Document 65pJ6gm7aEeDGXa2byVZBmnx3

30) Laboratory incineration study of PFBS and Fluorochemical polymers UDR-TR-2002-000153 SANITIZED DEC 0 9 2003 12/16/2002 Laboratory-Scale Thermal Degradation of Perfluoroalkyl Sulfonates and Perfluoroalkyl Sulfonamides 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 45469-0 132 In response to a verbal and written requ,est from: 3M Environmental Lab, ET&SS US-MNSPO2, 0002-03-E-09 P.O.Box 33331 St. Paul, MN 55133-3331 Final Report Laboratory-Scale Thermal Degradation of Perfluoroalkyl Sulfonates and Perfluoroalkyl Sulfonamides This report covers the efforts performed by the University of Dayton Research Institute (UDFU), Environmental Science and Engineering Group, Dayton, OH 45469-0 132, during the period from March 2001 to December 2002. The work was conducted under a Letter of Agreement dated March 20,200 1. The work was administered under the direction of the 3M Environmental Lab, ET&SS, and the Project Monitor was The UDRI Program Monitors were Philip Taylor and Tak Yamada. PI&> /L 7iLf16-b Dr. Philip Taylor" //7/0-3 Date J&A<d Dr. Tak Yamada I /7/03 Date 1 TABLE OF CONTENTS SECTION Executive Summary I Background 2 Phase I: Objectives and Test Protocol 3 Phase 11:Method Development 4 Phase 111: Revised Test Protocol 5 Experimental Results 5.1 SO;! Transfer Efficiency Test PAGE xii i 3 6 5.2 Laboratory Spike Analysis for PFOS and PFBS 9 5.3 Heated Blank Combustion Analysis 10 5.3.1 In-line GUMS Analysis 10 5.3.2 Off-line GCMS Analysis 12 5.3.3 ReactodTransfer Line Extraction and LC-MS Analysis 13 5.4 Combustion Tests of Seven Selected Compounds 5.4.1. Combustion Test 5.4.1.1 In-line G C M S Analysis 5.4.1.2 Off-line G C M S Analysis - 5.4.1.3 LC-MS Analysis of Extracts 5.4.1.4 LC-MS Analysis of PUFs 5.4.2 Combustion Test 5.4.2.1 In-line GUMS Analysis 5.4.2.2 Off-line GCMS Analysis -5.4.2.3 LC-MS Analysis of Extracts 5.4.2.4 LC-MS Analysis of PUFs 5.4.3. FC-1395 Combustion Test 5.4.3.1 In-line GC/MS Analysis 5.4.3.2 Off-line GC/MS Analysis 5.4.3.3 LC-MS Analysis of Extracts 5.4.3.4 LC-MS Analysis of PUF 5.4.4 FC-807A Combustion Test 5.4.4.1 In-line GUMS Analysis 5.4.4.2 Off-line GUMS Analysis 5.4.4.3 LC-MS Analysis of Extracts 5.4.4.4 LC-MS Analysis of PUF 13 14 14 18 19 - 19 19 20 21 22 23 23 24 25 26 26 27 28 29 30 31 .. 11 SECTION TABLE OF CONTENTS (Continued) 5.4.5 5.4.6 5.4.7 * . 5.4.5.1 Combustion Test In-line GC/MS Analysis 5.4.5.2. Off-line GUMS Analysis 5.4.5.3 LC-MS Analysis of Extracts 5.4.5.4 LC-MS Analysis of PUF Cartridges PFBS Combustion Test 5.4.6.1 In-line GUMS Analysis 5.4.6.2 Off-line GUMS Analysis 5.4.6.3 LC-MS Analysis of Extracts 5.4.6.4 LC-MS Analysis of PUF Cartridges PFOS Combustion Test 5.4.7.1 In-line GC/MS Analysis 5.4.7.2 Off-line GUMS Analysis 5.4.7.3 LC-MS Analysis of Extracts 5.4.7.4 LC-MS Analysis of PUF Cartridges 5.5 Revised Chemical Composition of 5.6 Heated Blank Combustion Analysis 5.6.1 In-line GUMS Analysis 5.6.2 Off-line GCMS Analysis 5.6.3 LC-MS Analysis of PUF Cartridges 5.7 Transport Efficiency Tests for PFBS and PFOS 5.7.1 Transport Efficiency Test 5.7.2 Transfer Efficiency Test 5.7.3 Transfer Efficiency Test 5.8 Sulfur Recovery Rate as Sol, S02F, and S02F2 .. 5.9 Extracted Ion Analysis 6 Discussion 7 Conclusions 8 References PAGE 31 32 33 34 34 35 36 37 38 39 39 41 42 43 43 44 44 I 45 46 46 47 47 48 49 52 . 54 60 64 65 ... 111 TABLE OF CONTENTS (Continued) SECT1ON APPENDICES I Timeline and Dates of Testing 2 Phase I1 Final Report and Raw Data 3 Phase 111Test Protocol and Addendum 4 The 3M Analytical Report 5 Spreadsheet L i h g the UDRI Combustion Tests with the 3M Analytical Results PAGE iv LIST OF FIGURES FIGURE 2.1 Schematic of the System for Thermal Diagnostic Studies 5.3.1 In-line GUMS Ion Chromatogram for Heated Blank at 600C 5.3.1.1 In-line GCMS Ion Chromatogram for Heated Blank ai 900C 5.3.3 Off-line GUMS Ion Chromatogram for Heated Blank at 600C 5.3.4. Off-line GUMS Ion Chromatogram for Heated Blank at 900C 5.4.1.1 5.4.1.2 In-line GC,/rjrSIon Chromatogram for at 600C Mass Spectra for the Wide Peak at 12 to 13 Minutes 5.4.1.3 5.4.1.4 In-line GCI'MS Ion Chromatogram for Off-line GCMS Ion Chromatogram for at 900C at 600C 5.4.1.5 .Off-line GUMS Ion Chromatogram for at 900C 5.4.2.1 In-line GUMS Ion Chromatogram for at 600C 5.4.2.2 In-line G C M S Ion Chromatogram for . .. 5.4.2.3 Off-line GC/MS Ion Chromatogram for at 900C at 600C 5.4.2.4 Off-line GUMS Ion Chromatogram for at 900C 5.4.3.1 In-line GCMS Ion Chromatogram for FC-1395 at 600C 5.4.3.2 In-line GCMS Ion Chromatogram for FC-1395 at 900C 5.4.3.3 Off-line GUMS Ion Chromatogram for FC-I 395 at 600C 5.4.3.4 Off-line GUMS Ion Chromatogram for FC-1395 at 900C 5.4.4.1 In-line GCMS Ion Chromatogram for FCr807A at 600C 5.4.4.2 In-line GUMS Ion Chromatogram for FC-807A at 900C V PAGE 4' 11 12 12 13 17 17 15 18 19 21 21 .- 22 22 25 25 26 26 29 29 LIST OF FIGURES (Continued) FIGURE 5.4.4.3 Off-line GC/MS Ion Chromatogram for FC-S07A at 600C 5.4.4.4 Off-line GUMS Ion Chromatogram for FC-807A at 900C 5.4.5.1 In-line GUMS Ion Chromatogram for at 600C 5.4.5.2 In-line GCIMS Ion Chromatogram for at 900C 5.4.5.3 Off-line G C M S Ion Chromatogram for at 600C 5.4.5.4 Off-line GCIMS Ion Chromatogram for at 900C 5.4.6.1 In-line GC/MS Ion Chromatogram for PFBS at 600C 5.4.6.2 In-line GC/MS Ion Chromatogram for PFBS at 900C 5.4.6.3 Off-line G C M S Ion Chromatogram for PFBS at 600C 5.4.6.4 Off-line GCMS Ion Chromatogram for PFBS at 900% 5.4.7.1 In-line GCMS Ion Chromatogram for PFOS at 600C I 5.4.7.2 In-line G C M S Ion Chromatogram for PFOS at 900C 5.4.7.3 Off-line GUMS Ion Chromatogram for PFOS at 600C 5.4.7.4 Off-line GC/MS Ion Chromatogram for PFOS at 900C 5.6.1 In-line G C M S Ion Chromatogram for Heated Blank at 600C 5.6.2 In-line GCMS Ion Chromatogram for Heated Blank at 900C 5.6.3 Off-line GC,'MS Ion Chromatogram for Heated Blank at 600C 5.6.4 Off-line GUMS Ion Chromatogram for Heated Blank at 900C 5.8.1 SO2 Calibration Curve (Molar Number vs. Peak Area) 5.9.1 Total Ion Chromatogram and Corresponding HFID Signal for Combustion o f . @, 600C (off-line sample) vi PAGE 30 30 33 33 34 34 37 37 38 38 41 42 42 43 45 46 47 45 53 56 LIST OF FIGURES (Continued) FIGURE 5.9.2 Extracted Ions (CF2H-51, SOF-67, CF3-69, C.FzCF2H-101, and C2Fj-119) and Corresponding HFLD Signal for Combustion of a; 600C (off-line sample) 5.9.3 Off-line H:FID Signal for PFBS Combustion at 600C (off-line sample) 5.9.4 HFID Signal for PFOS Combustion at 600C (off-line sample) 5.9.5 HFTD Signal for PFOS at 900C (off-line sampie) PAGE 57 58 58 59 vii .-. LIST OF TABLES TABLE 3.1 Linear Fit Equations and Detection Limits 3.2 Transport Efficiency 5.1.1 Transport Efficiency Test Results 5.2.1 Net Amount of Sample Loaded 5.2.2 PFOS Laboratory Spike Analysis 5.2.3 PFBS Laboratory Spike Analysis 5.3.1 Flow Rate Profile for Heated Blank Analysis at 600C 5.3.2 Flow Rate Profile for Heated Blank Analysis at 900C 5.3.3 Methanol Extraction Results for Heated Blank Analysis 5.3.4 PUF Extraction Results for Heated BIank Analysis 5.4.1.1 Net Amount of Gasified Sample for Combustion Test 5.4.1.2 Flow Rate Profile for Combustion Test at 600C 5.4.1.3 5.4.1.4 Flow Rate Profile for Combustion at 900C Methanol Extraction Results for Combustion Test 5.4.1.5 PUF Extraction Results for Combustion Test 5.4.2.1 Net ,4mount of Gasified Sample for Combustion Test 5.4.2.2 Flow Rate Profile for Combustion Test at 600C 5.4.2.3 Flow Rate Profile for Combustion Test at 900C PAGE 6 7 9 9 10 10 11 11 13 13 14 15 16 19 19 20 20 20 ... Vlll LIST OF TABLES (Continued) TABLE 5.4.2.4 5.4.2.5 5.4.3.1 Methanol Extraction Results for .. PUF Extraction Results for Combustion Test Combustion Test Net Amount of Gasified Sample for FC-1395 Combustion Test 5.4.3.2 Flow Rate Profile for FC-1395 Combustion Test at 600C 5.4.3.3 Flow Rate Profile for FC-1395 Combustion Test at 900C 5.4.3.4 5.4.3.5 Methanol Extraction Results for FC-1395 Combustion Test PUF Extraction Results for FC- 1395 Combustion Test 5.4.4.1 Net Amount of Gasified Sample for FC-807A Combustion Test 5.4.4.2 Flow Rate Profile for FC-807A Combustion Test at 600C 5.4.4.3 Flow Rate Profile for FC-807A Combustion Test at 900C 5.4.4.4 Flow Rate Profile for Blank Analysis between 600 and 900C 5.4.4.5 Methanol Extraction Results for FC-807A Combustion Test -~ 5.4.4.6 PUF Extraction Results for FC-807A Combustion Test 5.4.5.1 Net Amount of Gasified Sample for Combustion Test 5.4.5.2 Flow Rate Profile for Combustion Test at 600C 5.4.5.3 Flow Rate Profile for Combustion Test at 900C 5.4.5.4 Flow Rate Profile for Blank Analysis between 600 and 900C 5.4.5.5 Methanol Extraction Results for Combustion Test 5.4.5.6 PUF Extraction Results for Combustion Test PAGE 22 23 23 24 24 26 27 27 27 28 28 30 31 31 31 32 32 34 35 ix LIST OF TABLES (Continued) TABLE 5.4.6.1 Net Amount of Gasified Sample for PFBS Combustion Test 5.4.6.2 Flow Rate Profile for PFBS Combustion Test at 600C 5.4.6.3 Flow Rate Profile for PFBS Combustion Test at 900C 5.4.6.4 Flow Rate Profile for Blank Analysis between 600 and 900C 5.4.6.5 Methanol Extraction Results for PFBS Combustion Test 5.4.6.6 PUF Extraction Results for PFBS Combustion Test 5.4.7.1 Net Amount of Gasified Sample for PFOS Combustion Test 5.4.7.2 Flow Rate Profile for PFOS Combustion Test at 600C 5.4.7.3 Flow Rate Profile for PFOS Combustion Test at 900C 5.4.7.4 Flow Rate Profile for Blank Analysis between 600 and 900C 5.4.7.5 Methanol Extraction Results for PFOS Combustion Test 5.4.7.6 PUF Extraction Results for PFOS Combustion Test _- 5.5.1 5.5.2 Change of Atomic composition of Correction of Amount of Sample That Contains Equivalent Amount of Fluorine in 0.5 mg of PFOS 5.6.1 Flow Rate Profile for Heated Blank Analysis at 600C 5.6.2 Flow Rate Profile for Heated Blank Analysis at 900C 5.6.3 PUF Extraction Results for Heated Blank Analysis 5.7.1.1 Net ,4rnount of Gasified Sample for 1" Transfer Efficiency Test 5.7.1.2 Flow Rate Profile for lStTransfer Efficiency Testa 5.7.1.3 PUF Extraction Results for ISt Transfer Efficiency Test X PAGE 35 35 36 36 39 39 39 40 40 41 43 44 44 .- 44 45 45 47 47 47 48 LIST OF TABLES (Continued) TABLE 5.7.2.1 Net Amount of Gasified Sample for 2"d Transfer Efficiency Test 5.7.2.2 Flow Rate Profile for Znd Transfer Efficiency Testa . 5.7.2.3 Methanol Extraction Results for Znd Transfer Efficiency Test 5.7.2.4 PUF Extraction Results for 2"dTransfer Efficiency Test 5.7.3.1 Net Amount of Gasified SampIe for PUF Collection 5.7.3.2 Flow Rate Profile for PUF Collection (PFBS Gasification with Air) 5.7.3.3 Flow Rate Profile for PUF Collection (PFBS Gasification with He) 5.7.3.4 Flow Rate Profile for PUF Collection (PFOS Gasification with Air) 5.7.3.5 Flow Rate Profile for PUF Collection (PFOS Gasification with He) 1- 5.7.3.6 ReactorNalve Transfer Line Extraction Results 5.7.3.7 PUF Extraction Results 5.8.1 SO2 Calibration Results Using PLOT Column 5.8.2 Standard SO2 Transfer Efficiency 5.8.3 Sulfur Recovery Rate as SO2 5.9.1 Integrated Peak Area of Extracted Ion (m/z = 69) 5.9.2 Integrated Peak Area of Extracted Ion (m/z = 69) 5.9.3 Integrated HFID Peak Area at 600C PAGE 48 48 49 49 50 50 50 - 50 51 51 52 52 53 54 ~ 55 55 59 xi EXECUTIVE SUMMARY 3M requested that the Environmental Sciences and Engineering Group at UDRI evaluate the thermal decomposition of the following fluorcarbon-based compounds and polymers: FC-807A and FC-1395 (C8 perfluoroalkyl sulfonamides); C$gS 03-K' (PFBS), and C8F17S03-K' (PFOS). The overall goal of t h s study was to determine if incineration is a potential source of perfluoroalkyl sulfonates, e.g., perfluoroctanyl sulfonates (PFOS), which has been found in a number of wildlife tissue samples (Giesy, et al., 2001; Kannan, et al., 2001). A laboratory-scale study roughly simulating a full-scale hazardous waste incinerator was envisioned. Based on prior experience with halogenated compounds, we initially planned to use relatively modest conditions in the primary combustion zone (ca. 400C) to gasify the materials with more severe high-temperature (600 - 9OO"C), oxidative conditions representing a secondary combustion zone. TGAs of the active ingredients indicated that higher temperatures (- 600C) were necessary to gasifythese unique materials. The sponsor also requested that the experiment be designed to detect low-level (0.1%) transformation to perfluoroalkylsulfonates in the exhaust gases from the fluorinated portions of the test compounds. The combination of these factors necessitated the use of large amounts of material (milligram quantities) and high-temperature, long duration exposures (ca. 125OoC,40 sec) in a specially designed pyroprobe to fully gasify the material. These conditions, while representing quite severe conditions in the primary zone of an incinerator, e.g., a rotary kiln, are representative of the range of conditions that occur in a fullscale system. As such, the approach employed in the laboratory-scale combustion study is a reasonable extrapolation of a full-scale incineration study of perfluoroalkyl sulfonates and polymers that contain these active ingredients. Combustion tests were completed for seven fluorinated alkyl sulfonyl hydrocarbons: FC-1395, FC-807A, C$gS03'K' (PFBS), and C8F17S03-K' (PFOS) as requested by the sponsor. In-line and off-line GUMS analyses, reactor - effluent sample collection using PUF cartridges followed by LC-MS analysis, and chemical extraction of various transfer lines throughout the reactor system including the reactor itself followed by LC-MS analysis were conducted to investigate the following: 1) the extent of conversion of the active ingredients, 2) the formation of fluorinated organic incomplete combustion byproducts, and 3) the extent of conversion of the sulfur to sulfur oxides. The data presented herein clearly show thatjucineraticmof FC-1395 and FC- 807A does not release perfluorinated alkyl sulfonates. This conclusion is based mainly on the L C M S 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 varied from 40 to 120'31,depending on the fluorocarbon or fluorocarbon polymer combusted. The dominant sink for sulfur was SO*. G C M S analysis of perfluorinated alkyl sulfonate precursors indicated that such precursors were not present in the reactor effluent. This finding is consistent with the LCMS measurements, and strongly suggests that the C-S bond was completely destroyed (and did not reform) in the combustion tests. xii Several fluorinated organic intermediates were observed in the reactor effluent. These compounds were limited to fluorinated alkanes, fluorinated alkenes, and fluorinated aromatics. E g h e r molecular weight fluorinated polycyclic aromatic hydrocarbons were not observed. The data from t h s laboratory-scale incineration study indicates that properly operating full-scale municipal or hazardous waste incineration system can adequately dispose of these unique materials. Incineration of these fluorinated compounds is not likely to be a significant source of perfluorinated alkyl sulfonates into the environment. Fluorinated organic intermediates are also unlikely to be emitted from these facilities. xiii 1. Background The destruction efficiency (DE) of principal organic hazardous constituents (POHCs) is dominated by the temperature, time, file1 (waste)/air mixing, and fuel/air stoichiometry (excess air) experienced by the POHCs in the h g h temperature zones of incinerators (Dellinger, et al., 1991). Numerous calculations and experiments have shown that emissions of undestroyed, residual POHCk are kinetically, not thermodynamically controlled (Tsang and Shaub, 1982; Trenholm, et a[., 1954; Dellinger, et al. 1991). As a result, accurate assessment of POHC emissions require thermal stability testing and cannot be accuratery modeled based on thermodynamic equilibrium calculations. Simple conceprual and more complex computer models indicate that gas-phase residence time and temperature in the post-flame zones of incinerators control the relative emissions of most POHCs (Clark, et al., 1984; Dellinger, et al., 1956; Dellinger, etal. 1991). This is because all molecules entering the flame zone of an incinerator are destroyed completely to thermodynamic endproducts and only die minute fraction escaping the flame zone is actually emitted from the facility. Once in the post-flame zone, gas-phase thermal decomposition reactivity in the presence 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 volatilfzed at approximately the same rate, they will experience the same post-flame gas-phase residence time, temperature, and stoichiometry history I (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 predictLheir relative incinerability. The temperature for 99% destruction at 2.0 seconds gas-phase residence time, [Tgg (2)('C)] has been I I used previously to rank the thermal stability of POHCs (Taylor, et al., 1990). Other residence I times or levels of destruction may be used to develop a ranking. However, laboratory data I 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., 1956; Taylor and Dellinger, 1988). On the other hand, stoichiometry has been shown to be a significant variable in determining relative stability (Graham, et al., 1956; Taylor and Deliinger, 1988; Taylor, et al., 1991). Experimental and theoreti'cal considerations suggest that various flm e 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 fiirther 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 1 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 WCl ratio than the baseline set of conditions) both produced statistically significant correlations between product emission concentrations and their . gas-phase thermal stability rankings. For the thermal failure tests, correlations above the 99% confidence interval were observed. Full-scale studies (Dellinger, et al., 1993) of a sevencomponent hazardous waste mixture indicated that thermal failure and wastejair mixing failures also produced statistically significant correlations. Based on median destruction and removal efficiencies ( D E S ) ,the data indicated that both the mixing and thermal failure modes produced statistically significant correlations between product emission concentrations and their gas-phase thermal stability rankings. 3M Company requested that the Environmental Sciences and Engineering Group at UDRI evaluate the thermal decomposition of the following fluorcarbon-based compounds and polymers : FC-807A and FC 1395 (C, perfluoroalkyl sulfonamides): C89S03-K' (PFBS), The overall goal of this study was to determine if incineration is a potential source of perfluoroalkyl sulfonates, e.g., perfluoroctanyl sulfonates (PFOS), which has been found in a number of wildlife tissue samples (Giesy, et al., 2001; Kannan, et al., 2001). This report is broken into eight sections. The first four sections describe the background of our experience in incineration research, phase I: the initial test protocol and project objectives, phase II: the method development work, and phase 111: the revised test protocol. Sections five and six describe the experimental results followed by an interpretation of the results, respectively. Section seven gives conclusions and recommendations. Section eight provides a list of references. An appendix contains the following auxiliary information: 1) a timeline of the phase I, phase II,and phase 111studies and the actual dates of the combustion tests, 2) the phase IIfinal _. report and raw data, 3) the phase III test protocol and addendum, 4) the 3M analytical report and - 5 ) a spreadsheet linking the UDRI combustion tests with the 3M Analytical results. 2 2. Phase I: Objectives and Test Protocol The objectives of this program were the following: 1. To determine if perfluoroallylsulfonyl compounds can form combustion products that either are perfluoroalkyl sulfonates or are precursors of perfluoroalkyl sulfonates. Precursors are compounds that could form perfluoroalkyl sulfonates through transformation reactions llkely to occur in the environment. 2. I dentify the major organic combustion products of perfluoroalkylsulfonyl compounds. 3, Determine if the sulfur present in the samples is quantitatively converted to sulfur dioxide and/or thionyl fluoride (SOFz) and sulfuryl fluoride (S02Fz) at high temperature, fuel-lean combustion conditions. The development of the'test protocol was based on the use of batch-charged continuous flow reactors developed at UDRI to study the thermal stability of organic materials (Rubey and Carnes, 1985, Rubey and Grant, 1988). Briefly, these systems accept a small quantity of material (typically less than 1 mg). The sample and its decomposition products are volatilized, mixed with flowing dry air, transported through a high temperature quartz tubular reactor where the sample vapors are thermally stressed under controlled conditions of time, temperature, and excess air level. The materials surviving this exposure are then passed onto an in-line gas chromatography/mass spectrometry (GUMS) system for analysis. Quantification of parent species is based on transport and analysis of known quantities under nondestructive conditions. Typically, products are quantified using the response factor of the parent compound or the major parent compounds if from a complex mixture. In this study, the , analytical focus will be identification of stable fluorinated organic intermediates and the quantification of sulfiir oxides in an attempt to recover 100% of the initial sulfur in the sample. Sulfur quantification will be performed using a mass selective detector (MSD). Consideration - was also given to the use of a sulfur-specific detector that responds only to sulfur atoms. However, due to the universal nature of the MSD,i.e., its ability to detect both sulfiir and fluorinated orgznic 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 the 3iM samples the unknowns in exablishing the test protocoI centered around the issue of transportability. Specifically, transporting the sample to the reactor from the sample inlet and the products from the reactor to and through the analytical sub-systems. For example, it is likely that the test sample will decompose rather than evaporate and the central issue becomes whether the products from this decomposition process can be transported under acceptable conditions. Consequently, developing the test protocol for the 3M samples focused on the issues of sample feed and product transport and analysis. The first step in any gas-phase thermal stability analysis is converting the sample into a vapor where it is mixed with the desired carrier gas and transported through the reactor system by the bulk flow of the process stream. 