02-0969-4337l ISM-096943372 PFOS-AIR-TEB-Z E02-0969-43373 1302-0969433? TEB-BX-PFOS-R-Z 1102-0969433? 502-0969453376 TE-EX-PFOS-V-Z Bin-097143393 (Pt/"Ll <10.0 997 0.0 1908 35.4 696 22.8 4510.0 II. ?0.20 20 40.10 19 0.36 I .9 0.064 .00 PFOS result: we presented I: corrected for purity the anion. salt. Thecorroctionsuwdwu 0.8060 (0.869 pm?ity 0.9275 correction for pot-slim). These ample: arejust blanks oflhe methanol used in the study. There is no associated volume to calculne u: for the? samples. University of Dayton Incineration Study PFOS Corrected" fun) in (0.25 25 12 24 0.45 2.4 0.079 ti. Page 10 of30 3M Environmental Laboratory University of Dayton Incineration Study Appendix B: Laboratory Control Spikes Page 11 of30 3M Environmental Laboratory Table l: 1 uELaborat? Control Spikes PFOS percent Sample (pg/Ill.) recovery RPD 020913LCS-1 43.4 87% 4.9% 45.6 91% 020913LCS-1 45.6 91% 4.0% 020913LCS-2 47.4 95% 020923LCS-1 38.2 76% 14% 020923LCS-2 44.0 88% 020923LCS-1 37. 1 74% 19% 020923LCS-2 44.8 90% 020930LCS-1 35.3 71% 3.3% 020930LCS-2 36.5 73% 34.7 69% 10% 021001LCS-2 38.4 77% 020927LCS-1 41.5 83% 2.0% 020927LCS-2 42.3 85% Average 41.0 82% Standard Deviation 4.27 8.5% RSD 10% The true value of PFOS in the LCS samples is 50.0 pm (1.00 ug) RFD-Relative Percent Difference ITable2:10u Laborato Controls ikes PFOS percent Saple (pg/0L) recovery RPD 020913LCS-3 464 93% 6.8% 020913LCS-4 497 99% 489 98% 5.9% 020913LCS-4 519 104% 020923LCS-3 414 83% 4.6% 020923LCS-4 433 87% 020923LCS-3 434 87% 4.3% 020923LCS-4 453 91% 020923LCS-3 425 85% 4.6% 020923LCS-4 445 89% 020923LCS-3 458 92% 3.7% 020923LCS-4 476 95% Average 459 92% Standard Deviation 31.6 6.3% RSD 7% The true v?ue in the LCS samples in 500.0 (10.0 113) University of Dayton Incineration Study Page 12 01?30 3M Environmental Laboratory University of Dayton Incineration Study Appendix 0: Example Chromatograms Page 13 of 30 VI DI .- Hui1-: HUI IlI'll 1 II: samurnull 3p]. :m?o 31161233160; (Itlc1305?iI11 ?5 Iv :u ?adls ?21:31.; ?Jl realign-1:; II. VI 1,1[13 an ?Lun' rim?: 131:? mam) =ou :311 113; L, tap: on?) .. 99 air-urn: 0=Id311[ I a Immuiaa? .. . tint-3:434: 92 1-1: a? al I - at '31: .31 m: 011] mi go gm: 1 b! "It 1? 7.. 111 _mu_ 4 ark _h .I 353 2:33.. ?ts-"An?.5391.thaw I .r nan-1 mu ?52.4 I 1 ?will 3. ??dnd I?Wmamndu 27.. a LDOOH "n iptoint?ttca. .- ?u n. a .SDII:eanh-Fglm an? .1 mtOmFJ?mdeJmmr .. . I0 'm 5: '11 (c1 13; f] 13*! oi: an tu I Ila}. . i1c,Jykh!nao :7 ?ii? LE Hivtnwerw a: GH PI Pa 2 'ntli:h:hyi EETIT It?x? mu!? 9 ?gangs? $125: ED :nmtaat i i mnixnm -1 11 -: n: d?-inf gtcin\ncu 6 A a a5. ?23 :1 man 1.3. sum: was?any: ?1 a .q naguuo-u-unno-ugopg panhanoa all: .8 I I I i tilCm-cm. aptui.unh1y ttuyxln_ nan-Id - as If If! Inc ?Ii: lh nun? i IDO amnnJ - bu.1. sunnu_m I Elma - who :uni?did HuiLaban m? .u a .lpbobnt Ibtca. I a. to .Db-rglo mum .. . a r. 3'00 I mi of .ytt Inc :rat 13Hawnnma laainf .4 41?: 04 ll UH I304 I 2.1: ml 'yli IE1: Zl?'c miluungt'uudch 4134?: as: and .14 1" 2.1! than-93" E?tf: ?5'1351? A a . 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Date za-SKP-mioa muss C11 Pile: 1111330021.]: Ala bottle: 21 011 Factor: 1.000013 u; Integrator: Falcon Compound Sublisc: ?3 Target yer-ion: 4.12 1:0i PIWEIIJJIQ Hon: u! m1!" .Jj mm unu- 0.51 an" mu :2 nun- two-4 0.4 on. n-uu?I sun?u? a nu an: can I-?l ?mm mm dl.? me; all La? I.au um nuns In ?iwdi'ili'llu' Imam? Inn cl. . I. 2.4-: 1.:5 .. r- in?: Hi 33' '45 ill in ?Iin Page 22 of 30 3M Environmental Laboratory University of Dayton Incineration Study Data run: ?Run cum: et\chem it: Pa 1 Rupert nan: abun?zuo: agar: h? g. 3' m? as ani Laboratory u} Ni Barons-429? M. zs-szr-aaoz 19:21 Inst In: Data 2110 Sign Into Pros-an by 8 I ?Eta:urget\tatgal:\chen\1tchv. -b\!020926 .m 21-May-2003 09:35 nick Guam: lypes urn 35-SEP-2002 19:15 C11 Fill: {mil .4 a) 2 2' D11 Factor: 1.00900 Integrator; ?icon carpound sublist: ngeL Version: ILIZ Drool-ling East: '19555 In: um rm II In l'l' n.1- n' um {mid-i lulu t-I?n-o- .nno-n .4 I It?! 0" LilliPage 23 of 30 0?t'33. 1 :3 non)- :Itsdm?. gundnq?rmm ?51511 Ind Im?rl?x?q?llr?npmwa ?up muBIQGrnI.-..-mas_ I Mu ?0307.. n- on:- . ::Hm La IDI 2? i- . aluil r0910. ETI-IH. .I no.- 5 I . Huh? 3 9:5 M: In 5: i\'alnul: rm: s: w- Imzn I[Ian rosanc Id 31161531166: In. 1 ll" 1 CI u-mutxzalau AT: Lu_4 mt