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. T h ~psreliminary 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 reIatively simple tests was performed to determine if the gasification products could be transported under nominal flow reactor conditions. While the sample inlet systems of the UDRIreactors can be routinely heated to 4OO'C (with transient heating as high as 6OO0C),the sample transport lines to and from the reactors are typically limited to 250-300C. Experience has shown that under these conditions most organic compounds of interest can be transported without inducing thermal reactions thereby preserving the fidelity of the samples flowing from the inlet system to the reactor and the product stream flowing from the reactor to the analytical sub-systems. A key issue to be evaluated in this study will be the transport of the PFOS/PFBS and its precursors from the gasification system to the high-temperature reactor and from the reactor to the analytical sub-systems. The System for Thermal Diagnostic Studies (STDS) was used to perform the incineration study described herein. An overall schematic 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 fiill-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. Syalem for Thermal Dlagnostlc Studles - PLUS . GE H I . GC fllR MS K . - M I .MI M I Figure 2.1. Schematic of the System for Thermal Diagnostic Studies 4 Initially, the Advanced Thermal Photolytic Reactor System (ATPRS) was selected for this study. To satisfy the analytical requirements for PFOSIPFBS detection by LC/MS analysis at 3M Environmental Laboratory, we determined that relatively large amounts of sample, 0.5 to several mg, had to be gasified in the actual experiments. This amount of sample was much larger than initially estimated (ca. 10 to 100 pg) and could not be gasified with the inlet available with the ATPRS. Preliminary experiments also demonstrated that higher gasification temperatures (> 400C) were necessary to rapidly gasify the fluorocarbon-based samples. As such, the STDS, equipped with a high-temperature pyroprobe that can gasify milligram quantities of material, was selected for the actual combustion tests. In the original protocol, we originally planned sample combustion with a liquid hydrocarbon file1 (e.g., n-octane). Subsequently, it was determined that a substitute was necesary 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 oxygemdemand of any hydrocarbon fuel and is a satisfactory replacement. We decided instead to use methane as a fuel if the sample is hydrogen deficient and requires hydrogen source to convert F to HF, otherwise h e 1 will not be introduced to the reactor. In the original protocol, we also proposed to conduct combustion tests at three temperatures (600, 750, and 900C). Preliminary combustion tests with several samples indicated that many combustion byproducts were formed at 600C, but those combustion byproducts were not observed at higher temperature (750 and 900OC) and the GUMS total ion chromatograms for these higher temperatures were very similar. Therefore it was decided that two temperatures are sufficient to analyze the combustion phenomena of the selected samples (600 and 900C). 5 3. Phase 11:Method Development The following method development tests were performed in phase 11: 1. Verify that Cq and Cg perfluoroalkyl sulfonates can be gasified and transported through the UDRIthermal instrumentation system. 2. ' Establish recovery efficiencies and detection limits for stable sulfiir compounds and PFOS precursors. The sulhir compounds would include but not be limited to Sol, SOF2, and SOzF2. PFOS precursors would include but not be limited to perfluorobutane sulfonyl fluoride (PBSF) and perfluorooctane sulfonyl fluoride (POSF). 3. Establish recovery efficiencies and detection limits for volatile C I - C f~luorocarbons. 4. Develop a quantitative method of sampling the reactor effluent. O R B 0 PUF cartridges (Supelco, Inc.) will be used for sampling PFOS and its precursors from the reactor effluent. This section summarizes the results. Calibration curves and detection limits for SO2, SOF2, S02F2, POSF, PBSF, and C3F6 (hexafluoropropene (HFP)) have been established. The transport efficiency for each compound through the STDS was also examined. Verification that the Cq and Cg perfluoroalkyl sulfonates can be gasified and transported through the system was performed following the completion of the combustion tests. This decision was made based on the potential contamination of the system had the transport tests been done prior to the combustion study. PUF cartridge sampling of the reactor effluent was established as part of the revised phase I11 protocol. HFP was selected as the surrogate volatile fluorocarbon due to the lack of availability of CFq and CF3H from gas suppliers. The linear fit equations for each sample, their linear correlation coefficients (R) and detection limits are tabulated in Table 3.1. Further details regarding these calibration curves are available in the Phase I1 report. Sample Name so?_ S OF2 SO2F2 POSF PBSF HFP Table 3.1. Linear Fit Equations and Detection Limits Linear Fit (Y: peak area, X: concentration (pprn)) Y = 5.8813E3* X - 3.8541E5 Y = 8.3335E3* X - 7.0267E4 Y = 1.033lE4*X + 1.8273E6 Y = 1.0423Ej"X - 8.4043E5 Y = 1.564E5*X + 1.338E6 Y = 1.4975E4"X - 2.8253E6 R 0.997 1 0.99941 0.99705 1.o 0.998 0.9997 Detection Limit (PPrn) 78.5 30.3 20.1 14.1 10.0 3.9 The transport efficiency of each standard was estimated by comparing the measured sample peak area obtained when the sample was injected into injection port in GCI 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). 6 As illustrated in Table 3.2, the transport efficiencies for SOF2, S02Fz,and HFP were within analytical error. An uncertainty of +lo% is reasonable for this type of analysis. That for POSF was slightly higher, but is nonetheless acceptable. That for SO2was around 76%. The SO2 standard was analyzed as a two-component mixture with SOFZ. Since the transport efficiency for SOF2 was nearly loo%, the results indicate some sample losses for SO2 through the reactor and transfer lines. Because SO2 is expected to be one of the major combustion byproducts, we will repeat the efficiency test at the onset of the actual combustion tests (see section 5.1 SO2 Transfer Efficiency Test). We will estimate a SO2 correction factor based on SO2 efficiency test results to compensate for its measured concentration during the Phase III study. The efficiency for PBSF was not consistent b e h e e n the two injection methods. The cause of this discrepancy was discussed with other analytical specialists in our group. The major cause may be a mixing problem ,of this sample with the solvent, dichloromethane. PBSF is the only liquid phase sample among the six standards. Each time PBSF was diluted with dichloromethane in the GC vials, it was shaken thoroughly in an attempt to obtain a uniform mixture. The density of PBSF is unknown, but expected to be heavier than dichloromethane. This may have caused some settling of the PBSF at the bottom of vials during preparation of the standards. The transport efficiency of PBSF will be re-examined as well as the PBSF calibration if the Phase III combustion tests _. indicate this is an important combustion intermediate. Further details of the initial calibration - and transport efficiency tests can be found in the Phase I1 report provided in the Appendix. , 7 4.Phase 111:Revised Test Protocol The combustion tests consisted of S separate tests as listed below: 1. SO2Transfer Efficiency Tests, 2. Laboratory Spike Analysis for PFOS and PFBS, 3. Heated Blank Combustion Test, 4. Combustion Tests for FC-1395, FC-S07A, PFOS, 5. Heated Blank Combustion Test (repeat), 6. Transfer Efficiency Test for L-I6271, PFBS, and PFOS, 7. Sulfur Recovery Analysis as SOZ, 8. Extracted Ion Analysis. , PFBS, and Specific attention was being given to the potential formation of PFOS and PFBS during the incineration of these materials. In-line and off-line GUMS analysis, PUF (polyurethane foam) collection of the reactor effluent 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, PFBS, and potassium bis imide by LC/MS. Prior to the sample combustion analysis, the transfer efficiency for SO2 was reexamined and the laboratory spike analysis for PFOS and PFBS was performed. A heated blank line analysis was performed at the onset of the sample combustion tests. After the combustion tests, another heated blank line analysis was performed. Transfer efficiency tests for ,C4F9S0 3 - Kf (PFBS), and CgF17S03-K' (PFOS)were performed at the conclusion of the combustion tests. Due to resolution issues regarding the in-line sampling approach, the sulfur recovery rate as SO2 was reanalyzed using off-line G C M S analytical results. Further details are provided in the Phase I11 test protocol and addendum that are given in an appendix to this report. The 3M analytical report (LIMS Nos. E02-0820, E02-0821, E02-0822, E02-0839, E02-0840, E02-0867, E02-0895, E02-0896, E02-0898, E02-0899, E02-0916, E02- 0917, E02-0926, E02-0968, E02-0969, E02-0970, and E02-0971) is also provided in an appendix to this report. 1%should also be noted that the PFOS,PFBS, and data were not corrected for recovery from the PUF cartridges. Spike recoveries for PFBS and PFOS were ca. 80% with 1 pg addition of these compounds and ca. 90% with 10 pg addition of these compounds. 8 5 . Experimental Results 5.1, SO2Transfer Efficiency Test The SO2 transfer efficiency tests conducted in Phase I1 was repeated in Phase I11 to confirm the Phase I1 results. The results are shown in Table 5.1.1. The SO?standard was analyzed as a two- component mixture with SOF2. SO2 transport efficiency was 83.7%, slightly higher than previous results, 76.4%, which gives average value of 80.1%. The transport efficiency for SOFz was again nearly 100%. Sample s0 2 SOFz System Transport Peak Area 1 2nu Average (1) 8300590 8433620 21346398 20309703 8367105 20825051 Direct Injection Peak Area 1 2nu Average (2) 10134575 19612747 9995499 20444301 10065037 20028524 Efficiency (%I (1)/(2)x 100 83.7 101.9 5.2. Laboratory Spike Analysis for PFOS and PFBS PFOS and PFBS were dissolved with 10 ml methanol (Aldrich, HPLC grade) and 1 yl of soIution was placed into a reactor (4 mm (i.d.) x 6 mm (0.d.) x 7 cm length) and dried by blowing high purity nitrogen. The amount of samples 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) (n-4 PFOS 10.02 10 .~ PFBS 9.78 10 (Pl> Loaded (pg) I .o 1.o 1.o 1.o Tables 5.2.2 and 5.2.3 show the extraction results for PFOS and PFBS laboratory spike analysis, respectively. The combined first and second extracts recovered 149% of the PFOS and 86% of the PFBS. In addition, 0.08 pg of PFOS, equal to 8% of the PFBS added, was recovered from the PFBS spiked reactor. -The excess PFOS recovery, and the presence of PFOS in the PFBS spike is evidence of possible cross contamination. The possible source of the cross contamination is the inch tubing which connects the reactor and collection vial shown in Figure 2 in the Phase I11 protocol. A new reactodtransfer line was used for each sample, but the tubing in the extraction system was repeatedly used after cleaning using reagent grade alcohol and acetone. 9 Table 5.2.2. PFOS Laboratory Spike Analysis Sample Extracts PFOS (pg/pl) PFOS (pg) PFBS (pg/pl) PFOS 1'' Exrracts 232 PFOS zndExtracts 40.5 1.6 c10.1 0.28 40.1 PFBS (pg) c0.065 <0.065 Table 5.2.3. PFBS Laboratory Spike Analysis Sample Extracts PFOS (pg/pl) PFOS (pg) PFBS (pg/pl) PFBS 1Et Extracts 14.7 0.10 146 PFBS Znd Extracts c10.0 c0.68 10.2 PFBS (pg) 0.93 0.065 5.3. Heated Blank Combustion Analysis The heated blank reactodtransfer tubing was analyzed to examine if there was any system Contamination including PFOS and PFBS for the reactor temperature at 600 and 900C prior to series of combustion tests. Four analyses, in-line GUMS analysis, PUF collected off-gas sample analysis, off-line GC/MS,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 GCMS was mainly used to analyze compounds equal to or heavier than Cg compounds and off-line GUMS was used for Lighter compounds including SO2. PUF sample and methanol extracts were analyzed for ,PFBS, and PFOS detection. The experimental setup, reactor/transfer-line configuration, and experimental procedure followed the Phase I11 test protocol. The phase UT test protocol and addendum can be found in the appendix to this report. 5.3.1. In-line GUMS Analysis Table 5.3.1 and 5.3.2 show the flow profile and carrier flow volume used for the heated blank analysis at 600 and 9OO"C, respectively. Of the total gas flow, 1 ml/min was introduced to the in-line GUMS and the remainder introduced to either the PUF cartridge or the Tedlar bag for off-line analyses. A simple 1/16 in. tee was used as the flow splitter. Air was flowed to both the .. pyroprobe and reactor during the test except during the last time period, where helium was necessary to purge the pyroprobe and to perform the in-line GUMS analysis. A HP5890N5970B series GUMS with a DB-5 MS capillary column (30 m length, 0.25 mm i.d., Agilent Technologies, Lnc.) was used for the in-line GCMS analyses. The in-line GCMS was operated at constant pressure (10 psi). The MS was auto-tuned with perfluorotributylamine (PFTBA) and operated at an electron multiplier setting of 2000 inthe scanning mode sweeping a mass range from 45 to 550 d z . Figures 5.3.1 and 5.3.2 show total ion chromatograms for reactor temperahires of 600 and 9OO"C, 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 fiom the presence of si,gnificant amounts of condensed phase combustion byproducts. This expectation was confirmed and is consistent with the large amounts of fluorochemicals that were injected into the combustion system. 10 Table 5.3.1. Flow Rate Profile for Heated Blank Analysis at 600C Time Period Reactor Flow Pyroprobe Flow Total Flow Rate Total Sampled (set> Rate (mVmin) Rate (ml/min) (mI/m in) Volume Volumed 0 - 120 120 - 130 130 - 140 140 - 160 10.5 10.5 10.5 9.03 (He)b 0.80 0.80 3 4.63a 4.63 4.53 (He)' 11.30 11.30 3 14.63 15.13 13.56 (mu 22.60 2.16 2.52 4.52 (ml> 20.60 1.99 2.35 4.19 Total Volume (mi) 31.50 29.13 aLinear increase (approximate). bsc Switched to helium for sweep. Sampled volume for PUF and Tedlar bag collection. Table 5.3.2. Flow Rate Profile for Heated Blank Analysis at 900C Time Period Reactor Flow Pyroprobe Flow Total Flow Rate Total Sampled (set> Rate (ml/min) Rate (rnl/min) ( m hin) Volume Volumed 0 - 150 150 - 160 160 - 170 170 - 190 7.60 7.60 7.60 6.54 (He)b 0.70 0.70 3 4.63a 4.63 4.53 (He)' 8.30 8.30 3 12.23 12.23 11.07 (ml) 20.75 1.71 2.04 3.69 (ml) 18.25 1.54 1.87 3.36 Total Volume (nil) 28.19 25.02 a Linear increase (approximate). b9cSwitched to helium for sweep. Sampled volume for PUF and Tedlar bag collection. Figure 5.3.1. In-line G C M S Ion Chromatogram for Heated Blank at 600C A b " r . r l - r #Et?. 6500 E000 5SOO SO00 4500 4000 z3soo 1000 2500 2000 1 SO0 7 000 500 0 TIC I-le1-eoo P Tlrr,u--.- Figure 5.3.2. In-line G C M S Ion Chromatogram for Heated BIank at 900C 5.3.2. Off-line GC/MS Analysis A 0.5 L Tedlar bag (SKC, Inc.) was used to collect the off-gas. The samples were analyzed within 15 minutes after .collection. The flow profile was identical to the in-line GUMS analysis and PUF collection except the last time period, which was not necessary for Tedlar bag analysis. HP5890N5970B series GUMS with SPEL-Q PLOT (Porous Layer Open Tubular) column (30 m length, 0.53 mm i.d., Supelco, Inc.) was used for the analyses. The off-line GUMS was operated in the constant flow mode with 28 ml/min split flow. The MS was auto-tuned with perfluorotributylamine (PFTBA) and operated at an electron multiplier setting of 1600 in the scanning mode sweeping a mass range from 35 to 550 m/z. The Tedlar bags were heated to ca. 50 - 60C to minimize condensation on the bag surfaces. 1 ml sample volumes were injected using a gas-tight syringe (Hamilton Co.). Figure 5.3.3 and 5.3.4 show total ion chromatograms for the heated blank at 600 and 9OO"C, 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. ,-,,7,-- -40000 7 90000 -I ~ 0 0 0 0 7 7 0000 7 00000 eoooo eoooo 70000 .a0000 soooo 40000 30000 zooao 7 0000 -- 0 Figure 5.3.3. Off-line GC/NIS Ion Chromatogram for Heated Blank at 600C 12 .... .. - A D I..A:.-. I ..-I 0 . r . 1 *0000 7 30000 120000 1 ? 0000 100000 00000 a0000 70000 ~0000 soooo 40000 30000 20Q00 10000 0 r ,.,-..,,-.- 1.' , Figure 5.3.4. Off-line GC/I\/IS Ion Chromatogram for Heated Blank at 900C 5.3.3 ReactodTransfer Line Extraction and LC-NlS Analysis Following PUF sample collection and in- and off-line GUMS analysis at 9OO"C, extraction of the reactorhransfer 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 111 test protocol. The extractions were performed twice using 5.5 ml of methanol ((Aldrich, HPLC grade). The extracts were analyzed for PFBS,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 first heated blank combustion test. The amount found was 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 fluorochemical product 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 PFOS (pg/pl) PFOS(pg) PFBS(pg/pI) PFBS(pg) 14.9 0.10 <10.1 <0.065 <4 96 <o 078 Table 5.3.4 shows the analytical results for the two PUF sample collections. No cross contamination was detected. Table 5.3.4. PUF Extraction Results for Heated Blank Analysis Temp ("C) PFOS(pg/pl) PFOS(pg) PFBS(pg/pl) PFBS(pg) 600 C10.0 <0.25 <10.1 <0.23 <4.96 900 <10.0 CO.25 <lo.1 <0.23 <4.96 <0.10 <o. 10 5.4. Combustion Tests of Seven Selected Compounds Combustion product analyses were performed for seven compounds, FC- 1395, FC-S07A, . J CqF9S03-K' (PFBS) and CsF17S03-K' (PFOS). Four distinct analyses were conducted. Two GUMS analyses were conducted at UDRI:in-line 13 GUMS analysis and off-line GUMS analysis using Tedlar bags. The chemical extractions of the reactor transfer lines were performed at UDRI. The PUF cartridges were extracted at the 3M Environmental Lab. The experimental setup, reactodtransfer-line configuration, and experimental procedure followed the Phase 111test protocol. The GUMS operating conditions for the in-line and off-line analyses were the same as those used for heated blank analyses described in Section 5.3. In these combustion tests, the samples were first volatilized in a pyroprobe chamber. This chamber is considered analogous to the primary combustion chamber in an incinerator. The gases or air-entrained particulate matter then passed through transfer tubing, a heated tubular reactor, and additional transfer tubing and a valve to PUF cartridges. The heated reactor is I considered roughly analogous to a secondary cornbustion chamber or afterburner in a fdl-scale incinerator. 5.4.1. Combustion Test Table 5.4.1.1 shows the .net amount of sample gasified for the combustion tests. The sample probe was weighed before and after the combustion tests. Table 5.4.1.1. Net Amount of Gasified Sample for Combustion Test Temperature Usage Loaded Remained Net Amount of ("C) (mg) (mg) Gasified Sample (mg) 600 PUFa 2.03 0.02 . 2.01 T B ~ 2.11 0.01 2.10 900 PUF 2.22 0.14 2.08 TB 2.15 0.27 1.88 'In-line GC/h/lS analysis and off-gas collection using PUF. Off-line GCMS analysis using Tedlar Bag. Table 5.4.1.2 and Table 5.4.1.3 show flow rate profiles used for combustion tests at 600 and 900"C, respectively. Identical combustion conditions were repeated for PUF collection, inline GUMS analysis, and off-line G C M S analysis for each temperature. The first total volume - (3rdrow from the bottom) is the summation of all f l o w steps. A flow of 1 ml/rnin was always supplied to the in-line GC/MS system. Therefore, the volume passed through the PUF cartridge can be calculated by subtraction of the volume to the in-line GCIMS system from the total volume passed through the reactor as shown in the Znd row from the bottom: 45.3 1 ml - [1 ml/min. (269 - 25) sec.] / [60 sec./min.] = 412 4 ml To calculate the total amount of SO2 recovered using the off-line GCMS system, the volume supplied to the in-line GC/MS system also needs to be counted as well as the volume collected by Tedlar bag. This total volume can be calculated by subtraction of the first time step volume (10.97 ml) fror, the total volume passed through the reactor (45.3 1 ml) as shown in the last row, since the gas collectior. was started when the sample was inserted. At the onset of the experiment, air was flowed through the entire system for 1 minute prior to sample gasification. The pyroprobe/transfer line system was then opened to insert the sample probe within the pyroprobe. At that time, there was no appreciable gas flow through the system. 14 \ The sample was then gasified for 40seconds at 1250C. During and following t h s gasification, I air flow swept the gasified products from the pyroprobe to the reactor. For the 600C combustion test with , for example, this air flow rate was 0.47 mL/min at 23C for 2 I min., 24sec. At 260"C, the temperature of the oven containing the pyroprobe, this air flow would have expanded to sweep the volume of the pyroprobe approximately 2times. However, ! the 40 sec. heating to 1250Cto gasify the sample during this flow period would have also forced approximately 1.9 pyroprobe volumes of gas from the pyroprobe to the reactor. During cooling from 1250C to 260C following gasification, there was likely also a temporary back air flow into the pyroprobe as the gas pressure inside it dropped. To purge the pyroprobe/transfer line, air flow to the pyroprobe chamber was then increased to the maximum rate and held for 10 seconds. For the 600Ccombustion test on for example, this air flow rate was 4.63 mL/min at 23C. After 'gas f l o t~o the pyroprobe chamber was increased to the maximum, the total volume of the purging air and helium was 3.5 ml at 23OC,which corresponds to 6.9 ml at I 260C.Since the effective volume of the pyroprobe chamber with the sample probe inserted is 1.jcm3 (bottom of page 1'0in Phase I11 protocol), this volume completely flushes the pyroprobe chamber 4.6times. If one assumes the gas in the pyroprobe is completely mixed, a best-case 1 scenario, this would have carried 99.0% of the gasified from the pyroprobe to the reactor. This purging procedure was applied for all seven combustion tests, and the flow rates profile for each test is given below in tabular form. The head of the GC column was held at the temperature of -60Cduring the entire combustion period to concentrate effluent gas that was introduced at 1 ml/min flow rate. The G U M S temperature programming was started after the final helium purge. Table 5.41.2. Flow Rate Profile for Combustion Test at 600C Time Reactor Flow Pyroprobe Flow Total Flow Rate Volume to Period (sec) Rate (ml/min) Rate ( m h i n ) (ml/min) Reactor (ml) 0 - 60 10.2 0.47 10.67 10.67 60 - 85a 0.00 0.00 0.00 0.00 85 - 229 10.2 229 - 239 10.2 +0.47 0.47 4.63b 10.67 10.67 3 14.83 25.61 2.13 .- 239 - 249 10.2 4.63 14.83 2.47 249 - 269 8.77 (He)' 4.53 (He)d 13.3 4.43 Total volume passed through reactor (ml) Total volume passed throughPUF (ml) 45.31' 4 1.24' Total volume used for off-line GUMS SO1 quantitative analysis (ml) 34.64g a System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). '.*Switched to helium for sweep, e'rotal canier flow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. Volume used to calculate total amount of SOzrecovered using off-line GUMS system. 15 Table 5.4.1.3. Flow Rate Profile for Combustion at 900C Time Period Reactor Flow Pyroprobe Flow Total Flow Rate Volume (sec) Rate (ml/min) Rate (ml/min) (ml/min) 0 - 60 7.43 0.3 6 7.79 60 - 8 j a 0.00 0.00 0.00 85 - 265 7.43 0.36 7.79 265 - 275 275 - 285 285 - 305 7.43 7.43 6.39 (He)' 0.36 3 4.6jb 4.63 4.53 (He)d 7.79 3 12.06 12.06 10.92 Total volume passed through reactor (ml) Total volume passed through PUF (ml) Total volume used for off-line GC/MS SO?quantitative analysis (ml) (ml> 7.79 0.00 23.37 1.65 2.01 3.64 3 8 .46e 33.80f 30.67g a System opened due to sample insertion. Assumlng no outlet flow. Linear increase (approxunate). c*dSwitched to helium for sweep. Total carrier flow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. Volume used to calculate total amount of SO2recovered using off-line G C M S system. 5 4.1.1. In-line GC/iVlSAnalYsis: Figure 5.4.1.1 shows the total ion chromatogram for ' combustion at 600C. The first peak at 1.O min. was identified as pentafluoroethane and the following two peaks were identified as sulfiir dioxide. It was often observed for in-line GUMS analysis that one compound appears as two continuous peaks. These peaks at the beginning of chromatogram were investigated fitrther with off-line G C M S analysis as described in Section 5.4.1.2. The large peaks at 10 to 11 minutes were identified as benzene, fluorobenzene, difluorobenzene, trifluorobenzene, and their isomers. The largest peak corresponds to benzene. The wide peak which appeared at 12 to 13 min. has a strong mass signal at 85, indicative of tetrafluorosilane. Figure 5.4.1.2 shows original mass spectra (upper spectra) at the largest response time and tetrafluorosilane library spectra (lower spectra). Both have strong m/z = 8 5 and m/z = 5 5 signals. The original mass spectra do not contain m/z = 41 since the experimental scanning range was from 45 to 550 d z . Tetrafluorosilane would be formed in the pyroprobe chamber during the sample gasification at 1250C and not destroyed in the reactor at 600C. The peaks following tetrafluorosilane were identified as styrene at 15.5 min., benzaldehyde at 16.4 min., benzonitrile at 16.85 rnin., phenol at 16.93 rnin., and naphthalene at 20.2 min. No significant peaks were observed for molecules heavier than naphthalene. This suggests that molecular growth (free radical reactions leading to the formation of larger molecular weight compounds) does not occur for combustion at 600C. We have previously shown that larger multi-ring polycyclic aromatic hydrocarbons (PAH) and halogenated PAH can be detected with this combustion system in tandem with GUMS analysis (Taylor and Lenoir, 200 1; Sidhu et al., 2001). Figure 5.4.1.3 shows the total ion chromatogram for combustion at 900C. A similar chromatogram was obtained. The first peak at 0.5 to 1.Omin. was not clearly identified. The following peak at 2.0 rnin. corresponds to sulfur dioxide. The large peaks at 10 to 11 minutes are benzene, fluorobenzene, difluorobenzene, trifluorobenzene, and their isomers. The largest peak corresponds to benzene. The wide peak appeared at 12.5 to 15 minutes has strong spectrum of 85, suggesting tetrafluorosilane. The retention time and peak width of tetrafluorosilane differed from the 600C combustion results. Whlle the reasons for this are not completely clear, this is potentially due in part to differences in the time duration of the cryofocusing of the organic products and differences in the column head pressure because of the flow rate differences at the 16 Iast flow step. This phenomena was observed for a11 in-line G U M S total ion chromatograms. The peaks after tetrafluorosilane include styrene at 15.6 min., benzonitrile at 17.5min., and naphthalene at 20.25 min. Fewer aromatics were formed at 900C than at 600C. This suggests that fiirther molecular growth did not occur for combustion at 900C. Sulfur recovery rate as sulfur dioxide is reported in Section 5.7 of the experimental results. 2600000 i 2 4 0 0 0 0 0 2;200000 i =2000000 J 7 e00000 -le o o o o o 1400000 7~00000 1000000 eooooo 600000 400000 =ooooo 0 5.00 -a Figure 5.4.1.1. In-line G C M S Ion Chromatogram for at 600C 4000 -/ aooo { , , , ,&((I 0 40 so ,I , , ,,Ill , , , U T , , ;;-7 ,4, , , I , , . 1 , 0 7 , 50 70 ao so l o o ,, , , , , , , , , 7-0 ?=LO 7 3 0 ,, , , , ,., ., , , ,, 140 1 5 0 160 ,, , , 270 Figure 5.4.1.2. Nlnss Spectra for the Wide Peak at 12 t o 13 Minutes 17 TIC: FC1-90-1 .D 2000000 1 aooooo 1600000 1400000 1200000 1000000 800000 600000 400000 zooooo TIh - 1 6 - - - 0 Figure 5.4.1.3. In-line G C M S Ion Chromatogram for at 900C 5.4.1.2.Off-lineGC/MS Analysis: Figure 5.4.1.4 shows the total ion chromatogram for off-line GUMS analyses for combustion at 600C. The largest peak at the beginning is associated with air (see extracted ion analysis, section 5.9) followed by 1,l-difluoroethene at 1.O min., pentafluoroethane at 1.7 rnin., sulhr dioxide at 3 min. The wide peak at 4.7 to 5.4 min could not be clearly identified. The three peaks around 10 min. were identified as benzene, difluorobenzene (isomer unclear), and fluorobenzene, in t h s order. Figure 5.4.1.5 shows the total ion chromatogram for off-line GUMS analyses for combustion at 900C. The first 2 peaks before 1 min. are associated with air followed by sulfur dioxide at 3.0 min. No other significant peaks were observed for combustion at 900C. 240000 TIC. FCl-60-2.0 220000 200000 180000 160000 140000 120000 7 00000 eo000 60000 40000 20000 T icnm - -- 0 0.00 2.00 4.00 6.00 8.00 1 0 . 0 0 12.00 7 4 . 0 0 l 6 . 0 0 Figure 5.4.1.4. Off-line GCAVIS Ion Chromatogram for 18.00 at 600C 18 -%ooooo le0000 3eoooo 340000 3ZOOOO 300000 2aoooo =eo000 =?PO000 ~20000 200000 7 aoooo 9 80000 -7 P O 0 0 0 7 20000 00000 aoooo 60000 PO000 20000 0 0 0 0 2.00 -.-/m---.,. Figure 5.4.1.5, Off-line G C M S Ion Chromatogram for at 900C 5.4.1.3. LC-MS Analvsis of Extracts: Table 5.4.1.4 shows the analytical results of the reactor/ transfer line extractions. No detectable amount of PFOS, PFBS, was found. Table 5.4.1.4. Methanol Extraction Results for ' Extraction 1S t 2nd PFOS(pg/pl) 4.00 -6.00 PFOS(pg) <0.035 <0.035 PFBS(pg/pl) -3.05 4.05 PFBS(pg) <0.032 K0.032 Combustion Test . _~ <4.96 <4.96 .. <0.025 <0.028 5.4.I . 4. LC-hfS Analvsis ofPUFs: Table 5.4.1.5 shows the analytical results for the PUF sampling cartridges. No detectable amount of PFOS, PFBS, was found. Table 5.4.1.5. PUF Extraction Results for Combustion Test Temp Media PFOS PFOS PFBS PFBS .- . PUF (2lfld> G.00 <0.12 c5.05 4 . 1 2 ~ 4 . 9 6 cO.10 900 PUF (1") <5.00 ~ 0 . 1 2 <5.05 - 4 . 1 2 c4.96 <o. 10 PUF Qfld) <5.00 <0.12 <5.05 <0.12 <4.96 <o. 10 5.4.2. Combustion Test Table 5.4.2.1 shows net amount of sample gasified for the sample probe was weighed before and after the combustion tests. combustion tests. The 19 Table 5.4.2.1. Net Amount of Gasified Sample f o r Combustion Test Temperature Usage Loaded Remained Net Amount of ("C) 600 (mg) PUFa 2.85 (mg) 0.05 Gasified Sample (mg) 2.80 TBb 2.80 0.02. 2.78 900 PUF 2.82 0.06 2.76 TB 2.98 0.04 2.94 In-line GUMS analysis and off-gas collection using PUF. Off-line GUMS analysis using Tedlar Bag. Table 5.4.4.2 and 5.4.3.3 shows flow rate profiles used for combustion tests at 600and 900C, respectively. The detailed explanation for each value can be found in section 5.4.1 Table 5.4.2.2. Flow Rate Profile f o r Combustion Test at 600C Time Period Reactor Flow Pyroprobe Flow Total Flow Rate Volume (set> Rate ( m h i n ) Rate (ml/min) (rn l/m in) (mD 0 - 60 11.9 0.29 12.19 12.19 60 - 8Sa 11.9 85 - 301 11.9 301 -311 11.9 0.00 0.29 0.29 3 4.63b 0.00 12.19 12.19 3 16.53 0.00 43.88 2.39 311 -321 321 - 341 11.9 10.2 (He)' 4.63 4.53 (He)d 16.53 2.75 14.73 4.9 1 Total volume passed through reactor (ml) 66.12e Total volume passed through PUF (ml) 60.87f Total volume used for off-line GC/MS SOz quantitative analysis (ml) 53.93g a System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). "'Switched to helium for sweep. e Total carrier flow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. Volume used to calculate total amount of SO1recovered using off-line G U M S system. 1 Table 5.4.2.3. Flow Rate Profile for Combustion Test at 900C .. Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume - (set> Rate (mlhin) (rn Vm in) (m l/m in) (m 1) 0-60 9.1 1 0.2 1 9.32 9.32 60 - 85a 0.00 0.00 0.00 0.00 85 - 373 373 - 383 . 9.11 9.1 1 0.2 1 0.21 3 4.63b 9.32 9.32 3 13.74 44.74 1.92 383 - 393 393 - 413 9.1 1 7.83 (He)' 4.63 13.74 4.53 (He)d 12.36 Total volume passed through reactor (ml) 2.29 4.12 62.39' Total volume passed through PUF (ml) 55.92' '.' Total volume used for off-line GUMS SO2quantitative analysis (ml) 53.07g a System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). Switched to helium for sweep. Total carrier flow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. Volume used to calculate total amount of SO2recovered using off-line GUMS system. 5.4.2.1.In-line GC/MSAnaZvsis: Figure 5.4.2.1 showsthe total ion chromatogram for combustion at 600C. The first peak at 6.5 min. was identified as carbon disulfide and the largest peak at 10.4 min. was identified as benzene followed by fluorobenzene at 10.7 min. The 20 wide peak appearing at 12.5 to 15 minutes corresponds to tetrafluorosilane. The peaks after tetrafluorosilane include styrene at 15.3 min., benzaldehyde at 16.7min., benzonitrile at 17.2 min., phenol at 17.3 rnin., and naphthalene at 20.6 min. Figure 5.4.2.2 shows total ion chromatogram for combustion at 900C. A similar chromatogram was obtained. The first peak at 6.6 min. was identified as carbon disulfide and the largest peak at 10.5 min. was identified as benzene followed by fluorobenzene at 10.8 rnin. The peak at 12.8 min. was identified as toluene. The wide peak appearing at 13.3 to 14.2 minutes corresponds to tetraff uorosilme. The peaks after tetrafluorosilane include ethynylbenzene at 15.2 rnin., styrene at 15.4 min., indene at 18.3 rnin., naphthalene at 20.8 min., and acenaphthalene at 24.7 min. 3500000 3000000 - 1500000 1000000 500000 Time-->- 0 Figure 5.4.2.1. In-line GCm/lS Ion Chromatogram f o r at 600C J200000 J000000 zaaooooo aOOOOOO =-ooooo 1200000 --2 0 0 0 0 0 0 _I e 0 0 0 0 0 -00000 -00000 fI&...i__ I, =ooooo I ,.....-- - 0 5.00 Figure 5.4.2.2. In-line GChYIS Ion Chromatogram for 3s 0 0 at 900C 5.4 2.2. Off-line GC/ILSAnalysis: Figure 5.4.2.3 shows the total ion chromatogram for off-line GUMS analyses for combustion at 600C. The large peak at the beginning is associated with air. The major peaks found in this chromatogram were sulfur dioxide at 3.0 min., 21 carbon disulfide at 6.9 min., benzene at 9.9 min., and fluorobenzene at 10.1 min. Figure 5.4.2.4 shows ion chromatogram for off-line GC/MS analyses for combustion at 900C. A similar chromatogram was obtained for 900C combustion, but both sulfur dioxide and benzene peaks are slightly smaller than for the 600C combustion. P00000 380000 160000 340000 3zoooo 300000 280000 2eoooo 2aoooo z=ioooo ~00000 7 aaooo 7 60000 140000 ~z?,0000 7 00000 *oooo do000 00000 =oooo T 1 C : fC2--dO-- .D Ti,-n*..--r Figure 5.4.2.3. Off-line GC/MS Ion Chromatogram for at 600C Al>U.-.Cl=..l6W PO0000 3*0000 Jeoooo aPoo00 =10000 a00000 2.30000 ~eoooo ~aoooo =aoooo 200000 _I * o o o o ? cloooo 7 OOOOO ,= o o o o 7 00000 aoooo .30000 JdI n o 0 0 0 zoo00 0 0 . 0 0 4 00 ' .- -r,m.:.-- - e.00 e.00 -'0'00 ,,:oo. :P:oa .-.S:oo. Figure 5.4.2.4. Off-line G C M S Ion Chromatogram for -Ie:oo at 900C 54.2.3,LC-iV1.S Analysis of Extracts: Table 5.4.2.4 shows the analytical results of the reactor/ transfer line extractions. No detectable amount of PFOS,PFBS, was found. Table 5.4.2.4. Methanol Extraction Results for Extraction PFOS(pg/pl) PFOS(pg) PFBS(pg/pI) PFBS(pg) 1S t 4.00 <0.035 - 4 . 0 5 <0.032 2nd 4.00 C0.035 - 6 . 0 5 <0.032 Combustion Test <4.96 ~4.96 <0.028 <0.028 22 5.4.2.4.LC-iWSAnulysis ofPUFs: Table 5.4.2.5 shows the analytical results for the PUF sampling cartridges. No detectable amount of PFOS,PFBS, was found. Table 5.4.2.5. PUF Extraction Results for FC-4430 Combustion Test Temp ("C) lMedia PFOS (pg4-4 PFOS (PLg) PFBS (PdPl) PFBS (Pg> (pg/P.g> (4) 600 PUF (lst) 4 . 0 0 <0.12 - 4 . 0 5 <0.12 PUF (2"d) 6.00 < O X 6 . 0 5 <0.12 900 PUF (lst) -3.00 <0.12 < j . O j <0.12 PUF (2"d) G . 0 0 x0.12 ~ 5 . 0 5 <0.12 <4.96 <4.96 <4.96 <4.96 co.10 <0.10 CO.10 <o. 10 5.4.3. FC-1395 Combustion Test Table 5.4.3.1 shows netamount of sample gasified for FC-1395 combustion tests. The sample probe was weighed before and after the combustion tests. Table 5.4.3.1. Net Amount of Gasi-tiedSamDle for FC-1395 Combustion Test Temperature ("C) 600 Usage Loaded Mass (mg) PUF" 2.14 Dried Mass' (mg) 0.56 Remaining (md 0.04 Ne.t Amount of Gasified Sample (mg) 0.52 TB 2.22 0.58 0.06 0.52 900 PUF 2.20 0.57 0.02 0.55 TB 2.23 0.58 0.15 0.43 'In-line G C M S analysis and off-gas collection using PUF. Off-line GCIPIS analysis using Tedlar Bag. Calculated based on the water contents (74%). _. Table 5.4.3.2 and 5.4.3.3 shows flow rate profiles used for FC-1395 combustion tests at 600 and 9OO"C, respectively. The detailed explanation for each value can be found in section 5.4.1. 23 Table 5.4.3.2. Flow Rate Profile for FC-1395 Combustion Test at 600C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (sec:l Rate (mumin) (mI/m in) (mumin) (m0 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 - 157 157 - 167 167 - 177 177 - 197 9.53 9.53 9.53 8.20 (He)' 0.85 0.16 0.85 3 4.63b 0.16 4.63 0.16 4.53 (He)d 0 10.54 10.54 3 14.32. 14.32 12.73 12.65 2.07 2.39 4.24 Total volume passed through reactor (rnl) 3 1.8ge Total volume passed through PUF (ml) 29.0Zf Total volume used for off-line GUMS SO2 quantitative analysis (ml) 2 1.35g a System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). c,d Switched to helium for sweep. Total carrier flow volume that passed through the reactor. Total camer flow volume that passed through PLFs. Volume used to calculate total amount of SO2recovered using off-line G C M S system. Table 5.4.3.3. Flow Rate Profile for FC-1395 Combustion Test at 900C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (set> Rate (mumin) (m i/min) (m l/m in) (ml) Air Air CH4 0-60 7.14 0.63 0.12 7.89 7.89 60 - 85a 0.00 0.00 0.00 0.00 ' 0.00 85 - 179 7.14 0.63 0.12 7.89 12.36 179 - 189 7.14 0.63 3 4.63b 0.12 ..7.89 3 11.89 1.65 189- 199 7.14 4.63 0.12 11.89 1.98 199 - 219 6.14 (He)' 4.53 (He)d 0 10.67 3.56 Total volume passed through reactor (ml) 27.44e Total volume passed through PUF (ml) 24.20' Total volume used for off-line GUMS SO2quantitative analysis (mi) 19.S5g a System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). c,d Switched to _. helium for sweep. Total carrier flow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. g Volume used to calculate total amount of SO2 recovered using off-line G U M S system. 5.4.3.1.In-line GC/iVfSAnaZysis: Figure 5.4.3.1 shows the total ion chromatogram for FC-1395 combustion at 600C. The first peak at 0.4 to 1.O min. was not clearly identified. The second peak at 1.7 to 2.4 corresponds to sulfur dioxide. The peak at 7.1 min. was identified as carbon disulfide and the largest peak at 10 minutes was identified as benzene followed by fluorobenzene at 11.1 min. The wide peak appeared at 10 to 13 minutes corresponds to tetrafluorosilane. The peaks after tetrafluorosilane include benzonitrile at 17.7 min. and naphthalene at 21.1 min. Figure 5.4.3.2 shows the total ion chromatogram for FC-1395 combustion at 900C. The f r s t peak at 2.2 min. was identified as sulfur dioxide and the peak at 11 min. was identified as benzene. The sharp peak at 14.2 minutes and the subsequent wide peak both show a strong 85 signal that is attributed to tetrafluorosilane. 24 2oooooc 1.~0000c 1600000 1400000 1200000 1000000 aooooo 600000 400000 200000 1 TIC: FC3-60-7.D 5.00 10.00 -r,,-ne--r Figure 5.4.3.1,.In-line G C M S Ion Chromatogram for FC-1395 a t 600C T I C : F C 3 - - 9 0 - 7 .D sooooo 550000 500000 450000 400000 350000 . 300000 ~50000 ~00000 1 soooo 100000 50000 -. ,T C" e--i- 0- 5.00 0.0 Figure 5.4.3.2. In-line GC/MS Ion Chromatogram for FC-1395 at 900C 5.4.3.2. Off-lineGC/MSAnalwis: Figure 5.4.3.3 shows the total ion chromatogram for off-line GC/MS analyses for F(3-1-395combustion at 600C. The large peak at the beginning is associated with air. The next peak at 0.9 min. was identified as 1,2-difluoroethene followed by sulfur dioxide at 3 min ,difluorodimethylsilane at 4.8 min., benzene at 9.9 min. and fluorobenzene at 10.1 min. Difluorodimethylsilane also is likely produced during the gasification process. Figure 5.4.3.4 shows the total ion chromatogram for off-line GUMS analyses for FC- 1395 combustion at 9013C.The largest peak is associated with air. Sulfur dioxide at 3 min. was the only identifiable product. 25 I.\=L.. n C6.n n a m I400000 =.e0000 360000 540000 ==oooo 300000 ZeOOoO 16 0.00 0 Z?roooo azeoooo ~00000 f eo000 7 do000 740000 1~0000 7 00000 aoooo e)oooo 40000 ~0000 TIC: C C ~ - ~ O - Z . O 0 0 . 0 0 -1-8 r..w .--- Figure 5.4.3.3. Off-line GC/MS Ion Chromatogram for FC-1395 at 600C P00000 aaoooo 3BOOOQ 340000 azoooo ~00000 zeaoooo ~LIOOOO 1--0000 --2 l O O O O ~00000 eoooo e0000 -l--oooo 7 =oooo -I00000 1 eo000 eoooo - 40000 =oooo _- I 0 0 0 0 200 PO0 eo0 a00 1000 7z'oo -4'00 . . o ' o o %ra'OO - r e.>.--- I Figure 5.4.3.1. Off-line GC/i\/lSIon Chromatogram for FC-1395 at 900C 5.4.3.3. LC-&ISAnalysis ofExtracts: Table 5.4.3.4 shows the analytical results of the reactor/ transfer line extractions. No detectable amount of PFOS, PFBS, was found. Table 5.4.3.1. Methanol Extraction Results for FC-1395 Combustion Test Extraction PFOS(pglp.1) PFOS(pg) PFBS(pg/pl) PFBS(pg) 1St 6.00 <0.035 G.05 <0.032 <4.96 C0.028 2nd G.00 <0.035 <5.05 <0.032 <4.96 C0.028 5.4.3.4.LC-MS.AnnlYszs ofPUF: Table 5.4.3.5 shows the analytical results for the PUF sampling cartridges. No detectable amount of PFOS, PFBS, was found. 26. Table 5.4.3.5. PUF Extraction Results for FC-1395 Combustion Test Temp Media PFOS PFOS PFBS PFBS PUF (2""> 6.00 <0.12 6 . 0 5 ~0.12 <4.96 <Oslo 900 PUF (lst) 6 0 0 ~ 0 . 1 2 ~ 5 . 0 5 ~ 0 . 1 2 ~ 4 . 9 6 <0.10 PUF (znd) 6.00 <0.12 4 . 0 5 <0.12 ~ 4 . 9 6 <0.10 5.4.4. FC-807A Combustion Test Table 5.4.4.1 shows net amount of sample gasified for FC-807A combustion tests. The sample probe was weighed before and after the combustion tests. Table 5.4.4.1. Net Amount of Gasified Sample for FC-807A Combustion Test Temperature Usage Loaded Dried Remaining Net Amount of ("C) .. Mass Mass' (mg) Gasified (mg) (mg) - Sample (mg) 600 PUFa 2.68 0.59 0.00 0.59 T B ~ 2.68 0.59 0.00 0.59 900 PUF 2.43 0.53 0.08 0.45 TB 2.55 0.55 0.02 0.53 'In-line GUMS analysis and off-gas collection using PUF. Off-line GUMS analysis using Tedlar Bag. Calculated based on the water contents (78%). Tables 5.4.4.2, 5.4.4.3, and 5.4.4.4 show the flow rate profiles used for FC-807A combustion tests at 600 and 9OO"C, and the bIank test between 600 and 9OO"C, respectively. The detailed explanation for each value can be found in section 5.4.1. PUF samples were collected from the blank runs between the 600" and 900C test runs. The unheated valve/transfer line tubing downstream of the reactor/transfer line tubing was also extracted after the combustion test at 600C. The purpose ofthese analyses was to measure the carryover between the tests on a single - fluorocarbon product done at 600 and 900C. Table 5.44.:. FIow Rate Profile for FC-807A Combustion Test at 600C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (set> R.ate ( m l h i n ) (rnl/m in) (m l/m i n ) (ml) Air 0 - 60 9.70 Air CH4 0.84 0.15 10.69 10.69 60 - 85" 0.00 0.00 0.00 0.00 0.00 - 85 - 15:' 157 167 167 - 17'7 9.70 0.84 0.15 10.69 12.83 9.70 0.84 3 4.63b 0.15 10.69 3 14.48 2.10 9.70 4.63 0.15 14.48 2.41 177 - 19'7 8.89 (He)' 4.53 (He)d 0 13.42 4.47 Total volume passed through reactor (ml) 32.50e Total volume passed through PUF (ml) 29.64' Total volume used for off-line GCMS SO1 quantitative analysis (ml) 21.81g a System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). c*dSwitched to helium for sweep. e Total carrier flow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. Volume used to calculate total amount of SO2recovered using off-line GUMS system. 27 Table 5.4.4.3. Flow Rate Profile for FC-807A Combustion Test at 900C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (set> Rate (mumin) (ml/min) (ml/min) (mu Air Air CHJ 0 - 60 7.25 0.66 0.12 8.03 8.03 60 - 84a 0.00 0.00 0.00 0.00 0.00 84 - 178 178 - 188 18s - 198 198 - 218 7.25 7.25 7.25 6.27 (He)' 0.66 0.12 8.03 0.66 3 4.63b 0.12 8.03 3 12.00 4.63 0.12 12.00 4.53 (He)d 0 10.80 Total volume passed through reactor (ml) Total volume passed through PUF (ml) 12.55 1.67 2.00 3.60 27-88' 24.65' Total volume used for off-line G C M S SO1 quantitative analysis (ml) 19.8jg a System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). c*dSwitched to helium for sweep. Total carrier flow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. Volume used to calculate totaI amount of SO2recovered using off-line G U M S system. Table 5.4.4.4. Flow Rate Profile for Blank Analvsis between 600 and 900C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (set> 0 - 120 Rate (mumin) Air 9.70 (ml/min) Air cJ& 0.84 0.00 (ml/m in) 10.54 (mu 21.08 120 - 130 9.70 0.84 3 4.63a 0.00 10.54 9 14.33 2.07 130 - 140 140 - 160 9.70 8.89 (He)b 4.63 4.53 (He)' 0.00 14.33' 0.00 13.42 Total Volume (ml) 2.39 4.47 30.01 a Linear increase (approximate). bBcSwitched to helium for sweep 5.4.4.1. In-line GC/iMS Analvsis: Figure 5.4.4.1 shows the total ion chromatogram for FC-807A -. combustion at 600C. The hrst peak at 0.6 to 1.3 min. was not clearly identified. The second peak at 1.9 to 2.4 min. was identified as sulfur dioxide. Each compound has two consecutive peaks that have the same mass spectra and it apparently occurs as explained in Section 5.4.1. The peak at 7.1 min. was identified as carbon disulfide. The peak at 8.1 min. which shows strong spectra at m/z = 69 and 5 1 was not clearly identified. Peaks at 10.3 and 11,I min. were identified as benzene and-fluorobenzene, respectively. The wide peak that appeared at 11.2 to 12.6 min and the subsequent background correspond to tetrafluorosilane. The two major peaks after tetrafluorosilane were not clearly identified. Figure 5.4.4.2 shows the total ion chromatogram for FC-807A combustion at 900C. The first peak at 2.0 to 2.8 min. corresponds to sulfiir dioxide. The largest peak at 15.4 min. and the subsequent high background correspond to tetrafluorosilane. 28 7000OC L1~0000 e00000 5~0000 500000 4soooo 400000 3~0000 ~OOOOO ~soooo ~00000 150000 .100000 soooo 0 -,-#,r*---.- Figure 5.4.4.1, In-line GC/MS Ion Chromatogram for FC-807A at 600C A b u r id anCE C :FC4-90-1.O 800000 700000 600000 500000 400000 300000 200000 100000 0 I . I . , ' uI !.d.m r r m - I - 9 I..,.,.,..,.,,. 5.00 10.00 15.00 20.00 25100 JO!OO /"' 35.00 TIr T 1e--- Figure 5.4.4.2.In-line G C N S Ion Chromatogram for FC-807A at 900C 5.4.4.2. Offiline GC/kfSAnnlvsis: Figure 5.4.4.3 shows the total ion chromatogram for off-line G C N S analyses for FC-807A combustion at 600C. The largest peak at the beginning is associated with air. The second peak at 3.0 min. and the t h r d peak at 4.8 min. were identified as sulfilr dioxide and difluorodimethylsilane, respectively. There were no further identifiable peaks. Figure 5.4.4.4 shows the total ion chromatogram for off-line GUMS analyses for FC-807A combustion at 900C. Similar results were obtained. The largest peak at the beginning is associated with air. The second peak at 3.0 min. and the third peak at 4.8 min. correspond to sulfur dioxide and difluorodimethylsilane, respectively. 29 A- L I r. Q 0 ,-,0 - dOOOOO =moo00 7eo000 lPO000 azoooo TIC: PCO--QOT.D ~00000 280000 1eoooo ~~0000 ==oooo -7 0 0 0 0 0 -I* o o o o ~0000 7 *OOOO -l~0000 -I0 0 0 0 0 e.OOO0 so000 40000 =oooo ,-a, 7,..,--..- 0 0 Figure 5.4.4.3,.Off-line GCm'LS Ion Chromatogram for FC-807A at 600C doaooo zsaoooo 300000 zcJ0000 240000 ~20000 700000 7 aoooo 7 00000 740000 1O O O O O eo000 ' dOOOO T I C : FCd--OOT. D Figure 5.4.4.4. Off-line GCMS Ion Chromatogram for FC-807A at 900C 5.4.4.3. LC-MS Analysis ofExtracts: Table 5.4.4.5 shows the analytical results of the reactor/transfer line extractions. No detectable amount of PFOS,PFBS, was found. 'Table 5.4.4.5. Methanol Extraction Results for FC-807A Combustion Test Extraction PFOS(pg/pl) PFOS(pg) PFBS(pg/pl) PFBS(pg) 1St 6.00 <0.035 <5.05 <0.032 c4.96 c0.028 2nd 6.00 ~ 0 . 0 3 5 <5.05 <0.032 4.96 <0.028 30 5.4.4.4. LC-MSAnalysis ofPUF; Table 5.4.4.6 shows the analytical results for the PUF sampling cartridges. No detectable amount of PFOS, PFBS, Table 5.4.4.6. PVF Extraction Results for FC-S07A Combustion Test Temp Media PFOS PFOS PFBS PFBS (" C) (PdN) (149 (Pg/PU (Pg) (Pg/Pd (111) 600 PUF (lst;) 6 . 0 0 <0.12 4 . 0 5 <0.12 <4.96 <o. 10 PUF (2"d) 4.00 c0.12 6 . 0 5 4 . 1 2 <4.96 <0.10 900 PUF (1":1 6.00 <0.12 G . 0 5 <0.12 <4.96 P-UF (2"d) G . 0 0 <0.12 -4.05 ~0.12 <4.96 <0.10 <O.lO 5.4.5. Combustion Test Table 5.4.5.1 shows the net amount of sample gasified for sample probe was weighed before and after the combustion tests. ;ombustion tests. The Table 5.4.5.1. Net Amount of Gasified Sample for Combustion Test Temperature Usage Loaded Remaining Net Amount ("C) Mass (mg> of Gasified (mg) Sample (mg) - '600 PUFa 0.55 0.03 0.52 T B ~ 0.58 0.06 0.52 900 PUF 0.56 0.01 0.55 TB 0.54 0.00 0.54 "In-line GUMS analysis and off-gas collection using PLJF. Off-line GUMS analysis using Tedlar Bag. Tables 5.4.5.2, 5.4.5.3, and 5.4.5.4 show flow rate profiles used for combustion tests at 600 and 900"C, and the blank test between 600 and 9OO"C, respectively. The detailed I explanation for each value can be found in section 5.4.1. PUF samples were collected from -- blank runs between the 600" and 900C test runs to measure the carryover between the tests on a single fluorocarbon product done at 600C and 900C. Table 5.4.5.2. Flow Rate ProfiIe for Cornbustion Test at 600C Time Period Reactor Flow (set> Rate (ml/rnin) Pyroprobe Flow Rate (ml/m in) Total Flow Rate (mUrnin) Volume Air Air CH4 0-60 9.69 0.85 0.21 10.75 60 - 82a 0.00 0.00 0.00 0.00 82 - 154 154 - 164 164 - 174 9.69 9.69 +0.85 0.85 4.63b 0.21 0.21 +10.75 10.75 14.53 9.69 4.63 0.2 I 14.53 174 - 194 8.31 (He)' 4.53 (He)d 0.00 12.84 Total volume passed though reactor (ml) Total volume passed through PUF (ml) Total volume used for off-line GCMS SO2quantitative analysis (ml) 10.75 0.00 12.90 2.1 1 2.42 4.28 32.46' 29.59' 21.71' " System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). csd Switched to helium for sweep. Total carrier flow volume that passed through the reactor. Total carrier flow volume that passed through PUFs, Volume used to calculate total amount of SO2recovered using off-line GUMS system. 31 Table 5.4.5.3.Flow Rate Profile for Combustion Test at 900C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (sec) Rate (mVmin) (ml/m in) (ml/rnin) (mu Air 0 - 60 7.06 Air CH, 0.66 0.16 7.88 60 - 83a 83 - 177 177 - 187 0.00 0.00 0.00 0.00 7.06 0.66 0.16 7.88 7.06 0.66 3 4.63b 0.16 7.8s 3 11.85 187 - 197 7.06 4.63 0.16 11.85 197 - '17 6.05 (He)' 4.53 (He)d 0 10.58 Total volume passed through reactor (ml) Total volume passed through PUF (ml) Total volume used for off-line G C M S SO1 quantitative analysis (ml) 7.88 0.00 12.35 1.64 1.98 3.53 27.37' 24. 14f 19.4gg a System opened due to sample insertion. Assuming no outlet flow. Linear mcrease (approximate). csd Switched to helium for sweep. e Total carrier flowvolume that passed through the reactor. Total carrier flow volume that passed through PUFs. Volume used to calculate total amount of SO2recovered using off-line GUMS system. Table 5.4.3.4. Flow Rate Profile for Blank Analysis between 600 and 900C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Total Sampled (set) Rate (ml/min) (ml/min) (mVmin) Volume Volumed 0 - 120 120 - 130 130 - 140 140 - 160 Air 9.69 9.69 9.69 8.89 (He)b Air 0.85 0.85 3 4.63a 4.63 4.53 (He)' CIG 0.00 10.54 0.00 10.54 3 14.32 0.00 14.32 0.00 12.84 Total Volume (ml) (mu 21.08 2.07 2.39 4.28 29.82 (ml> 19.08 1.91 2.22 3.95 27.15 aLinear increase (approximate). bsc Switched to helium for sweep. Sampled volume for PUF and Tediar bag collection. 5.4.5.1I.n-line GC/MS Analysis: Figure 5.4.5. I shows the total ion chromatogram for _. combustion at 600C.The first peak at 0.5 to 1.9 min. was identified as pentafluoroethane and - the second peak at 1.9 to 2.8 was identified as suIfir dioxide. The peak at 6.9 min. corresponded to carbon disulfide. The peaks at 10.4, 10.6, and 10.8 corresponded to benzene, difluorobenzene, and fluorobenzene, respectively. The wide peak appeared at 10.9to 12.5 rnin and following background corresponded to tetrafluorosilane. Figure 5.4.5.2 shows the total ion chromatogram for combustion at 900C.The first peak at 0.2 to 1.3 min. was identified as pentafluoroethane and the second peak at 1.9 to 2.4 min. was identified as sulfur dioxide. The largest peak at 12.2 to 12.8 min. and following high background was attributed to tetrafluorosilane. The peak at 14.0 min. was not clearly identified. 32 -00000 3.aoooo 3QOOOO 140000 320000 300000 ~80000 200000 ~~0000 ~~0000 =?OOQOO _1 a0000 7 00000 fPOO0O 7 =oooo _I 0 0 0 0 0 aoooo do000 AOOPO 10000 .-- 0 . a-I .- 5.00 7 0 a0 7 - 00 Z O oa 30 0 0 Figure 5.4.5.1. In-line G C M S Ion Chromatogram for 3s 0 0 at 600C 550000 500000 - 450000 400000 - 350000 300000 ~50000 zooooo 750000 100000 I TIC:FC5--90-1. D LJ4-T J TI,..---=- Figure 5.4.5.2. In-line G C M S Ion Chromatogram for at 900C 5.4.5.2. Off-lineGC/M.S'Analysis: Figure 5.4.5.3 shows the total ion chromatogram for off-line GUMS analyses for - combustion at 600C. The largest peak at the beginning is associated with air. The small peak next to air at 0.97 min. corresponds to l,1-difluoroethene. The next small peak at 1.65 min. corresponds to pentafluoroethane. The second largest peak at 3.0 min. corresponds to sulfur dioxide. The small peak at 4.8 min. corresponds to difluorodimethylsilane Figure 5.4.5.4 shows the total ion chomatogram for off-line GUMS analyses for ;ombustion at 900C. Similar results were obtained. The largest peak at the beginning is associated with air. The second peak at 3.0 min. corresponds to sulfur dioxide. The small peak at 4.8 min. corresponds to difluorodimethylsilane. 33 400000 TIC: I-CS-e30-r.D 1*0000 3eloooo 3n0000 320000 300000 Z~OOOO 2*0000 2POOOO 320000 T+OOOOO -4 e o 0 0 0 7 =oooo -740000 ~20000 7 00000 a0000 eoooo *OOOO 20000 0 0 -,,"..."_ -.,- P- 4.bo a.00 A - - - e.00 -4o:oo 7 j 1 . 0 0 -4.00 .e.oo Figure 5.4.5.3: Off-line G U M S Ion Chromatogram for 7cI.00 at 600C . A I >L * IC1 a,1 n l ~00000 ~80000 ~~0000 340000 3ZOOOO ~00000 280000 2-0000 Z40000 ==oooo zooooo -Ie o 0 0 0 -3 eoooo -4 4 0 0 0 0 -4 ~ 0 0 0 0 -4 00000 eo000 eoooo -0000 ~0000 TIC: C C S - 6 . O T . D TI,.lr----i- 0 0 . 0 0 Figure 5.4.5.4. Off-line G U M S Ion Chromatogram for ' at 900C 5.4.5.3 LC-MS Ancrtvsis ofExkctcts: Table 5.4.5.5 shows the analytical results of the reactor/transfer line extraction samples. No detectable amount of PFOS, PFBS, found. was Table 5.4.5.5.Methanol Extraction Results for Combustion Test Extraction PFOS(pg/$) PFOS(pg) PFBS(pg/pl) PFBS(pg) 1S t <.j.OO <0.035 c5.05 <0.032 4.96 <0.02s i 2 nd <5 .oo <0.035 c5.05 <0..032 <4.96 <0.028 5.4.5.4.LC-MS Annlvsis of PUF Cartrickex: Table 5.4.5.6 shows the analytical results for the PUF sampling - cartridges. No detectable amount of PFOS, PFBS,. was found. 34 Table 5.4.5.6. PUF Extraction Results for Combustion Test 600 PUF (:lSt) <5.00 <0.12 6 . 0 5 <0.12 C4.96 PUF (2"d) 6.00 ~ 0 . 1 2 4 - 0 5 <0.12 <4.96 900 PUF (1") <5.00 <0.12 ~ 5 . 0 5 <0.12 C4.96 PUF (2"d) <5.00 <0.12 ~ 5 . 0 5 ~ 0 . 1 2 <4.96 <0.10 <0.10 <0.10 <0.10 5.4.6. PFBS Combustion Test Table 5.4.6.1 shows net amount of sample gasified for PFBS combustion tests. The sample probe was weighed before and after the combustion tests. T a b l e 5.4.6.1. Net-Amount of Gasified Sample f o r PFBS C o m b u s t i o n Test Temperature ("C) Usage Loaded Remaining Net Amount Mass (mg) of Gasified (mg) Sample (mg) 600 PUF" 0.64 0.30 0.34 T B ~ 0.59 0.11 . 0.48 900 PUF 0.62 0.16 0.46 TB 0.59 0.17 0.42 a In-line G C M S analysis and off-gas collection using PUF. Off-line GCMS analysis using Tedlar Bag. Table 5.4.6.2, 5.4.6.3, and 5.4.6.4 show flow rate profiles used for PFBS combustion tests at 600 and 900C, and the blank test between 600 and 9OO"C, respectively. The detailed explanation for each value can be found in section 5.4.1. PUF samples were collected from blank runs between the 600 and 900C test runs to measure the carryover between the tests on a single fluorocarbon product done at 600 and 900C. .- T a b l e 5.4.6.2. Flow R a t e Profile for PFBS C o m b u s t i o n T e s t at 600C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (set> Rate (rnl/min) (ml/min) (rnl/m in) (mu Air Air CHJ - 0 - 6 0 60 8Cla - 9.79 0.00 0.83 0.22 0.00 0.00 10.84 0.00 10.84 0.00 80 - 152 152 - 162 162 - ,i72 172 - 192 9.79 9.79 9.79 8.31 (He)' 0.83 0.22 0.83 -3 4.63b 0.22 4.63 0.22 4.53 (He)d 0.00 +10.84 10.84 14.64 14.64 12.97 13.01 2.12 2.44 4.32 Total volume passed through reactor (ml) 32.73' Total volume passed through PUF (rnl) Total volume used for off-line GUMS SO2quantitative analysis (ml) 29.87f 2 1.89' a System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). Switched to helium for sweep. e Total carrier flow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. g Volume used to caIculate total amount of SOz recovered using off-line GUMS system. I 35 c Table 5.4.6.3. Flow Rate Profile for PFBS Combustion Test at 900C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (set:) Rate (mUmin) (mUrn in) (ml/min) (mu Air Air CH, 0-60 60- 80a 80 - 174 174- 184 184 - 194 7.14 0.00 7.14 7.14 7.14 0.65 0.00 +0.65 0.65 4.63b 4.63 0.17 0.00 0.17 0.17 0.17 7.96 0.00 +7.96 7.96 11.94 11.94 7.96 0.00 12.47 1.66 1.99 194 - 214 6.24 (He)' 4.53 (He)d 0.00 10.77 Total volume passed through reactor (ml) Total volume passed through PUF (ml) 3.59 27.67' 74.44' Total volume used for off-line G U M S SO2 quantitative analysis (ml) 19.71g a System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). c,d Switched to helium for sweep. e TotaIcarrier flow volume that passed through the reactor. Total carrier flow volume that passed through PtJFs. Volume used to calculate total amount of SO2recovered using off-line GUMS system. Table 5.4.6.4. Flow Rate Profile for Blank Analysis between 600 and 900C Time Reactor Flow Pyroprobe Flow Rate Period (sec) Rate (rnllmin) (rnl/rnin) Total Flow Rate (ml/min) Total Volume Sampled Volumed 0 - 120 120 - 130 130 - 140 140 - 160 Air 9.79 9.79 9.79 8.44 (He)b Air CH4 0.83 0.00 10.62 0.83 3 4.63" 0.00 10.62 3 14.42 4.63 0.00 14.42 4.53 (He)' 0.00 12.97 Total Volume (mi) (ml) 2 1.24 2.09 2.40 4.32 30.05 (ml> 19.24 1.92 2.24 3.99 27.39 aLinear mcrease (approximate). b,c Switched to helium for sweep. Sampled volume for PUF and Tedlar bag collection. _. 5.4.6.1.In-line GC/MSAnaZvsis: Figure 5.4.6.1 shows the total ion chromatogram for PFBS combustion at 600C. The peak at 0.6 was identified as pentafluoroethane and that at 1.Omin., which has strong 85 m/z signal, was not identified. Tetrafluorosilane is not likely because of the different retention time. The peak at 1.7 to 2.5 min. corresponds to sulfLir dioxide: The largest peak at 10.0 to 12.0 min. corresponds to tetrafluorosilane. Figure 5.4.6.2 shows the total ion chromatogram for PFBS combustion at 900C. The first peak at 1.8 to 2.5 min. corresponds to sulfur dioxide. The peak at 10.6 corresponds to benzene. The largest peak at 14.2 min. and following background correspond to tetrafluorosilane. 36 TIC: F C B - d O - , .D 70000 do000 ~0000 40000 ~0000 ~0000 7 0000 0 *IC, F i g u r e 5.4.6.1. In-line GCIICIS Ion C h r o m a t o g r a m f o r PFBS a t 600C TIC:FC6-00-1 .D 1000000 900000 a00000 700000 e00000 sooooo 400000 900000 200000 100000 .. 0 L-__ 5.00 70.00 .OO 20.00 25.00 30.00 35.00 Tlmu--- Figure 5.4.6.2. In-line G C M S Ion Chromatogram for PFBS at 900C 5.3.6.2. Off-lineGC/iMSAnalvsis: Figure 5.4.6.3 shows the total ion chromatogram for off-line GUMS analyses for PFBS combustion at 600C. The largest peak at the beginning is associated with air. The second peak at 3.0 min. corresponds to sulflir dioxide. Figure 5.4.6.4 shows the total ion chromatogram for off-line GCMS analyses for PFBS combustion at 900C. Similar results were obtained. The largest peak at the beginning is associated with air. The second peak at 3.0 min. corresponds to sulfur dioxide. 37 m - -TIC: FC6-60T.D 400000 350000 300000 250000 200000 150000 100000 50000 -- 0 I 0. 2.00 4.0l 0" ' ' 6 ., 0 0~ ~ ~ 8.. 0, 0 ~ .1 0~ . .0 0, I 1 2I .I 0 0I , I 1 4 , . 0,.0 . , , 1,6.0,0, , 1,8.00 I T imir;--r Figure 5.4.6.3. Off-line GC/MS Ion Chromatogram for PFBS at 600C Ahu nd a n cn 400000 350000 300000 -: I 250000 - 200000 ~ 150000 - TIC:FC6-90T.D Figure 5.4.6.4. Off-line G C M S Ion Chromatogram for PFBS at 900C 5.4.6.3. LC-hfS Analysis ofExtracts: Table 5.4.6.5 shows the analytical results of the reactorhransfer line extraction samples. The first and second extracts of the PFBS reactodtransfer line done after the 900C run totaled to about 0.22% of the PFBS added. A small amount of was also found fiom the extracts. The contamination source may be the outer pyroprobe surface (not the insert, which is replaced with each test) where combustion was conducted in the previous test. New reactodtransfer lines were used for each combustion test. The reactor/transfer line extraction for combustion test was performed prior to PFBS combustion extraction, but no was detected from the prior extraction. The extraction system tubing was cleaned following every sample extraction. 38 Table 5.4.6.5. Methanol Extraction Results for PFBS Combustion Test Extraction PF0S(pg/pl') PF0S(pg) PFBS(pg/pl) PFBS(,ug) 1St G.00 <0.035 169 1.1 15.4 0.087 2nd G.00 <0.035 60.3 0.39 <4.96 <0.025 5.4.6.4.LC-MSAmlysis ofPUF Cartridges: Table 5.4.6.6 shows the analytical results for the PUF sampling cartridges. A little less than 0.6%' of PFBS was detected at 600C and surprisingly, a larger 1.10,/0amount of PFBS was detected from the 900C test. The distributiori between the 1' and 2ndPUF was about equal at 600"C, but 97% of PFBS was captured in the first PUF at 900C. An amount of carryover equivalent to 0.066% of PFBS added in the preceding 600C tests was extracted from the PUF in the PFBS interim blank. In addition, an amount of equivalent to 0.09% of the that would have been added in a test was found in the PFBS interim blank. The presence of the is another indication of possible low level cross contamination between tests. Table 5.4.6.6. PUF Extraction Results for PFBS Combustion Test Temp("C) Extraction PFOS PFOS PFBS PFBS PUF (2nd) -3.00 <0.12 85.6 2.0 900 PUF (1") G.00 <0.12 320 7.4 PUF (2"d) 6.00 <0.12 9.63 0.22 Interim blank PUF (I") C5.00 <0.12 19.3 0.45 <4.96 <4.96 <4.96 26.2 <0.10 <0.10 <0.10 0.54 5.4.7. PFOS Combustion Test Table 5.4.7.1 shows net amount of sample gasified for PFOS combustion tests. The sample probe was weighed before and after the combustion tests. .- T a b l e 5.4.7.1. Net Amount of Gasified S a m p l e f o r PPOS C o m b u s t i o n Test 'Temperature Usage Loaded Remaining Net Amount ("C) Mass (mg) of Gasified (mg) Sample - (mg) -- 600 PUF" 0.47 0.02 0.45 TB 0.48 0.10 0.38 900 PUF 0.50 0.00 0.50 . TB 0.50 0.00 0.50 a In-line GC/rdS analysis and off-gas collection using PUF. Off-line G U M S analysis using Tedlar Bag. ' The percentages that indicate the sample recovery here and hereafter are not corrected for the fraction of air flow that was diverted to the in-line GUMS. The correction for this fraction is too complicated and ambiguous to make accurately because of the complexity of the flow scheme, mainly due to changes in both concentration and split ratio with time. If corrected, these recoveries would likely be 10 to 15 percent higher. 39 Tables 5.4.7.2, 5.4.7.3 and 5.4.7.4 show flow rate profiles used for PFOS combustion tests at 600 and 900C, and the blank test between 600 and 9OO"C, respectively. The detailed explanation for each value can be found in section 5.4.1. PUF cartridge samples were collected from blank runs between the 600 and 900C test runs to measure the carryover between the tests on a single fluorocarbon product done at 600 and 900C. Table 5.4.7.2. Flow Rate Profile for PFOS Combustion Test at 600C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate Volume (set> 0-60 60 - 5Sa as - 157 157 - 167 167 - 177 177 - 197 Total Rate (ml/min) Air 9.86 0.00 9.86 9.86 9.56 8,61 (He)' volume used for (mumin) Air cH4 0.85 0.2 1 (mllmin) 10.92 0.00 0.00 0.00 0.85 0.2 1 10.92 0.85 3 4.6Jb 0.21 10.92 3 14.70 4.63 0.2 1 14.70 4.53 (He)d 0.00 13.14 Total volume passed through reactor (ml) Total volume passed through PUF (ml) off-line GCfifS SOzquantitative analysis (ml) (m0 10.92 0.00 13.10 2.14 2.45 4.35 32.99' 30.12' 22.07g a System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). c*dSwitched to helium for sweep. Total carrier flow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. Volume used to calculate total amount of SOzrecovered using off-line G C M S system. Table 5.4.7.3. Flow Rate Profile for PFOS Combustion Test at 900C Time Period Reactor Flow Pyroprobe Flow Rate Total Flow Rate VoIume (see) Rate (ml/min) (mumin) (ml/min) (mu Air Air cH4 0-60 7.12 0.65 0.16 7.93 7.93 60 - 8Sa 0.00 0.00 0.oo 0.00 0.00 a5 - 179 7.12 0.65 0.16 7.93 12.42 179 - 189 7.12 0.65 4.63b 0.16 7.93 3 11.91 I .65 . - .- 189 - 199 7.12 4.63 0.16 11.91 1.99 199 - 219 6.15 (He)' 4.53 (He)d 0 10.68 3.56 Total volume passed though reactor (ml) 27.55' Total volume passed through PUF (ml) 24.3zf Total volume used for off-line GUMS SO2 quantitative analysis (ml) a System opened due to sample insertion. Assuming no outlet flow. Linear increase (approximate). c3dSwitched to helium for sweep. e Total carrier flow volume that passed through the reactor. Total carrier flow volume that passed through PUFs. Volume used to calculate total amount of SOz recovered using off-line G C M S system. '+ 40 Table 5.4.7.4. Flow Rate Profile for Blank Analysis between 600 and 900C Time R.eactor Flow Pyroprobe Flow Rate Period (sec) Rate (mumin) (mumin) Total Flow Rate (m I/m in) 0 - 120 120 - 130 130 - 140 ' 140 - 160 Air 9.86 9.86 9.86 8.61 (He)b Air CH4 0.85 0.00 0.85 3 4.63a 0.00 4.63 0.00 4.53 (He)' 0.00 10.71 10.71 3 14.49 14.49 13.14 Total Volume (ml) Total Volume (ml> 2 1.42 2.10 2.42 4.35 30.32 Sampled Volumed w> 19.42 1.93 2.25 4.05 27.65 aLinear increase (approximate). b,c Switched to helium for sweep. Sampled volume for PUF and Tedlar bag collection. 5.4.7.1. In-line GC'hlS Analysis: Figure 5.4.7.1 and 5.4.7.2 show total ion chromatograms for PFOS combustion at 600 and 9OO"C, respectively. A single sulfur dioxide peak was the only identifiable peak for both combustion tests. No tetrafluorosilane peak was observed for PFOS combustion tests. It is not clear why the total ion chromatograms for PFOS combustion at 600 and 900C differ from the others. 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 late stage of the testing. 40000 3a000 SSOOO 34000 52000 JOOOO =eo00 26000 z4000 22000 20000 '1 aooo 16000 -In000 1 ZOO0 10000 eo00 6000 0 TIC: FC7--30-1 .o . L : 4.00 1 0 ., 0 0 . ' T' S ,. 0 0 ZO.00 25:OO 3O:OO 35.00 Figure 5.4.7.1. In-line G C M S Ion Chromatogram for PFOS at 600C 41 i 6 5 0 0 C 6000C TIC: F C 7 - S O - 1 . O 5500C 5oooc dsooa 40000 35000 30000 25000 zoooo 7 so00 7 0000 5000 0 Time--=- Figure 5.4.7.2. In-line G C M S Ion Chromatogram for YFOS at 900C 5.4.7.2. Off-lineGCAWSAnnlvsis: Figure 5.4.7.3 shows the total ion chromatogram for off-line GCMS analyses for PFOS combustion at 600C. The largest peak at the beginning is associated with air. The second peak at 1.O min. was identified as 1,1-difluoroethene. The peak at 3.O min. was identified as sulfur dioxide. Figure 5.4.7.4 shows the total ion chromatogram for off-line GUMS analyses for PFOS combustion at 900C. Similar results were obtained. The largest peak at the beginning is associated with air. The second peak at 3.0 min. corresponds to sulfix dioxide. Y tau c. .=.* ..l-,-* I TIC P C 7 - - d O T D -00000 JIOOOO 320000 ~00000 220000 7 eoooo _I - 0 0 0 0 -~ c r 0 0 0 0 00000 eoooo 00000 -0000 20000 T I . . , . - --.. 0 00 100 400 e 00 -0.00 00 1 - s oo 7 - 00 7 - 00 Figure 5.4.7.3. Off-line G C M S Ion Chromatogram for PFOS at 600C 42 400000 ~aoooo 3.SOOOO ~POOOO 520000 ~00000 zaooao ~=oooo ~POOOO ~20000 200000 1 eo000 1 eOOoQ -l~0000 - I ~ O O O O ' 1 00000 *oooo 00000 i-0000 -1 ~0000 F0 0 . 0 0 T 1 C : CC7--BOT.D Figure 5.4.7.4. Off-line GC/MS Ion Chromatogram for PFOS at 900C 5.4.7.3. LC-MSAnaZvsisofExtmcts: Table 5.4.7.5 shows the analytical results of the reactor/ transfer line extraction samples. Extracts of reactorltransfer line tubing afler the 900C test summed to oniy about 0.04% of the PFOS added. A small amount of PFBS, 0.04 pg, was detected from the extract, which could be formed during PFOS combustion or could have been carryover from the previous PFBS combustion tests. Table 5.4.7.5. Methanol Extraction Results for PFOS Combustion TeF1.+ Extraction PFOS(pg/pl) PFOS(pg) PFBS(pg/pI) PFBS(pg) 1st 15.4 0.11 7.1 1 0.045 ~~ < C4.96 <0.025 2nd 8.61 0.059 x5.05 <0.032 ~4.96 <0.025 5.4.7.4L.C-MSAnaIvsisofPUF Cartridges: Table 5.4.7.6 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 600C. Only about 0.05% was captured by the PUFs at 900C. Surprisingly, somewhat larger amounts of PFOS were extracted from the second PUF in a two-PUF series at both 600C and 900C. This suggests that some PFOS could have passed completely through the system, but in the third transfer efficiency tests, much larger amounts of PFOS and PFBS were captured in the first PYF in the series showing that the first PUF typically collects more. An amount of carryover equivalent to 0.026% of PFOS added in the preceding 600C tests was extracted from the PUF in the PFOS interim blank. A small amount of PFBS was found from ' the combustion test at 9OO"C, which could have been carryover or a combustion byproduct of PFOS combustion. 43 Table 5.4.7.6. Temp Extraction ("C) 600 PUI; (1") PUT (2""> 900 PUF (1") PUF (znd) PUF Extraction Results for PFOS Combustion Test PFOS PFOS PFBS PFBS L-16271 L-16271 W P l ) (Pi9 (Pg/pl) ( P d (FJg/Pl) (Pi9 25.1 0.62 <5.05 < O X 4 . 9 6 <0.10 64.0 1.6 C5.05 <0.12 <4.96 <o. 10 4.31 0.11 -3.05 CO.12 <4.96 <0.10 9.01 0.22 25.8 0.60 c4.96 <o. IO 5.5. Revised Chemical Composition of Table 5.5.2 shows the changes in the necessary amount of sample that have the equivalent amount of fluorine in 0.5 mg of PFOS and the corresponding stoichiometric amount of air. The actual amount of samples gasified for combustion tests were 1.88 to 2.10 mg and 2.76 to 2.94 mg, respectively, which were ca. 10% different fiom the ideal amounts. This - _. difference is well within the overall error of the measurements and does not impact the validity of the test results. Table 5.5.2. Correction of Amount of Sample That Contains Equivalent Amount of Fluorine in 0.5 mg of PFOS 5.6. 2"d Heated B 1 . d Combustion Analysis After the combustion tests for the seven compounds were completed, the heated blank reactor/ transfer line tubing was analyzed again to examine system cross contamination at temperatures of 600 and 900C. In-line GUMS analysis, off-line GUMS analysis using Tedlar bags, and 44 PUF cartridge sampling were conducted. The same process used for the first heated blank analysis before the sample combustion tests was performed for this second heated blank analysis. The PUF samples were sent to 3M Environmental Laboratory for LC/MS analysis. 5.6.1. In-line W / M S Analysis Table 5.6.1 and 5.6.2 shows flow rate profile and carrier flow volume used for heated blank analysis at 600 and 900C7 respectively. Figure 5.6.1 and 5.6.2 shows total ion chromatograms for reactor temperatures at 600 and 900"C7respectively. The chromatograms show only background noise and no contamination was found for either temperature. Table 5.6.1. Flow Rate Profile for Heated Blank Analysis at 600C Time Period Reactor Flow Rate (mumin) Pyroprobe Flow Rate Total Flow Rate (ml/min) Total Volume Sampled Volumed 0 - 120 120 - 130 130 - 140 140 - 160 10.0 -10.0 10.0 8.83 (He)b (ml/min) 0.81 0.81 3 4.63a 4.63 4.53 (He)" 10.81 10.81 3 14.63 14.63 13.36 Total Volume (ml) (m 1) 21.62 2.12 2.44 4.45 30.63 (mu 19.62 1.95 2.27 4.12 27.97 'Linear increase (approximate). b2c Switched to helium for sweep. Sampled volume for PLTF and Tedlar bag collection. Table 5.6.2. Flow Rate Profde for Heated Blank Analysis at 900C Time Period Reactor Flow Pyroprobe Total Flow Rate Total Sampled (set> Rate ( m l h i n ) Flow Rate (ml/min) Volume ~ o l u r n e ~ (mi/min) (ml) (ml> 0- 150 7.1 1 0.62 7.73 19.33 16.83 150 - 160 160 - 170 7.1 1 0.62 3 4.63" 7.73 3 11.74 7.1 1 4.63 1 1.74 1.62 1.46 1.96 1.79 170 - 190 6.16 (He)b 4.53 (He)" 10.69 3.56 3.23 - Total Volume (mi) 26.47 23.30 =Linear increase (approximate). b.CSwitchedto helium for sweep. Sampled volume for PUF and Tedlar bag collection. 45 Figure 5.6.2. In-line G C M S Ion Chromatogram for Heated Blank at 900C 5.6.2. Off-line GC/NlS Analysis Figure 5.6.3 and 5.6.4 show total ion chromatograms for the heated blank at 600 and 900C respectively. The large peaks at the beginning are associated with air. No other peaks were observed. A I S L . "r.le,n 0- -l zoooo TIC; H E = - 6 O T . O 7 -l 0 0 0 0 100000 OOOOO eo000 70000 soooo 50000 POOOO 70000 ~0000 -loo00 0 z.00 4.00 6.00 8.00 10. Tir v * . f - - 3 - Figure 5.6.3. Off-line G C M S Ion Chromatogram for Heated Blank at 600C i2dOOOO 2;COOOO zooooo 7 aoooa 7 60000 140000 ' 1~0000 7 00000 e0000 60000 rroooo ~0000 T o..--.--- 0 0.00 - :oo. .*:oo ' ' ' Figure 5.6.4. Off-line G C M S Ion Chromatogram for Heated Blank at 900C 46 5.6.3. LC-MS Analysis of PUF Cartridges Table 5.6.3 shows the analytical results.for the PUF sampling cartridges. No cross contamination was detected. Temp ("C) 600 900 Table 5.6.3. PUF Extraction Results for Heated Blank Analysis PF0S(pg/pl) PF0S(pg) PFBS(pg/ pl) PFBS(pg) 40.0 <10.0 <0.25 <0.25 <10.1 <10.1 CO.23 <0.23 -4.96 C4.96 <0.10 <0.10 5.7. Transport Efficiency Tests for PFBS and PFOS Sample transfer efficiency tests were conducted to investigate how efficiently PFOS, PFBS, and would be transferred through reactor/transfer line system. Three types of tests were conducted for each sample, Ivhich were described in the Phase 111protocol and its addendum. 5.7.1. 1'' Transport Efficiency Test In the first transfer efficiency test, PFOS, PFBS, were volatilization in the pyroprobe chamber and the reactor and transfer lines were heated to 260C. PUF cartridge sampling of the off-gases was performed. This test examines the transfer efficiency of samples gasified in the pyroprobe and transported through reactor. Table 5.7.1.1 shows the net amount of gasified sample for the 1St transfer efficiency test, Table 5.7.1.2 shows flow profiles used for ,PFBS, and PFOS. Table 5.7.1.1. Samule PFBS PFOS Net Amount of Gasified Sample for 1"Transfer Efficiency Test Loaded Remained after Net Amount of Mass (mg) Gasification (mg) Gasified Sample (mg) 0.53 0.00 0.53 0.54 0.00 0.54 0.53 0.05 0.45 Table 5.7.1.2. Flow Time Period Reactor Flow (set) Rate (mumin) . I 0 - 60 16.0 60 - 84 0.00 84 - 156 16.0 156 - 166 16.0 166 - 186 16.0 Rate Profile for Pyroprobe Flow Rate (ml/min) 0.82 0.00 +0.82 0.82 4.53b 4.53 1"Transfer Efficiency Test" Total Flow Rate Total (ml/min) Volume 16.82 (mi) 16.82 0.00 +16.82 16.82 20.53 20.53 0.00 20.1 8 3.1 1 6.84 Sampled Volume' (mi) 15.82 18.95 2.9: 6.5 1 Total Volume (ml) 46.95 44.26 "Helium was used for all carrier flow. Linear increase (approximate). Sampled volume for PUF collection. Table 5.7.1.3 shows the PUF cartridge sampling results for ,PFBS, and PFOS, respectively. No sample was recovered from the PUF cartridge. This result indicates that the 47 sample was either thermally dissociated in the pyroprobe chamber or the gasified sample was completely condensed in the pyroprobeheactor transfer line tubing. Table 5.7.1.3. YUF Extraction Results for 1" Transfer Efficiency Test --7 Sample PUF PFOS PFOS PFBS PFBS(pg) - c -, - PFBS PFOS Extracts 1 2nd 1S t 2"d 1S t 2"d ~5.00 6.00 -4.00 600 6.00 -3.00 (!%> <0.12 <0.12 <0.12 <0.12 <0.12 co.12 (P3W 6.05 <5.05 <5.05 G.05 G.05 6.05 <o. 12 <0.12 <o. 12 <0.12 <o. 12 co.12 (P&) 4.96 4.96 4.96 4.96 c4.96 4.96 (PI) ' ' <o. 10 <o. 10 <0.10 <0.10 <0.10 co.10 5.7.2. 2"dTransfer Efficiency Test To investigate the possibility that the sample condensed on the walls of the pyroprobeheactor transfer line, the sample was collected directly from the pyroprobe upstream of the reactor. PUF sample cartridges were connected to the pyroprobe using the shortest possible transfer line. The pyroprobe and transfer line were extracted using methanol. Table 5.7.2.1 shows the net amount of gasified sample for 2"dtransfer efficiency test. Table 5.7.2.2 shows flow profiles for PFBS, and PFOS 2"dtransfer efficiency test, respectively. Table 5.7.2.1. Net Amount of Gasified Sample for 2"dTransfer Efficiency Test Sample Loaded Remained after Net Amount of iMass (mg) Gasification (mg) Gasified Sample (mg) 0.52 0.02 0.50 PFBS 0.60 0.16 0.44 PFOS 0.47 0.00 0.47 Table 5-7.2.2. Flow Rate Profile for 2"dTransfer Efficiency Test' Time Period Pyroprobe Flow Volume (set> Rate (rnl/min) (ml) 0 - 60 0.63 0.63 60 - 82 0.00 0.00 82 - 176 176 - 186 +0.63 0.63 4.53b 0.99 0.43 186-216 4.53 2.27 Total Volume (ml) 4.32 aHelium was used for carrier flow. Linear increase (approximate). Table 5.7.2.3 shows the analytical results for the extracts. Table 5.7.2.4 shows the analytical results for PUF cartridge samples. Substantial amounts, 3.4% of PFOS and 2.6 YOof PFBS, were found in the pyroprobe transfer line extracts. Very little was detected in the PLF cartridge samples. This test shows that measurable amounts of PFOS and PFBS survive pyrolysis conditions of the pyroprobe, and enter the heated transfer lines up to the reactor. Larger amounts 48 of PFOS and PFBS condense in the heated transfer lines downstream of the pyroprobe and upstream of the high-temperature reactor. Analytical results on the 2ndtransfer efficiency test also showed some indications of cross contamination. Significant amounts of PFOS were found in the first PUF (equivalent to 0.5%) and the transfer line extract (equivalent to 0.8%) when PFBS was combusted. The analytical characterization of the PFBS used, does not indicate the presence of PFOS, and it seems unlikely that it would be formed through thermal rearrangement of PFBS in the pyroprobe. Also a small amount of PFOS (equivalent to 0.13%) was found in the transfer line extract of the transfer efficiency test. Additionally, a very small amount of PFBS (equivalent to 0.037%) was found in the second PUF in the two-PUF series of the transfer efficiency test. Again, PFOS is not listed as an impurity of the 1 in its analytical characterization. PFBS is a possible thermal degradation product of the but if so, it is surprising that it is seen only in the second PUF in the series. Table 5.7.2.3. .Methanol Extraction Results for 2"dTransfer Efficiency Test Sample Extracts PFOS PFOS PFBS PFBS (Pg/Pl) (Pd W P I ) (Pg) ( P W ) (Pd 1j t 35.0 0.82 G 5 . 2 <OS6 6.89 0.13 2nd 4 0 . 0 <0.24 4 0 . 1 <0.22 <4.96 <0.097 PFB S PFOS 1 23 3 5.5 805 IS <12.4 C0.25 2nd <10.0 <0.24 <10.1 <0.22 <4.96 <0.097 1st 8 97 21 <63.0 4 . 3 9 4 2 . 4 c0.25 2nd C10.0 X0.24 c10.1 <0.22 <4.96 <0.097 Table 5.7.2.4. PUF Extraction Results for 2"dTransfer Efiiciency Test Sample PUF PFOS PFOS PFBS PFBS PFBS PFOS Extracts - 1St 2nd - 1St 2nd - 1st 2nd - (pg/pl) <10.0 <10.0 119 c10.0 <~o.o 40.0 (P.g>. <0.25 <0.25 3.0 CO.25 ~0.25 <0.25 (pg4-4 G5.2 11.2 ~25.2 <10.1* ~25.2 <10.1 (,Ud <0.23 0.26 <0.23 <0.23 ~0.23 ~0.23 (Pg/P1) <4.96 c4.96 <4.96 c4.96 <4.96 <4.96 (Pg) <0.10 <o. 10 <O.IO <o. 10 <o. 10 <0.10 5.7.3. 3rdTransfer Efficiency Test A 3'd transfer efficiency test was conducted to examine how much PFBS and PFOS can be transferred throulgh 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 5.7.3.1 shows the net amount of gasified sample for each test. The experiments were carried out using both air and helium to compare the results. M e r a sample was placed in the reactor and the system was closed, the temperature of GC oven was increased to prevent the condensation of gasified sample. When the GC oven temperature reached 260C, the furnace temperature was set to the temperature shown in Tables 5.7.3.2, 49 5.7.3.3, 5.7.3.4 and 5.7.3.5. The off-gas collection using PUF cartridges was initiated when the GC oven started heating. Table 5.7.3.1. Net Amount of Gasified Sample for PUF Collection Sample Carrier Lozded Remained after Net Amount of Gas Mass Gasification Gasified Sample (mg) (mg) (mg) PFBS Air 0.56 0.09 0.47 PFBS He 0.59 0.20 0.39 PFOS Air 0.48 0.00 0.48 PFOS He 0.50 0.04 0.46 Tables 5.7.3.2, 5.7.3.3, 5.7.3.4, and 5.7.3.5 show flow rate profiles for PFBS and PFOS gasification under oxygen-rich and oxygen-deficient conditions. Table 5.7.3.2. Flow Rate Profile for PUF Collection (PFBS Gasification with Air) Time Period Temperature Carrier Gas Used Total Volume Sampled Volumea (set> Condition ("C) and Flow Rate (mvmin) (ml> (ml) 0-421 421 - 650 650 - 950 950 - 1010 + GC Oven 25 3 260 Furnace 99 575 GC = 260, Furnace = 575 GC = 260, Furnace = 575 Air 10.8 Air 10.8 Air 10.8 He 8.9 75.78 4 1.22 54.00 8.90 65.76 37.40 49.00 7.90 Total (ml) 179.90 163.07 a Sampled volume for PUF collection. Table 5.7.3.3. Flow Rate Profile for PUF Collection (PFBS Gasification with He) Time Period Temperature Camer Gas Used Total Volume Sampled Volumea , (set> 0 - 423 428 - 623 623 - 983 Condition ("C) GC Oven 25 3260 Furnace 110 3 550 GC = 260, Furnace = 550 and Flow Rate (mvmin) He 10.8 `He 10.8 He 10.8 Total (ml) (ml) 77.04 35.10 64.80 176.94 (ml> . 69.91 31.85 58.80 160.56 a Sampled volume for PUF collection. Table 5.7.3.4. Flow Rate Profile for PUF Collection (PFOS Gasiiication with Air) Time Period Temperature Carrier Gas Used Total Volume Sampled Volume' (set> 0 - 439 439 - 637 637 - 937 Condition ("C) CiC Oven 25 3 260 Furnace 103 3 575 GC = 260, Furnace = 575 and Flow Rate ( m h i n ) Air 10.7 Air 10.7 Air 10.7 (mi> 78.29 35.3 1 53.50 (ml) 70.97 32.01 45.50 937 - 997 GC = 260, Furnace = 575 He 8.6 8.60 7.60 Total (ml) 175.70 159.08 a Sampled volume for PUE; collection. 50 Table 5.7.3.5. Flow Rate Profile for PUF Collection CpPOS Gasification with He) Time Period (set) 0-410 410- 615 615 - 975 Temperature Condition ("C) GC Oven 30 -9 260 Furnace 140 3 575 GC: = 260, Furnace = 575 Carrier Gas Used and Flow Rate (mumin) He 10.8 He 10,s He 10.8 Total Volume (ml> 73.80 36.90 64.80 Sampled Volumea (m0 66.97 33.45 55.80 Total (rnl) 175.50 159.25 a Sampled volume for PUF collection. Tables 5.7.3.6 and 5.7.3.7 show the amount of recovered sample from the extracts and the PUF cartridges, respectively. The 3'd transfer efficiency test showed quite clearly that some measurable PFOS (3.8% air, 11% He) and PFBS (4.5% air, 1.7%He) could pass from the heated reactor, where it was volatilized in this test, to the PUFs. Larger amounts of PFOS (4.4% air, 30% He) and PFBS (3.3% air, 20% He) also accumulated in the reactor/transfer lines upstream of the PUF cartri.dges. The majority of the PFOS and PFBS accumulated in the portion of the transfer line heated to 260"C, suggesting that both of these compounds could condense, or were in a particulate form, at t h s temperature. Table 5.7.3.6. ReactorNalve Transfer Line Extraction Results Sample Gasification Location Extracts PFOS PFOS PFBS PFBS Air 2"d c10.0 C0.12 12.8 0.15 <4.96 <0.052 Valve 1 c10.0 <0.035 3524 12 5.17 0.024 PFB S 2nd <10.0 <0.035 69.9 0.23 <4.96 <0.014 Reactor 1 <10.0 <0.12 10454 124 c4.96 CO.052 He 2"d 4 0 . 0 c0.12 420 5 .O 11.9 0.12 Valve 1st K10.0 <0.035 2510 8.2 x4.96 C0.014 2nd x10.0 <0.03.5 71.6 0.23 <4.96 <0.014 Reactor I St 1905 24 81.4 0.96 <4.96 <0.52 .- Air 20d 35.4 0.45 5.79 0.069 <4.96 <OS2 - Valve 1 696 2.4 52.0 0.17 <4.96 <0.014 PFOS 2"d 22.5 0.079 <S.OS C0.016 X4.96 <0.014 Reactor 1st 13530 171 23 7 2.5 <4.96 <0.052 He 2"d 150 1.9 4 . 0 5 <0.060 <4.96 <0.052 Valve 1 2215 7.7 47.4 0.15 <4.96 <0.014 2nd 102 0.3 5 <5.OS C0.016 <4.96 <0.014 51 Table 5.7.3.7. PUF Extraction Results Sample Carrier Cartridge PFOS PFOS PFBS PFBS Air 2 997 <10.0 25 c0.12 14.7 4.05 0.34 c4.96 <0.12 <4.96 <1.0 c1.0 5.8. Sulfbr Recovery Rate as S 0 2 , SOF2, and S02F2 Based on the in- and off-line GS/MS analyses, sulfur was found mainly as S 0 2 . No SOF? and S02F2 was detected. Suifur recovery rate as SO2 using in-line GUMS system was not quantitatively repeatable. This was due primarily to the low SO2 peak resolution using the cryogenic focusing method at -60C with a holding time of ca. 4 min. Because the SO2 peaks using the off-line GC/MS system were much sharper than SO2peaks observed using in-line GUMS, we decided to use off-line GUMS analytical results to quantitatively analyze the sulfur recovery analysis as S 0 2 . The detailed operational procedures were described in Section 5.4. Table 5.S.1 and Figure 5 3 . 1 show the calibration results. The sulfur recovery rate is reported on a molar basis. The formula obtained from this calibration was: SO2 (Mol) =[Area + 4949801 / [1.7997x Table 5.8.1. SO2 Calibration Results Using PLOT Column Conc. (mm) Mol. ## Area 1 Area 2 Area fAve) 1000 4.09E-08 7191079 6950771 7055925 700 . 2.86E-08 4414365 4366705 4390535 400 1.63E-08 2304394 2295497 2300046 100 4.09E-09425431 416699 42 1065 52 8.0 IO6 y = -4.949&+05.+ 1.7997e+14x R= 0.99656 0 1 2 3 4 5 Mol Figure 5.8.1. SO2 Calibration Curve (MoIar Number vs. Peak Area) Prior to the sulfur recovery analysis as Sol,a third SO2 transfer efficiency test was conducted using the off-line analysis approach. Table 5.8.2 shows the results. Air was flowed through the reactor at 8.85 mVmin for 2 min.30 sec. while the SO2 standard was being injected and the offgas 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 5.5.3 shows sulfur recovery rate as SO2 for the seven compounds tested. The rate varies from 22.0 to 96.2 %. The last column shows sulfur recovery rate taking into account a transfer efficiency rate of 75.6%. The recovery rate as SO2 for FC-1395 and is nearly 100% and that for FC-807A is greater than 100%. The recovery rate at 600C was better than at 900C for all compounds. Table 5.8.2. Standard SO2 Transfer Efiiciency Volume (ml) Area Calculated Mol. # # of M 01. Used Transfer Efficiency (%) 22.13 10591947 1.36E-06 1.63E-06 83.4 22.13 8515987 1.11E-06 1.63E-06 67.8 Average 75.6 53 Compound FC-1395 FC-807A PFBS PFOS Temp. (C> 600 900 600 900 600 900 600 900 600 900 600 900 600 900 Table 5.5.3. Sulfur Recovery Rate as SO2 Volume Area Calculated Gasified # of Mol. of Recovery (mu 34.64 Mol. # 8069545 Mass (ms> 2.10 Gasified Sample Rate (%) 48.4 30.67 8136877 1.88 45.2 53.93 4025040 2.75 36.0 53.07 3508967 2.94 29.7 21.35 4159651 5.52E-07 0.52 7.15E-07 77.2 19.55 3402701 4.23E-07 0.43 5.91E-07 71.6 21.81 6587231 8.5SE-07 0.59 9.1SE-07 93 .8 19.85 6354547 7 . 5 5 ~ - 0 7 0.53 8 . 2 2 ~ - 0 7 91.9 21.71 10495604 0.52 78.9 19.49 10366292 0.54 67.4 21.59 4495370 6.07E-07 0.48 1 . 4 2 ~ ~ 0 6 42.8 19.71 2000176 2.73E-07 0.42 1.24E-06 22.0 22.07 2169530 3.27E-07 0.35 7.06E-07 46.3 19.62 2676600 3.46E-07 0.50 9.29E-07 37.2 Recovery Rate after Efficiency Correction (%j 64.0 63.8 47.6 39.3 102.1 94.7 124.0 121.5 104.4 89.2 56.6 29.1 61.2 49.2 5.9. Extracted Ion Analysis The following ions (69-CF3, 119-C~F5a, nd 67-SOF) were extracted from the total ion chromatograms of all combustion tests (in-line and off-line G C M S analyses) to analyze for the presence of perfluorinated and sulfonate-containing intermediates. The purpose of th.~sanalysis was to provide additional information regarding the potential formation of volatile fluorocarbons and volatile fluorinated oxysulfur compounds that were not identified in the GUMS approach .- outlined in the previous sections. The analyses indicated that the 67 ions exist in negligible amounts thus indicating that all gas-phase sulfi-ircompounds were indeed accounted in the analysis of the total ion chromatograms (as sulfur dioxide and carbon disulfide). T h s analysis hrther indicated that 6 9 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 fluorocarbons were present that were not identified in the analysis of the total ion chromatograms. Table 5.9.1 shows integrated 69 ion area counts from the in-line GCMS analysis for the seven tests compounds when combusted at 600 and 900C. The total areas at 900C were smaller than those at 600C by ratio ranging from 0.01 1 to 0.979. The analysis indicates that perfluorinated compounds were efficiently destroyed at 900'C for ,FC-1395, FC-SO'IA, and PFBS. Because large amounts of volatile fluorocarbons exist for combustion at both 600 and 900C, there is ordy a slight difference of 69 ion peak area for both temperatures. No 69 ion was detected from the PFOS combustion chromatograms. Table 5.9.2 shows integrated 69 ion peak areas from the off-line GUMS analysis for the seven test compounds. The results again show 54 that perfluorinated compounds were efficiently destroyed at 900C with the exception of ,which is again due to the large amounts of volatile'fluorocarbons formed as intermediates. Table 5.9.1. Integrated Peak Area of Extracted Ion (m/z = 69) (In-line GCMS Data) Compound 600C 900C Peak Area Ratio (900 " C/600" C) FC-1395 FC-807A PFBS PFOS 1.34E+07 4.38E+06 1.23E+07 1.12E+07 1.85E+07 1.27E+07 O.OOE+OO 1.05E+O6 1.56E+06 1.37E+05 1.80E+06 1.82E+07 1.64E+05 O.OOE+OO 0.079 0.357 0.01 1 0.160 0.979 0.013 --- Table 5.9.2. Integrated Peak Area of Extracted Ion ( m h= 69) (Off-line G C M S ) Compound 600C 900C Peak Area Ratio (900"C/600"C) FC-1395 FC-807A PFBS PFOS 5.69E+O6 2.96E+05 3.84E+05 8.11E+05 3.31E+06 3.83E+05 O.OOE+OO 3.43E+05 O.OOE+OO O.OOE+OO O.OOE+OO 1.94E+O6 O.OOE+OO O.OOE+OO 0.06 0.00 0.00 0.00 0.584 0.00 --- During the analysis of the off-line samples, we collected hydrogen flame ionization detector .. (HFID) as well as mass spectral data. Due to the suspect results from the extracted ion analysis of the total ion chromatograms generated from PFOS combustion, the FID data for PFBS, and PFOS were analyzed in an attempt to provide an indication of the potential formation of volatile tluorocarbons from the combustion of PFOS as related to the other active ingredients. This analysis does not give quantifiable results, but does have the potential to show the existence of fluorocarbons in the byproducts from PFOS combustion. I Figure 5.9.1 shows the total ion chromatogram and the corresponding HFID signal for off-line GC/MS analysis at 600C. A W I D peak appears with same retention time as the "air" peak for the total ion chromatogram. Since the FID does not respond to the molecular constituents in air (N2, 0 2 , Ar,COz) but does respond to fluorocarbons, it is apparent that volatile fluorocarbons are eluting from the GC column simultaneously with the air constihients. Mass spectral ions corresponding to volatile fluorinated compounds, including CFzH-51, SOF-67, CF;69, CFZCFzH-101, and CzFj-119, were extracted from the total ion chromatogram and are shown in Figure 5.9.2 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 fluorocarbon ions: 5 1,69, and 119. The 5 1 ion occurs near the tail of the FID signal while the 69 and 119 ions occur near the peak of the FID signal. Likely candidates that can be attributed to 55 the 51 and 69 ions are tri- and tetrafluoromethane. Likely candidates for the 119 ion are penta or hexafluoroethane. Pentafluoroethane is detected at longer retention times and also contains a strong 101 ion that is not present in the unknown peak. It is plausible that hexafluoroethme would elute earlier than pentafluoroethane due to its lower boiling point. Thus, the most probable candidates that correspond to the HFID signal at 0.8 min. are tri- and tetrafluoromethane and/or hexafluoroethane. A tau n i.c a,1 E_ 1000000 ~ 0 0 0 0 40 1 1 7 80 o0 oo0o0o0 ~00000 500000 400000 J00000 700000 -I00000 od 9.00 ~ TIC: FCS--60T.D . 0 __c___ 0 __ 1 4 . 0 0 76.00 1 8 - 0 0 Figure 5.9.1. Total Ion Chromatogram and Corresponding HFID Signal for Combu-stio.n of at 600C (off-line sample) 56 eoooo $on 5 1 .oo (50.70t o 51.70):F C S - B O T . 0 -!-irnGl--=. /* bch n cianc e - ;.bo ' ' 4.50 ' ' i.bo ' 5.50 ' ' A . 0 0 ' ' 3.50 ' '4.00' ' d.50 ' ' ' I i eoooo 60000 40000 zoooo 0- T ,,7-!.33-->- Abundance I O " 07.00(08.70t o 67.70):FCS-BOT.D ..,.,..,....,....,....,, 0.50 1.00 1.50 2-00 z . s o ,.,..,. ,,,, ,,,, 3.00 3.50 4.00 4.50 4 aoooo 50000 A 40000 20000 0 ... / . 0.50 ,, l-irne.--> A b u I, I 3 is c.3 ion r 5 S . o o (?,C3.70 I O ( 3 0 . 7 0 ) r = c ! s - e o - r , 1 3 .TI... ,....,.,..,.. ,,... 7.00 1.50 2.00 2.50 3.00 3.50 4.00 4.50 1 e.0000 60000 40000 zoooo 01 T i I-"---- Ab u n d z h 13ce I o n 7 0 1 .OO (1 00.70t Q 1 0 1 . 7 0 ) : F C 5 - 6 O T . D .. , , . . . , . , . . , . , . . , .: 0.50 1.00 7.50 2.00 . , , , , , . , , ., ~ , ,,, , ,, , ,,, , , , ,, 2.50 3.00 3.50 4.00 4-50 ion 1 7 0 . 0 0 (1 1 8 . 7 0 to 119.70):FCS-eOT.D ;gg:g/, e.0000 , , , , ,./{ 0 Ti",*--:- At,""da.-rc". r 0.50 1.00 1.50 2.00 2.50 3.00 3.50 4.00 4-50 7sooo 70000 65000 60000 SSOOO so000 45000 40000 SSOOO 30000 Z5000 20000 P C S - S O T . D\FI D 7 A 5000 - h 0 0.00 r_ O.SQ _, 1.00 ..? 1.50 Z.OO =.so 1.00 a.50 4.60 &.so -rI"..*--2- Figure 5.9.2. Extracted Ions (CFlH-51, SOF-67, CF3-69, C.FtCF2H-101, and C2Fj-119) and Corresponding HFID Signal for Combustion of at 600C (off-line sample) Figure 5.9.3 and 5.9.4show the HFID signal for PFBS and PFOS combustion at 600C, respectively, and the integrated HFID peak areas for PFBS, and PFOS are shown in Table 5.9.3. The peak for PFOS shows the largest area with the smallest amount of gasified sample. The HFID signal for PFOS combustion at 900C is also shown in Figure 5.9.5. The peak is negligible compared to one at 600C, thus indicating nearly complete destruction of fluorinated compounds under these conditions. 57 1 so00 1 eo00 1 1 1000 10000 e000 7000 3000 1000 -I. .cr..*---- 0 0 b .- ' 4 . 0 0 ' 1.50 2.06 =.bo ' 3.00' ' 3 . 5 0 4.00 4 . 5 0 ' ' ' Figure 5.9.3. Off-line W I D Signal for PFBS Combustion at 600C (off-line sample) Abundance 1 SOOOC F C 7 - G O T . D\FIO1A 120000 1 1 0000 7 00000 90000 aoooo 70000 60000 50000 40000 30000 20000 10000 Time--- ~ 00.00 0.50 -' ""I""~"""' 1.00 7.50 2.00 2.50 '8'" 3.00 3.50 4.00 4.50 Figure 5.9.4. HFID Signal for PFOS Combustion a t 600C (off-line sample) 76 0 0 C 1500C 1400C 13000 120013 1 1 000 1 oooa SOOCJ 8000 7000 6000 5000 4000 3000 2000 1 000 0 0 0 2.00 4.00 6.00 8.00 10.00 1 2 . 0 0 1 4 . 0 0 1 6 . 0 0 1 8 . 0 0 I -r,me--=- Figure 5.9.5. HFID Signal for PFOS at 900C (off-line sample) Table 5.9.3. Integrated HFID Peak Area at 600C Sample Peak Area Net Amount of Gasified Sample (mg) 1190193 0.52 PFBS 512226 0.48 PFOS 35476 14 0.3 8 59 6 . Discuss:ion The motivation of this study was to assess the incinerability of perfluoroalkyl sulfonate compounds and polymers that contain these active ingredients. A laboratory-scale study roughly simulating a full-scale hazardous or municipal 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. 400OC) to gasify the materials with more severe high-temperature (600 - 9OO"C), oxidative conditions applying to the secondary combustion zone. TGAs of the active ingredients indicated that higher temperatures (- 600C) were necessary to gasify these unique materials. The sponsor also requested that the experiment be designed to detect low-level (0.1%) transformation to perfluoroalkyl sulfonates in the exhaust gases from the fluorinated portions of the test compounds. The combination of these factors necessitated the use of large amounts of material (milligram quantities) and hightemperature, long duration exposures (ca. 1250"C, 40 sec) in a specially designed pyroprobe to fully gasify the material. These conditions, while representing quite severe conditions in the primary zone of an incinerator, e.g., a rotary kiln, are representative of the range of conditions that occur in a full-scale system. As such, the approach employed in the laboratory-scale combustion study described in the phase III test protocol is a reasonable extrapolation of a full- scale hazardous or municipal waste incineration study of peffluoroalkyl sulfonates and polymers that contain these active ingredients. Combustion tests were completed for seven fluorinated alkyl sulfonyl hydrocarbons: , FC-1395, FC-807A, , CP9S01-Kf (PFBS),and C8FI7SO1-Kf(PFOS) as requested by the sponsor. In-line and off-line GUMS analyses, reactor effluent sample collection using PUF cartridges followed by LC-MS analysis, and chemical extraction of various transfer lines throughout the reactor system including the reactor itself followed LC-MS analysis were conducted to investigate the following: 1)the extent of conversion of the active ingredients, 2) the formation of fluorinated intermediate organic products, and 3) the extent of conversion of the sulfur to sulfur oxides. - _. There was no indication that perfluoroalkyl sulfonate compounds PFBS, and PFOS) were generated from FC-1395, and FC-807A combustion. No quantifiable amount of perfluoroalkyl sulfonyl compounds (ca. 10 ng/ml) was detectable at a detection limit of ca. 10 ndml. Combustion of also showed no quantifiable amount of perfluoroalkyl sulfonyl compounds including itself. During PFBS combustion, small amounts of PFBS were detected in the reactor/transfer lines and the PUF sample cartridges, specifically, 0.22% of gasified sample in the reactodtransfer line system, 0.6% in the PUF cartridges at 6OO0C,and 1.1% in the PUF cartridges at 900C. Similarly, during PFOS combustion, small amounts of PFOS were detected in the reactor/transfer line system and the P W sample cartridges, specifically, 0.04% of gasified sample in the reactor/transfer line system, less than 0.4% in the PUF cartridges at 600"C, and 0.05% in the PUF cartridges at:900C. The correction for this fraction is too complicated and ambiguous to make accurately because of the complexity of the flow scheme, mainly due to changes in both concentration and split ratio with time. If corrected, these recoveries would likely be 10 to 15 percent higher. 60 Minor evidence of cross contamination was found from several LC/MS analyses. The crosscontamination was only observed in tests of the active ingredients and do not invalidate the earlier combust.ion tests of the fluorinated polymers. The contamination sources are likely the pyroprobe and the methanol extraction tubing (separate from the combustion apparatus). All reactodtransfer lines were replaced with each subsequent combustion test. Both pyroprobe and methanol extraction tubing were cleaned following each combustion test. They were not replaced during the tests. To validate the experimental results pertaining to the sampling and analysis of PFOS, PFBS, and where in many instances the analytical results were below the level of quantitation, a series of transfer efficiency tests were conducted. The goals of the transport (or transfer) efficiency tests were: 1) to see if parent compounds and reference compounds, particularly those that were potential thermal transformation products, e.g., PFOS and PFBS, could pass through the combustion system under nondestructive conditions and reach the PUF cartridges and, 2) to determine recovery efficiencies and analytical detection limits. In the 1" transfer efficiency test where the ability of the combustion system to transport all three active ingredients was assessed, analysis of the PUF cartridges indicated the lack of any detectable material. This result indicated that the sample was either thermally destroyed in the pyroprobe chamber (1250C) or the gasified sample condensed in the pyroprobeheactor transfer lines and never reached the PUF sample cartridge. Based on the results of 1'' transfer efficiency test, a 2"d transfer efficiency test was conducted to investigate the latter possibility. In these tests, substantial amounts, 3.4% of PFOS gasified and 2.6% of PFBS gasified, were indeed found in the pyroprobe/transfer line extracts. However, once again, analysis of the PUF cartridges positioned downstream of the pyroprobe/transfer line were negative. The 2ndtest showed that measurable amounts of PFOS and PFBS survive pyrolytic conditions in the pyroprobe and the heated (260C) transfer lines. The question now was how much PFBS or PFOS was transferred through the reactodtransfer line tubing and sampled by PUF cartridges if these materials were formed in the combustion chamber. A 3'd transfer efficiency test was then conducted to address this question. In this test, PFOS or PFBS were placed in the combustion chamber and not into the - - pyroprobe. T h e temperature of the combustion chamber and transfer line system was then heated to 260C. 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 600C while the transfer lines remained as 260C. When the combustion chamber was heated, some of the PFOS or PFHS must have been entrained into the gas stream, and a larger proportion was probably destroyed. Nevertheless, a substantial portion of the PFOS and PFBS was transported through the transfer lines to the PUFs where it was detected. PFOS and PFBS were also found in the transfer lines. Specifically, results showed that measurable PFOS (3.8% air, 11%He) and PFBS (4.5% air, 1.7%He) passed from the combustion chamber to the PUF sampling cartridges. Results also showed that larger amounts of PFOS (4.4%air, 30% He) and PFBS (3.3% air, 20% He) accumulated in the reactorhransfer lines upstream of the PUF cartridges. These results demonstrated that if PFOS or PFBS were formed in the combustion chamber, they would be detected in the PUFs. Therefore, when no PFOS or PFBS was observed in the transfer lines or PUFs downstream of the combustion chamber in tests of potential PFOS or PFBS precursors, 61 one could conclude that there must have been very little, if any, PFOS or PFBS formed during combus tion. A sulfur mass balance was attempted based on the premise that all of the sulfur in the samples would be oxidized to S02, SOF2, and SO2Fz under high-temperature oxidative conditions. The GCMS analyses indicated that the sulfur was recovered as either SO2 or carbon disulfide, CS2. A large SO2 peak was observed for all of species and a much smaller CS2 peak was observed for FC-1395, FC-807A, . Recovery rates were variable. Nearly 100% sulfur recovery was obtained from FC-1395 and I Greater than 100% of recovery rate was obtained from FC-807A. Recovery rates for the other compounds were typically less than 60%. 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 , 3 0 2 . Three SO:!transport efficiency tests yielded an efficiency of 78.6k4 %. The SO2 transport efficiency 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 condensation of the active ingredients and their primary degradation products. G C M S analysis of the reactor effluent was conducted to assess the formation of combustion intermediates, Le., products of incomplete combustion. The most abundant combustion byproduct was benzene. Benzene was observed for the all of the samples except PFOS. Heavier aromatic hydrocarbons were only observed in the two cases where fuel was not supplied with the fluorocarbon sample due to constraints on the reaction stoichiometry. In these cases, 1, commonly observed high molecular weight aromatic hydrocarbons included styrene, benzaldehyde, benzonitrile, phenol, and naphthalene. The combustion tests were performed under oxygen-rich conditions. The excess air ranged approximately from 50% (for combustion) to 140% (for FC-807A combustion). However, during sample gasification, _. it is plausible that an excess amount of sample was introduced into the reactor due to thermal expansion and a fuel-rich condition was created and might be responsible f o r the formation of light polycyclic aromatic hydrocarbons (PAHs). This is roughly analogous to fuel-rich conditions that sometimes occur in full-scale systems due to the uneven loading of solid fuel into the primary combustion chamber and the lack of control of the gasification process. Besides relatively light hydrocarbons, several fluorinated compounds were also observed. The intermediate in highest concentration at 600C was a C1 fluorocarbon alkane, most likely tri- or tetrafluoromethane. This compound or compounds was observed from the combustion of each fluorochemical. At 9OO"C, the concentration of this compound was much lower in comparison with the 600C results. The nature of this byproduct and its thermal stability is consistent with other tests we have conducted on fluorinated samples that show that perfluorinated alkanes are stable intermediates and require temperatures in the secondary combustion zone in excess of 900C for high levels of destruction (Ciba Special Chemicals Corp., 2002). Pentafluoroethane and 1,l-or 1,2-difluoroethenewere also observed in several tests, i.e. , FC-1395, PFBS, and PFOS combustion. The formation of perfluoroalkanes and alkenes was not unexpected and is consistent with the molecular structure of the starting materials, particularly the active ingredjents, where a CJ or Cs saturated fluorocarbon chain is present. There was no 62 evidence to suggest that fluorinated acids were significant combustion products. Fluorinated acids have been observed by G C M S analysis in combustion studies of other fluorinated materials (Ciba Special Chemicals Corp., 2002), but were not observed in this study. Fluorinated aromatics, i.e., mono-, di-, and trifluorobenzene, were observed from most of the samples in relatively low yields. These compounds are also stable intermediates and were not unexpected. Projected yields of fluorinated aromatics were low compared to the nonfluorinated aromatic hydrocarbons. There was no evidence of molecular growth of the fluorinated aromatic compounds. There was no evidence to suggest that polyfluorinated biphenyls or dioxins could have formed under these conditions. Further analytical testing was conducted to verify that the following compounds, potential precursors to PFOS and PFBS, were not formed during the combustion tests: POSF, PBSF, C&S02NH2, CsF17SO&T"H. In all cases, there was no evidence that these precursors formed during the combustion of the seven samples. Further examination of the total ion chromatograms for the SOF ion also indicated the lack of formation of secondary amine precursors, i.e., N-MeFOSE alcohol (CgF1+02N(CH;)C2&0H), and - -- , during the combustion of the seven samples. Fluoro-organic sulfur compounds were not observed in the effluent indicating that the C-S bond in the fluorinated polymers was completed destroyed. This was also likely the case for the active ingredients, PFOS, PFBS, and In these latter studies, a small amount of undestroyed starting material was observed in the L C M S analyses. It is unlikely that these starting materials were 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 fluorochemical product results in significant concentrations of H atoms that efficiently scavenge F atoms as HF and prevent the reformation of long perfluoroalkyl chains. The hydrocarbon fuel to fluorochemical ratio will likely be even higher under actual incineration conditions, further limiting the reformation of perfluoroalkyl chains. Perfluorinated alkanes, necessary building blocks to the formation of precursors to PFOS and PFBS, were limited to C1 and C2 compounds, further indicating that reformation of PFOS, PFBS, requiring CJ and Cg perfluoroalkyl chains, did not occur in the combustion system. 63 7 . Conclusi.ons I The data presented herein clearly show that incineration of FC-1395 and FC- 807A does not release perfluorinated alkyl sulfonates to the environment. This conclusion is based mainly on the LCMS 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 varied from 40 to 120%,depending on the fluorocarbon or fluorocarbon polymer combusted. The dominant sink for sulfur was ,502. GCNS analysis of perfluorinated alkyl sulfonate precursors indicated that such precursors were not present in the reactor effluent. This finding is consistent with the L C M S measurements, and strongly suggests that the C-S bond was completely destroyed (and did not reform) in the combustion tests. Several fluorinated organic intermediates were observed in the reactor effluent. These compounds were limited to fluorinated alkanes, fluorinated alkenes, and fluorinated aromatics. Higher molecular weight fluorinated polycyclic aromatic hydrocarbons were not observed. Recent combustion tests at UDRI with related highly fluorinated polymers (Ciba Specialty Chemicals, 2002) indicate that secondary chamber temperatures of ca. 950C are required to achieve destruction efficiencies of 99.99%. Other tests with Cl-Ca fluorinated alkanes indicate that temperatures between 1040 to 1050C are required to achieve similar destruction efficiencies. The data from this laboratory-scale incineration study indicates that properly operating full-scale incineration systems can adequately dispose of these unique materials. Incineration of these fluorinated compounds is not likely to be a significant source of perfluorinated alkyl sulfonates into the environment. Fluorinated organic intermediates are also unlikely to be emitted from these facilities. 64 8. References Carroll, G. J., Thurnau, R. C., Lee, J. W., Waterland, L. R., Dellinger, B., and Taylor, P. H., J . Air Waste Manuge. Assoc., 1992, 43, 1430. Ciba Specialty Chemicals Corporation, Final Report, 2002, Clark, W., Heap, M., Richter, W. and Seeker, R., The Prediction of Liquid Injection Hazardous Waste Incinerator Performance, ASME/AIChE 2ZndNational Heat Transfer Conference, 1984. Dellinger, B., Torres, J., Rubey, W., Hall, D., Graham, J., and Carnes, R., Hazard. Waste Hazard. ibfater., 1984, 1, 137. Dellinger, B., Rubey, W., Hall, D., and Graham, J., Hazurd. Waste Hazard. iMater., 1986, 3 , 139. Dellinger, B., Graham, M., and Tirey, D. A., Hazard. Waste Hazard Mater., 1956, 3 , 293. Dellinger, B., Taylor, P. H., and Tirey, D. A., Minimization and Control of Hazardous Combustion By-products, Final Report and Project Summary, EPA/600/S2-90/039, 1991. Dellinger, B., Taylor, P. H., and Lee, C. C., J Air Waste Manage. Assoc., 1993,43,203. Giesy, J. P. and Kannan, K., Environ. Sci. Technol., 2001, 35,.1339. Graham, J., Hall, D., and Dellinger, B., Environ.Sci. Technol., 1956,20, 703. Kannan, K., Koistinen, J., Beckmen, K., Evans, T., Gorzelany, J. F., Hansen, K. J., Jones, P. D., Helle, E., Nyman, M., and Giesy, J. P., Environ. Sci. Technol., 2001, 35, 1593. Rubey, W. A., and Carnes, R. A.,Rev. Sci. Instrum., 19S5, 56, 1795. . .. Rubey, W. A., and Grant, R. A., Rev. Sei.Instrum., 1988, 59, 265. Sidhu, S., Graham, J., and Striebich, R., Chemosphere, 2001, 42, 681. Taylor, P. H. and Dellinger, B., Environ. Sci. Technol., 19S5, 22, 435. Taylor, P. H., Dellinger, B., and Lee, C. C., Environ. Sci. Technol., 1990,24, 316. Taylor, P. H., Dellinger, B., and Tirey, D. A., Int. J. Chem. Kinet., 1991,23, 1051. Taylor, P. H. and Lenoir, D., Sci. Total Environ. 2001, 269, 1. Trenholm, A., Gorman, P., and Jungelaus, G., Performance Evaluation of Full-Scale Incineration, M.RI Report under EPA Contract 68-02-3177, 1984. Tsang, W. and Shaub, W., Chemical Processes in the Incineration of Hazardous Materials, DetoxzJication ofHazarcIous Wasfes,J. Exner, Ed., Ann Arbor, 1982,41. 65 Appendix I Timeline and Dates of Testing Date 211, 2/4,2/7,2115, 2/18,2/19,2/24 3119 - 7/29 713 0 812 815 817 . 818, 819 8119, 8/20 812 1 8/22 8/23, 8/26 8/27 812 8 813 0 913 - 915 916 9118 - 9/20 March 2001 - October 2001 February 2002 iMarch 2002 - September 2002 Combustion Test Schedule - 2002 Description Standard sample calibration Combustion test system and method development PFOS and PFBS extraction Heated blank extraction before combustion test combustion test combustion test FC-1395 combustion test FC-807A combustion test ,ombustion test PFBS combustion test PFOS combustion test Heated blank extraction after combustion test PFBS, and PFOS transfer efficiency test 2nd .'FBS, and PFOS transfer efficiency test Off-line GCIMS SO2 calibration Non-heated blank extraction 3rd. . PFBS, and PFOS transfer efficiency test Appendix 2 Phase I1 Final Report and Raw Data August 1,2002 31M Phase I1 Final Report: Laboratory-Scale Thermal Degradation of Perfluoroalkyl Sulfonates and Perfluoroalkyl Sulfonamides Prepared by: Environmental Sciences and Engineering Group University of Dayton Research Institute Summary Calibration curves and detection limits for SO2, SOF2, SO2F2, POSF, PBSF, and C3F6 (hexafluoropropene (HFP)) have been established. The transport efficiency through the UDRI thermal instrumentation system for each compound was also examined. This report describes experimental setup, operating procedure, analytical methods and their results. The calibration plots, h e a r fit equations, detection limits, and transport efficiency are provided in this report. Verification that Cq and Cg perfluoroallcyl sulfonates can be gasified and transported through the system will be performed following the completion of the phase I11 tests. This decision was made based on the potential contamination of the system had the transport tests been done prior to the phase lIIcombustion study. HFP was selected as the surrogate volatile fluorocarbon due to the lack of availability of CFI,and CF3H fi-om gas suppliers. Experimental Setup Six standards (SOZ, SOFz, SOzFz, POSF, PBSF, and HFP) were injected through the STDS reactor configuration that will be used for the Phase III combustion test. The same samples were also injected directly into the GCMS system and compared with the earlier tests to derive the transport efficiency for each material. Figure 1 shows a schematic diagram of reactor and in-line GCMS system that was used for the Phase IT study. Data Acquisition Exhaust Line G C2 GCI Figure 1.Schematic Diagram of Experimental Setup for the Phase II Study. August 1,2002 The system consists of two GCs, the first GC (GCI in Figure 1) was used to maintain reactor and transfer h e at 260C to transport samples efficiently and the second GC (GC2 in Figure 1) was used for sample analysis. The fiunace in GC1 was also maintained at a temperature of 260C. Helium (He) was used as canier flow and flow was set as 21 It 1 d m i n using a differential flow controller (Porter Instruments). A flow splitter was installed between reactor and GC column to vent excess gas. A 21 rnUmiTl flow rate was used to define a residence time of 1 sec in the combustion reactor. The combustion reactor used in this study (and the Phase III combustion test) is 4 mm x 6 mm (i.d.xo.d.) with an effective length of 5 cm. While the sample was being collected, the switching valve was opened toward exhaust line ((1) position in Figure 1. The valve was then switched to (2) position to pressurize GC column when sample analysis was started. The pressure was maintained at approximately 6 psi during sample analysis and the pressure was monitored using a pressure gauge. The GCMS system used in Phase II analysis was a Hewlett Packard 5890N5970B incorporating a DB-5 MS capillary column (30 m length, 0.25 mm id., Agilent Technologies, Inc.). All samples except PBSF'were diluted in helium (Research Grade, Air Products, h c . ) to establish calibration curves and detection limits. PBSF, which is a liquid phase at room l temperature, was diluted in dichloromethane (99.9% HPLC grade from Aldrich, Inc.). The amount of sample injected was 1ml for gas-phase samples (S02, S02F, S02F2, POSF, and HFP) and 1 pl for liquid-phase sample (PBSF). 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 -60C. After sample injection, the flow was vented for approximately I rnin. to purge the sample from the reactor/transport system. The system was . then pressurized by turning the switchmg valve to the (2) position, and the GC oven temperature programming was started. The GC oven was initially held at -60C for 1 min., heated to 50C at 10"C/min. and held for 1 min. The GC was heated to 250C for 10 miTl after each analysis to flush out any residual material from the column. The MS was auto-tuned with perfluorotributylamine (PFTBA) and operated at EMY (2000V) in the scanning mode sweeping from 45 to 550 AMU. Direct Injection All conditions, GC oven temperature programming, total flow, split ratio, injection port temperature, and column pressure, were set at the same condition that was used for the calibration study. The temperature progammin,o was started immediately after sample injection. 2 August 1,2002 Results Calibration In most cases, calibrations were made based on four even interval concentrations for each sample. The detection limit was determined using a similar approach to EPA's detection limit criteria for identifjmg 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 specified as the lowest concentration that has the target ions and all of the major ions whose relative intensity agrees with the reference spectra within ca. It 20%. For example, Fi,we 19 and 20 in the Appendix illustrate the total ion chromatogram and mass spectra for S02F2 (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 ( d zwill not be shown thereafter). The ions of 102, 53, 67, and 45 correspond to'S02F2, S02F, SOF,and SO, respectively and it is reasonable to choose these ions to quantify S O ~ F ZF.igures 24 and 25 in the Appendix show the total ion chromatogram and mass spectra for a concentration of 20.1 ppm. m e 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 SO2F2 was determined as 20.1 ppm. Similar analysis was conducted for all of i standards and the results are briefly discussed below. Figures 2 to 7 show calibration plots for SOz, SOF2, SO2F2, POSF, PBSF, and HFP, respectively. The linear fit equations for each sample, their linear correlation coefficients (R) and detection limits are tabulated in Table 1. Table I Linear Fit Equations and Detection Limits - Sample Name so2 SOF2 S O2F2 POSF PBSF KFP Linear Fit (Y:peak area, X: concentration (pprn)) k'= 5.S813E3* X - 3.8541E5 Y = 8.3335E3* X - 7.0267E4 Y =-1.0331E4*X + I .8273E6 Y = 1.0423E5"X - 8.4043E5 Y = 1.564E5*X + 1.338E6 Y = 1.4975E4"X - 2.8253E6 R 0.9971 0.99941 0.99708 1.o 0.998 0.9997 Detection Limit (PP4 78.5 30.3 20.1 14.1 10.0 3.9 The linear fit for each calibration shows reasonable high correlation coefficients. Because only 2 concentrations could be measured above the detection limit for POSF, the R value is 1.O. Based on the linear fit equation, the detection limit for HFP is 189 ppm. However, the detection limit , analysis described above indicates a much smaller value (3.9 ppm). This is due to non-linear GCNS response throughout the concentration range examined. 3 August 1,2002 The concentration range used to obtain the SO;! 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 for SO;! (1570 pprn). The ions of 45 (SO) and 64 ( S 0 2 ) 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. so2 110' , I e m < 0 200 4W 6W 800 1000 1200 1400 1600 Conc. (pprn) Figure 2. Calibration Plot for SO2 The concentration range used to obtain the SOF;! calibration was 3034 to 303.4 ppm. Figure 9 in the Appendix shows the mass spectra for SOF2. The ion of 67 (SOF) was chosen as target ion and the ions of 86 (SOF2) and 48 (SO) were chosen as major ions. All ions exist at a concentration of 30.3 pprn. At 6.1 ppm, there was no G C M S response to the sample. Therefore, the detection limit was determined as 30.3 pprn. 4 SOF2 August 1, 2002 z m m - T F 500 f.- 1000 1500 2000 Cone. (pprn) 2500 3000 3500 Figure 3. Calibration Plot for SOFl The concentration range used to obtain S02F7 calibration was 7034.3 to 100.5ppm. The detection limit was determined as 20.1 ppm as discussed above. S02F2 m a e 0 1000 2000 3000 4000 5000 6000 7000 8000 Conc. (ppm) . Figure 4. Calibration Plot for S02F2 The concentrations used to obtain the most accurate POSF calibration were 20.1 and 14.1 ppm. T h s 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 (C~FS)1,31 (C~FS)a,nd 169 5 August 1,2002 (C3F7) were chosen as the major ions. The 100 and 131 ions were not present at a concentration of 8 ppm (Fig.33), and the detection limit was determined as 14.1 ppm. 1 4 lo6 POS F -y = - 8 . 4 0 4 3 e h 5 + 1 0423e+05x R= 1 I 0.0100~ 1 I I 0 Ij I I, I,I I , 5 10 I;, ( 15 ,,j , 20 ,, I 25 Conc. (pprn) Figure 5. Calibration Plot for POSF The concentration range used to obtain the PBSF calibration was 1000 to 100 ppm. Figure 35 in the Appendix shows mass spectra for PBSF (1000 ppm). The 69 ion (CF3) was chosen as target ion and 67 (SOF),100, and 131 (CjF5) were chosen as major ions. The 100 and 131 ions were not present at a concentration of 5 pprn (Fig.42). The detection limit was thus determined as 10.0 pprn. 6 PES F August 1,2002 m E a m i , , , 1 , , , , , I I I II , 1 I I,III , I 1wo 2w 1 -0 400 6W 8W 1200 Cam. (ppm) Figure 6. Calibration Plot for PBSF The concentration range used to obtain the HFP calibration was 10,000 to 1,000ppm. Figure 44 in the Appendix shows mass spectra for HFP (10,000 ppm). The 69 ion (CF3) was chosen as target ion and 50 (CFz), 81 (C2F3), 100, 131 (C~FS)a,nd 150 were chosen as major ions. The ion of 81 was not present at a concentration of 1.9 ppm (Fig. 51). The detection limit was thus determined as 3.9 ppm. HFP m ?2 0 2000 4000 6000 8000 110' corn. (PPW Figure 7. Calibration Plot for HFP 1.210' 7 August 1,2002 Transport Efficiency The transport efficiency of each standard was estimated by comparing the measured sample peak area obtained when the sample was injected into injection port in GC1 and passed through combustion reactor and transfer line (system transport) with that obtained when the sample was injected directly into the injection port of GC2 (direct injection). Table 2. Transport Efficiency Sample so2 S OF2 ~ SO:!Fz POSF PBSF HFP System Transport Peak Area 1St 2nd AVG (1) 9130332 8980717 9055525 25244352 25203780 25224066 86850304 5'5572509 86211557 1280370 1223718 1254544 159824697 148389773 154107235 145679354 145606343 147142849 Direct Injection Peak Area lSf 2"d AVG (2) 11952302 11762267 11857285 24862639 24773683 24818161 84435720 797383 16 82087018 1064431 1067947 1666189 25091 128 25284200 25187664 148372504 142271896 145322200 Efficiency (%) (1)/(2)x 100 76.4 101.6 105.0 117.7 611.8 101.3 The transport efficiencies for SOF2, SOzF:!, and HFP were within analytical error. An uncertainty of _+ 10 % is reasonable for this type of analysis. That for POSF was slightly higher, but is nonetheless acceptable. That for SO:! was around 76%. The SO2 standard was analyzed as a two-component mixture with SOF2. Since the transport efficiency for SOF2 was nearly 1OO%, the results indicate some sample losses for SO2 through the reactor and transfer lines. Because SO:!is expected to be one of the major combustion byproducts, we will repeat the efficiency test as part of the Phase IIIstudy. We will estimate a SO2 correction factor based on SO2 efficiency test results to compensate for its measured concentration during the Phase III study. The efficiency for PBSF was not consistent between the two injection methods. The cause of this discrepancy was discussed with other analytical specialists in our group. The major cause may be a mixing problem of ths sample with the solvent, dichloromethane. PBSF is the only liquid phase sample among the six standards. Each time PBSP was diluted with dichloro_methanein the GC vials, it was shaken thoroGgkly in an attempt to obtain a uniform mixture. TheTdensity of PBSF is unknown, but expected to be heavier than dichloromethane. This may have caused some settling of the PBSF at the bottom of vials during preparation of the standards. The transport efficiency of PBSF will be re-examined as well as the PBSF calibration if the Phase 111 combustion tests indicate this is an important combustion intermediate. 8 August 1,2002 Appendix (Raw Data for Phase I1 Report) The totaI ion chromatograms of the 6 standards (SO*, SOFs, SOzFz, POSF, PBSF, and hexafluoropropene (HFP)) and the mass spectra corresponding to standard peaks are presented below. Mass spectra are shown for the highest, detection limit, and below detection limit concentrations for each standard. * F L c '1 August 1,2002 T I C : CLSOF3.0 400000 350000 300000 250000 zooooo 150000 100000 soooo 0 TIme --> Figure 8. Total Ion Chromatogram for SOFz (3034 ppm) and SO2 (1570 ppm) . . Abundance 220000 - - Scan 39 ( 0 . 4 5 1 rnln): CLSOF3.D (-) 97 zooooo iaoooo ieoooa 140000 Ab u n d i.nc o Figure 9. Mass Spectra for SOP2 (3034 ppm) e4 5000 I 07.. ,,. SO I ! , . . ,. ~ . . . . , . . . , , .. BeS , , , ,I ,I 2 Abundant'a TIC:C L S O F 5 . D .. August I, 2002 5001 ;d < 0 , ..,.II./....,III.,...,/ ................................ , , , . , , . , . , , , , , , , , , , ( , , ,,,, 0.~00.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.40 Time--> Figure 11.Total Ion Chromatogram for SOF2 (2124 ppm) and SO2 (1099 ppm) iaoooo - 1eo000 140000 - - 1 ~ 0 0 0 0 TI,C: CLSOF7.D 100000 - aoooo 4 60000 - - 40000 70000 - 0 -. . . . , . ' ~ . . . . , . . . .. , . . . , . . , . , . . . ~ , ,,... ,....,.,..,... ,,- o . ~ o o . - a o o . e o o . 8 o i . o o~ . z o i . - a o ? . 6 i0. a o z . o o ~ . ~ o z . 4 o ~ . . s o z . a o 3 . o o 3 . ~ o 30000 - - 25000 200t30 15000 - 3 Abundance 1 14000 J 12000 10000 I8000 j J 6000 I 4000 TIC: CLSOF12.D August 1,2002 Ab""d.d*C* m,z=-> 130C 120c 110c 1 ooc soc aoc 70C soa 500 400 300 200 100 0 F Scan 164 (1.832 min): CLSOF12.1 Figure 15. Mass Spectra for SO2 (78.5 ppm) 4 August 1,2002 Ab....>W.,.. ,.>., =no0 TIC: CLLSOFl- .O 2600 2400 zzzoo ZOO0 1 NO0 T el00 1400 '1z100 f 000 aoo 600 400 100 0 -rim-- -- Figure 16. Total Ion Chromatogram for SOF2 (30.3 pprn) and SO2 (15.7 ppm) eo Figure 17. Mass Spectra for SOFz (30.3 ppm) I:: z c EC>O 5 August 1,2002 7soooo T I C : NCCSF2zzLP.D 700000 850000 600000 5s0000 500000 ~50000 ~00000 3S000O ~00000 =2 S O O 0 C 3 20o o o c 3 15 0 0 0 c > 1 00000 soooo -l-,.v,e--- , * / , , 0 ,, , 0.20 O.-+o 0.eO 0 . 8 0 7 - 0 0 '1.20 7 . 4 0 1.60 1.ao 7 . 0 0 7 . Z o Figure 1.9.Total Ion Chromatogram for SOIF*(10049 ppm) =.-a A b u nciancer 300000 2a0000. 260000 240000 220000 200000 - i 1 f s6o0o0o00 o Sca 2 9 (0.336rnin): NCLSF224.0 I 1 140000 120000 67 100000 80000 60000 40000 20000 0 ~ m/z-=- i,-.._1! , , , . ,7*., , , , ? ' l, , ,I1 1 0 120 40 50 60 70 80 SO 1 0 1 4 0 120 130 140 Figure-20.Mass Spectra for SOzFz (10049 ppm) 152 165 150 1 6 0 1 7 0 a 6 August 1,2002 T ,r.,..- 700000 d=5OOOO 000000 SSO0OO 500000 asoooo 400000 350000 300000 1~0000 ~00000 ?~ 0 0 0 0 100000 s0000 0 - = I- TIC: NCLSEF2Z3.0 - 4 3 5 TIC. NCLSF217 0 650000 eoOoOO ~soooo SO0000 450000 -a00000 7SOOOO aooooo Z50000 2OQOOO 150000 1 00000 50000 0 0.20 0.40 0.60 0.60 1 . 0 0 1 . 2 0 1 . 4 0 1 . 6 0 1 . 8 0 2 . 0 0 2.20 2.40 _. l-,rne--- Figure 22. Total Ion Chromatogram for SOtFz (4020 ppm) - 3 TIC: N C L S F Z 7 S . O 170000 -l60000 1 50000 7 40000 130000 7 ZOO00 7 7 0000 100000 soooo aoooo 70000 80000 50000 40000 30000 20000 7 0000 7 TIC: N C L s F z ~ a . 0 August 1,2002 Figure 24. Total Ion Chromatogram for SOzF2(20.1 ppm) Z40 12200 ` "P1 -i = S c r a m 32 (0.373man): N C L S F Z Z a . 0 ,,./ 1 I 1 -I200 '400 [;;;1 ,,,, ,,,,,,,,,, ,,,,, 1 02 I , , , , , , , , , , , , ,! , , , , , , , , , , , , , , , , , , , , , , , , ,m/z--= 400 200 0 40 45 50 55 eo es 70 7 5 ao as so a5 T O O Figure 25. Mass Spectra for SOtF2 (20.1 ppm) 10s 1 7 0 8 August 1,2002 Figure 26. Total Ion Chromatogram for SOzF2 (4.0 ppm) Figure ,27.Mass Spectra for S02F2(4.0 ppm) 9 August 1,2002 5SOOO - ~ 0 0 0 -0 Z5000 - 20000 - 7 5 0 ' 3 0 -i 7 0000 5000 - -V,,n---- 0 7-00 2.00 3.00 r.00 5-00 e.00 7.00 e.00 0 . 0 0 A lo!< Figure 25. Total Ion Chromatogram for POSF (20.1 ppm) Figure 29. Mass Spectra for POSF (20.1 ppm) 10 40000 4 35000 4 30000 4 Z5000 20000 'I so00 1' SO00 ~ T I C : NCLPSF4.D August 1,2002 Abundarice sooo 1 8000 7000 6000 sooo - 4000 ~ I 3000 - ---* Scan 922 (10.235 rnin): NCLPSF4.0 looo 4,8 0 L--L-T- 40 50 60 I ,.,. ,.., ,,,,I,,,, , 7 0 80 90 1 0 0 1 1 0 I 120 I I""I""I"'I""1'''~ 1 3 0 140 1 5 0 1 6 0 I 170 Figure 31. Mass Spectra for POSF (14.1 pprn) 11 August 1, 2002 Abundance 7000 ~ 6000 - so00 - 4000 ~ 3000 - J1 2000 j 1 0 0 0 TIC: NCLPSF6.D Abundance 3500 F a e Scan 922 ( 1 0 . 2 3 6 min): NCLPSF6.D 3000 2500 2000 1500 ",/=e--=- 1000 500 0 119 -SO Figure 33. Mass Spectra for POSF (8.0 ppm) - 4 16s 12 August 1,2002 1700000 TIC: P B S F f . 0 1600000 1 so0000 1 a00000 1 =ooooo 1 zooooo 'I 1 ooooa -looooo0 sooooa aooooo ~OOOOO 600000 500000 400000 300000 200000 100000 0 3.203.40 3.003 . S O 4.00 4.20 4 . P O 4.60 4.80 S . 0 0 4 . 2 0 5 . 4 0 5 . 8 0 S . 8 0 S . 0 0 'r i __=- Figure.34. Total Ion Chromatogram for PBSF (1000 ppm) - * -=7 Figure 35. Mass Spectra for PBSF (1000 ppm) 13 August 1,2002 \ =ooooL J 0 7-,----=- =_SO d.00 4.00 s.00 -_bo 0.00 Figure 36. Total Ion Chromatogram for PBSF (700 ppm) -.e0 I.'i------ -=4= S5OOOO 600000 550000 500000 450000 400000 350000 300000 250000 zooooo i5 0 0 0 0 i00000 50000 0 ....,..,.,...,,....I.. TIC: P6SFB.D 3.203.403.603.804.004.204.404.804.805.005.205.405.605.806.006.20 l-,",.y--2 Figure 37. Total Ion Chromatogram for PBSF (400 ppm) Abundance TIC:P B S F 8 . D 1 10000 100000 9OOClO 80000 70000 60000 50000 40000 30000 20000 1 i - , . , , .- lOo0: 3.2CI 3.40 3. ?, , . , , . , , , , , , I , , , , , , ;, , , , , , , , , , , , , ,-, 13.804.004.204.404.604.80 5.00 5.20 5.40 5.60 5.806.006.20 Time-=- Figure 38. Total Ion Chromatogram for PBSF (100 ppm) 14 TIC:P B S F 1 O . D August 1,2002 Tirne-> i1 1 0 0 0 500 500 0 ,, ., ,, , 3.20 , . , . , 3.40 , .,, . 3.60 , , , . , 3.80 .,~ .I 4.00 ..,r I 4.20 I ,-~----,-rn~i---7 4.40 4.60 4 . 8 0 5.00 5 . 2 0 Figure 39. Total Ion Chromatogram for PBSF (10 ppm) 7 7 5.40 Figure 40. Mass Spectra for PBSF (10 ppm) 15 August 1,2002 Abundance 1 eo0 1700 1 e00 1 500 7 400 1300 1 zoo -I '100 1000 900 800 700 '300 500 400 300 200 100 0 TIC: PESF1Z.D I 3.20 3.40 3.60 3 . 8 0 4.04 Figure 41. Total Ion Chromatogram for PBSF (5 ppm) Figure 42. Mass Spectra for PBSF (5 ppm) 16 Abundance 2 4 0 0 0 0 0 2200000 2000000 1800000 1600000 1400000 1200000 7 000000 800000 TIC:P F P 1 . D August 1,2002 0 ~ , , . ~ l , , ~ , ~ , . ~ ~ .I ., l ~. ,, . , ,, , I, .. , , , , , . l . , , , I , / , , , . , , , ,,,, ,,,, ,,,. ,,,-~ , 0.200.400.600.801.001.201.401.601.802.002.202.402.602.803.003.203.40 Time--- Figure 43. Total Ion Chromatogram for Hevafluoropropene (HFP) (10,000 ppm) 1 900000 800000~ 700000 -. 600000 - S c a n 36 ( 0 . 4 1 4 rnin): PFPi .D GIQ 500000 ' 400000 - 300000 - 7 00 131 200000 J 50 I , , 100000 ' 0 ,, ,, 81 ,i,. ) I , , i , ! , 62 55 , ,I,, I ! ,I., 74 , 93 , , , , , , , , 1, 1 ,, 2 , , , I , , , , 150 ,,I,, ,, ,,, , ~ 17 TIC: PFP3.D August 1,2002 1 1 OOOOO 7 000000 OOOOOO 800000 700000 600000 soooao 400000 300000 /I Figure 45. Total Ion Chromatogram for HFP (7,000 ppm) SOOOOO TIC: PFP5.D a50000 eOOOoO t. 750000 700000 ~50000 600000 550000 500000 450000 4000OO 350000 3OOOOO ZJOOOO ZOOOOO 150000 100000 soooo 0 . . . . , . . . , . . .-., 0.50 1 .oo 1.50 2.00 2.50 , 3.00 3.50 Figure 46. Total Ion Chromatogram for HFP (4,200 ppm) - ~00000 f eo000 _I 8 0 0 0 0 170000 --* eooao is o o o o idoooo aoocao zoocao 1 7 OOClO *O O O C ~ O SOOClO aoooo 1 70000 4t 60000 i dooao 3ooc,o 1 ~0000 3 0000 K 0 0 . ~ 0 0.40 0 . 0 0 o.ao 1.00 -.=to7 . 4 0 1.00 -.eo 2 . 6 0 a.20 2.4 TI...---;- Figure 47. Total Ion Chromatogram for HFP (1,050 ppm) 18 August 1,2002 eooc: T I C : PPPt,.D 740C 700C S5OCl 600.3 SSO0 SO00 4soa dooa 3S00 3000 =so0 zooa ....id 1 SO0 so0 0 0.20 0.40 . h v h M A . A . . A fl . A . 0.6 , 9 0.80 7.00 1 .I2 0 . . 7 - ,4 0 .1.,60 . 3 . ,6 0. , l-lmo--- Figur.e. 48. Total Ion Chromatogram for HFP (3.9 ppm) Abundance I 3SOC S c a n 48 ( 0 . 5 5 Z min): P F P Z 1 . D 1 3ooc 25oc zooc 1 1 iso0 7 000 SO0 0- 50 100 1'1 1 19 August 1,2002 7 I I 0 . ~ , . . . . , . . . . , . . . . /. . . , , Figure 50. Total Ion Chromatogram for HFP (1.9 ppm) m o 55 eo os . .. Figure 51. Mass Spectra for HFP (1.9 ppm) 20 Appendix 3 I Phase 111Test Protocol and Addendum July 30,2002 I' Phase III Protocol: Laboratory-Scale Thermal Degradation of Perfluoroalkyi Sulfonates and Perfluoroalkyl Sulfonamides Prepared by: Environmental Sciences and Engineering Group University of Dayton Research Institute Summary The phase IDstudy will consist of 6 separate tests as shown in Fi,.ure 1. The main objective of this study is the simulation of the incineration of seven fluorocarbon-based samples provided by 3M. Specific attention is being given to the potential formation of PFOS and PFBS during the incineration of these materials. In-line and off-line GUMS analysis, PUF Cpolyurethane foam) sample collection and condensed phase sample extraction will be conducted. In the latter two tests, the PUF cartridges and theextracts will be delivered to 3M for analysis of PFOS and PFBS by LCMS. Prior to the sample combustion analysis, the transfer efficiency for SO;! will be reexamined and the laboratory spike analysis for PFOS and PFBS will be performed. A heated blank line analysis will be performed at the onset of the sample combustion tests. After the combustion tests, another heated blank line analysis will be performed. Transfer efficiency tests for CQF9S03'Kc, and C*F17S03X+will be performed at the conclusion of the phase 111study. I 1. SO, Transfer Efficiency Tests I t 1 I 3. Heated Blank Combustion Test I 4. Combustion Tests for FC-1395, FC-807A, If I f 5. Heated Blank Combustion Test (repeat) 6. Transfer Efficiency Test for C$9SO3-K+, and C8F17S03-Kf Figure 1. Chronological summary of tests to be conducted during Phase ]UT. 1. SO2 Transfer Efficiency Tests In the phase IT transfer efficiency test, sulfbr dioxide (SO21 showed recovery efficiency of 76.4 %. The SO2 standard was analyzed as a two-component mixture with SOFz ( h o n y l fluoride) and the SOFz recovery rate was nearly 100%. Therefore, it is quite conceivable that SO2was absorbed on the surface of reactor and transfer line. We will conduct another analysis to confirm t h s result and to estimate the recovery coefficient for the calculation of SO2 concentration from the combustion tests. 2. Laboratory Spike Analysis for PFOS and PFBS A 1 pg sample will be used for the PFOS and PFBS spike analysis. This is the amount of PFOS or PFBS that would be formed if 0.1% of the perfluoroalkyl portion of the fluorochemical products used in this study were converted to one of these compounds in the reactor. Analysis of the extracts from these spiked reactor/transport systems will show if this amount of PFOS or PFBS can be extracted and ddected accurately. 10 mg of PFOS and PFBS will be dissolved with 10 ml methanol (AldricK HPLC Fade) and 1 pl of solution (containing 11-19of PFOS and PFBS) will be placed into a reactor (4 mm (i.d.) x 6 mm (0.d.) x 7 cm length) and dried by blowing high punty nitrogen, or bottled dry air over it at a rate that won`t blow droplets out the other end. M e r 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 ml: as calculated (0.2 cm x 0.2 cm x 3.14 x 7 cm) Total = 1.1 ml The concentration of PFOS and PFBS in the spike that is extracted with five times volume of reactor/transfer line (using methanol as the solvent) will be 180 ng/ml. T h s is 18 times 3M's estimated detection limit for PFOS and PFBS (ca. 10 ng/ml). Figure 2 shows a schematic of the PFOS and PFBS laboratory control spike extraction system. The extraction procedure will be based on the perspective that only the condensation of PFOSPFBS subsequent to the high-temperature combustion stage would be indicative of likely PFOSPFBS release to the environment &om actual incineration systems. Thus, the extraction procedure will focus on the high-temperature reactor (downstream 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 pnor to extraction. The total amount of methanol used will be 5.5 ml, five times the volume of the reactor/transfer line. The methanol will be stored in 40 ml vials (Wheaton CLEAN-PAJS, clear certified 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 (Wheaton CLEAN-PAK, clear certified with pre-cleaned lined cap) using 1/8" stainless tubing. Methanol will be slowly injected into the system by pressurizing a methanol reservoir by helium gas flow (2.7mUmin) until all methanol is injected 2 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 confirming 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. _- 0 -- Vent l/S Tubing --- - Figure 2. Experimental set up for PFOS and PFBS laboratory control spike tests. 3. Heated Blank Combustion Analysis Before and after the sample combustion tests, a heated blank combustion test will be conducted for a reactor temperature at 600 and 900C to examine system contamination. The sample _. collection will be performed twice for each temperature (one for the sample collection using - polyurethane foam (PUF, (Supelco ORB0 PUF Cartridge)) and one for the sample collection using Tedlar sampling bags (0.5L, SKC Inc.). Two GC-MS analyses with different GC columns will be conducted for the heated blank exhaust gas analysis (one with in-line GC-NfS 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 GCMS 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 GUMS analysis, the PUF shown in Fi,we 3 will be replaced by a Tedlar bag. Compressed air will be delivered both to the pyroprobe chamber and the reactor. The total air flow rate will be 10.3 and 7.6 rnl/min (with 0.8 and 0.7 ml/min to the pyroprobe chamber) for reactor temperatures of 600 and 900C, respectively. The residence time in the reactor (4 mm i.d. X 6 mm 0.d. X 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 flow rate will be controlled w i b &IO % error. A majority of the 3 effluent will pass through the PUF cartridge for sample collection and 1 ml/min will be directed into the GC column for in-line analysis. In-line GC-MSAnalysis: A HP5890N5970B series GC-MS with DB-5 kfS capillary column (30 m length, 0.25 mm i.d., Agilent Technologies, h c . ) will be used for the phase III study. The initial temperature of GC2 will be held at -60C and sample will be concentrated at the head of the column for 2 and 2.5 (35%) min for reactor temperature of 600 and 9OO"C, respectively. During t h s time period, PUF combustion effluent sample collection will also take place. Two PUF cartridges will be placed in series as shown in Figure 3. After the sample collection, switching valve 1 will be turned to (1) position in Figure 3 to pressurize the GC column. As soon as pressurization begins, the temperature programming 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 260C. The final temperature will be held for 5 minutes. Also after the switching valve I 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 Environmenta-l Laboratory with one blank PUF. Offlline 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 w i t h 15 min. of collection and analyzed using HP5890N5970B series GC-MS with SPEL-Q PLOT (Porous Layer Open Tubular) column (30 m length, 0.53 mm i.d., SUPELCO). The Tedlar bags will be heated to ca. 50 - 60C to ensure that all of the s u l h r compounds that are soluble in the condensed water vapor present in the bag are partitioned into the gas-phase. This column will capture the light compounds (<c6)that the DB-5 MS capillary column may not effectively retain during in-line gas sampling. The initial temperature will be held at 35C and 1 ml of sample will be injected using a 1 ml gas-tight syringe. The initial temperature will be held for 1minute and the temperature will be raised at 15"C/min up to 245C. The final temperature will be held for 5 minutes. All of reactor/transfer line systems including pyroprobe chamber and sample insert probes used - - in the Phase 111analyses will be appropriately packaged and stored for the hture analysis. 4 effluent will pass through the PUF cartridge for sample collection and 1 mumin will be directed into the GC column for in-line analysis. In-line GC-iMSAnnlvsrs: A HP5890N5970B series GC-MSwith DB-5 MS capillary column (30 m length, 0.25 mm id., Agilent Technologies, Inc.) will be used for the phase IIIstudy. The initial temperature of GC2 will be held at -60C and sample will be concentrated at the head of the column for 2 and 2.5 (+5%) min for reactor temperature of 600 and 9OO"C, respectively. During b s time period, PUF combustion effluent sample collection will also take place. Two PUF cartridges will be placed in series as shown in Figure 3. After the sample collection, switching valve 1 will be turned to (1) position in Figure 3 to pressurize the GC column. As soon as pressurization begins, the temperature programming 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 260C. The fmal 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 Enviromiental Laboratory with one blank PUF. ..9 ? Off-line GC-MSAnalvsis: 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 HP5890A/5970B series GC-MS with SPEL-Q PLOT (Porous Layer Open Tubular) column (30 m length, 0.53 mm id., SUPELCO). The Tedlar bags will be heated to ca. 50 - 60C to ensure that all of the s u l h r compounds that are soluble in the condensed water vapor present in the bag are partitioned into the gas-phase. This column will capture the light compounds (<c6) that the DB-5 MS capillary column may not effectively retain during in-line gas sampling. The initial temperature will be held at 35C and 1 ml 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 245C. The finaltemperature will be held for 5 minutes. -- All of reactorjtransfer line systems including pyroprobe chamber and sample insert probes used - in the Phase I11 analyses will be appropriately packaged and stored for the future analysis. 4 22 cm Pyroprobe Chamber (7 x 9.5mm x Scm) 1/16 Tubing 1/8 Tubing Reactor /\A. Y h,mi m x 14cm) 1/16 Tee 2cm 118 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 9OO"C, and the sample collection will be performed twice for 5 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. M e r the gas phase analysis and collection, the reactor will be cut in half and extraction of condensed phase products will be performed using the method previously outlined in Section 2 and 3. Figure 4 shows the schematic diagram of the experimental setup to conduct effluent in-line GCMS analysis and PUF sample collection for the combustion test of the selected compounds. For o f f - h e GC-MS analysis, the PUF cartridges in Figure 3 will be replaced by a Tedlar bag. Au and methane (if necessary) will be introduced into the pyroprobe chamber and the reactor to simulate incineration of the samples. The flow rate of He and air will be controlled by a flow controller (Porter Flow Instruments, DFC1400) and methane will be introduced using a calibrated syringe pump (KDS101,kdscientific). Because the methane flow rate is very low, it is necessary to use syringe pump to obtain accurate flow rates. The solid and liquid phase samples will be gasified using a pyroprobe (Chemical Data Systems, Model 120) and mixed with air and methane (if necessary) in the pyroprobe chamber. The temperature and the duration time of ignition will range from 1000 to 1250C and 20 to 40 seconds, respectively, depending on the actual sample being gasified.=The gasified mixture will be mixed with the air stream and undergo incineration in the fused silica reactor. A portion of the effluent (1 mumin) will be delivered to the GC-MS for product analysis and rest of effluent will be passed through two PUF cartridges for detection of PFOS andor PFBS using LCMS analysis at 3M environmental laboratories. Further details are provided below. Ventilation m L Data Acquisition High Voltage DC Power i- Con troller Figure 4. Experimental setup for the combustion tests. 6 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 development of the stoichiometric equations, it is assumed that C is converted to COz, F is converted to JXF, N is converted to NZ, and S is converted to SO;?. Phosphorous and potassium were excluded fiom 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 deficient samples to supply hydrogen to convert F to HF. In that case, additional oxygen was supplied to convert C in methane to CO?. stoichiometric I . . F 1 1 1 I I 1 Atomic Contents of Samples Sample Icl H N oP Gas s K o2 CH, Products co2 1 H ~ OI HF I so2 I N~ PFBS PFOS 409 8 0 17 0 3 0 115.5 0 3 0 1 1 11.5 2 6 0 80.5 0 412 016 1 0 From the table above, stoichiometric equations can be derived for all of the samples as shown below. For 2. Calculation of Necessary Amount of Sample (Equivalent Amount of Fluorine in PFOSl The amount of sample that will be incinerated was calculated to conserve the same amount of fluorine for each sample and is tabulated in Table 2. All samples have the equivalent amount of fluorine that is contained in 0.50 mg of PFOS. To facilitate calculations, we define 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. For example, the pseudo-molecular weight of The amount of air necessary for stoicbometric incineration for each sample was also calculated and is included in Table 2. .~ 7 I 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 Ax for Molecular Fraction by be incinerated Stoichometric Sample Name Weight (g) weight (W Incineration (ml) PFBS 338 0.506 0.59 1.33 PFOS 538 0.600 0.50 1.35 a,b Values in parenthesis will be used for the actual combustion test. See sample amount adjustments. For example, the amount of = PFOS can be calculated as: that contains equivalent amount of fluorine in 0.5 mg of I and the amount of air for stoichiometric incineration can be calculated as: The necessary amount of sample and air for other six compounds can be calculated in a similar manner. 3. Sample Amount Adjustments Since FC-1395 and FC-807A were provided in aqueous solution (water contents of 74 and 78 % by weight, respectively), the amount of sample to be loaded will be 2.19 and 2.63 mg, respectively. also contains 10 % (by weight) impurity and the necessary amount that has the equivalent amount of fluorine in 0.5 mg of POSF will be 16.38 mg. This mass of material is approximately one magnitude larger than the other compounds and combustion of such a large mass is beyond the capability of our laboratory-scale apparatus. One-third of the necessary mass is the maximum amount that can be incinerated and satisfy near-stoichiometric combustion and a residence time of 2 s. 4. Sample Loading Method will be placed directly into the sample probe (1 x 2 mm (id. x 0.d.) x 2 crn length). FC-1395 and FC-807AYboth ofwhich are in aqueous solution, will be placed into a slightly larger sample probe (2 x 4 mm (i.d. x 0.d.) x 1.5 cm length) and dned with He and moderate heat (less than 100C) before being mounted into the 8 pyroprobe. (The slightly larger sample probe will be used to enhance the drying process.) Ths process will aid the gasification process by requiring less energy to gasify the active ingredients of the sample. Thermal gravimetric analysis show that significant amounts of mass are lost for both of these samples at temperatures of ca. 150 to 160C (see Fi,we 5 and 6). The ratio of the mass at ca. 160C to the ori,&al mass is an indication of the mass lost due to water evaporation. The mass of FC-1395 and S07A before and after this drymg process will be measured to confirm that the active ingredients of the sample are not vaporized prior to insertion in the pyroprobe. C4F9S03-Kf, and C S F ~ ~ S Ow~hXc h~ a, re solid powders, will be placed into the sample probe (1 x 2 mm (id. x 0.d.) x 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 0 i aa zoo 300 400 500 600 Temperature. C Figure 5. Thermal Gravimetric Analysis (TGA) of FC-1395 s rm' 40 - 4 20 - 0 9 5. Experimental Flow Rate Setting and Calculations Table 3 and 4 summarize the experimental flow settings at temperatures of 600 and 900C, respectively. The flow rates for He and Air can be controlled w i t h i: 10 %, and the methane flow rate can be controlled within i: 5 %. Because it is necessary to load a large amount for all of available air will be used to obtain near-stoichiometric (ca. 20 % excess air) sample combustion for Other compounds will be incinerated under high excess air condition ran,$ng from ca. 100 to 450 % excess air. The concentration profile of the gasified sample is not measured directly and assumed to be an average value in the excess air calculations described above. Oxygen and methane-deficient conditions may occur in the reactor during the gasification process for some of the samples while the pyroprobe is heated to high temperatures (1000 to 1250C) and the volume of the gas expands by a factor of u p to 2.5. In other words, during the gasification process, the flow rate of the gasified sample to the reactor may be faster than the calculation shown in Tables 3 and 4. T h ~ situation is expected to be most serious for the where the level of excess air is ca. 20%. For the other six samples, the much higher excess air levels infer that oxygen- deficient conditions in the reactor are unlikely to occur. The calculations shown in Table 3 and 4 are described below with FC-807A as an example. The calculation can be conducted in a similar manner for other six compounds. The numbers in Table 3 and 4 are calculated using a spreadsheet program and the numbers are rounded to the appropriate number of significant digits. Therefore, the calculation may not exactly reproduce the numbers shown in Table 3 and 4. In Table 3, the necessary amount of C& for FC-807A can be calculated as: __ 0.58 (mg) x 0.001 (g/mg) / 51.6 (g/mol) x 0.106 (stoichiometric CH4 requirement, see Table 1) x 0.0821 (atm L / (mol K) x 298 (K) / 1 ( a b ) x 1000 ( d L )='0.03 ml The necessary amount of C& was then doubled to provide an excess of hydrogen atoms to scavenge fluorine atoms as HF. The (2% flow rate and sweeping time through the pyroprobe were calculated as shown below: 0.06 (ml) / 1.OO (min) = 0.06 (mUmin) The air flow rate to pyroprobe was added to sweep the sample out of the volume in 1 min. The volume of pyroprobe is 1.5 ml(0.35' x3.14 (cm') x 4.5 cm - 0.2 (an3). The necessary flow rate to sweep the sample out of the volume at 260C is: 1.5 (ml) / 1 (min) x 298 (K) / (260 + 273) (K) = 0.84 mUmin 10 Table 3 . Experimental Conditions at G00"C Sample Stoichiometric Amount of Sweeping Air Flow CH4Flow Amount o f h r CH4 as I1 Time Rate to Rate to for Sample (ml) Source (ml) (min) Pyroprobe Pyroprobe A r Flow Rate to Reactor for Air Flow Additional Total Gas Rate to AirFlow Flow Reactor for (ml/min) (ml/min) Residence Excess Time (s) Air ("h) (necessary amount x 2) (ml/niin) (mllmin) Sample CH4 Combustion Combustion I __ (mumin) (mllmin) -~ FC-1395 1.50 FC-807A 1.37 PFB S 1.33 PFOS 1.38 0.02 1 .OO 0.82 0.02 1S O 0.06 1.00 0.78 0.06 1.37 0.22 1.OO 0.62 0.22 1.33 0.21 1 .OO 0.63 0.21 1.38 0.15 8.00 10.49 1.96 485 0.57 7.50 10.28 2.00 381 2.07 6.00 10.24 2.01 176 1.98 6.00 10.20 2.02 179 Sample Stoichiometric Amount of Air for Sample (nd) Amount of CH4 as H Source (nil) (necessary amount x 2) I m i e 4.fiXpEriXleilIa1 L O U G K ~ O ~aSt YUU'L Sweeping Air Flow CH4Flow Air Flow Air Flow Time Rate to Rate to Rate to Rate to (min) Pyroprobe Pyroprobe Reactor for Reactor for (nd/min) I1 - (nd/min) Sample CH4 Combustion Combustion (mllmin) (mllmin) Additional Air Flow (ml/min) .. -.. . - ..- -.- ..- - .-.. Total Gas Residence Excess Flow Time (s) Air (%) (inl/min) FC-1395 1.50 . 0.02 1.30 0.63 0.01 1.15 0.12 5.80 7.72 1.99 457 FC-807A 1.37 0.06 1.30 0.60 0.05 1.05 0.44 5.50 7.63 2.01 369 I PFBS 1.33 I PFOS 1.38 0.22 1.30 0.48 0.17 1.02 1.59 4.50 7.76 1.97 172 0.2 1 1.30 0.48 0.16 1.06 1.53 4.50 7.73 1.98 174 Since 0.06 mYmin of 0.84 mumin is provided by CH4, the air flow rate will be 0.84 - 0.06 = 0.78 mumin. The necessary air flow rate to the reactor for sample combustion can be calculated by the stoichometric amount of air for sample and sweeping time: 1.37 (ml) / 1 (min) = 1.37 d m i n The stoichiometric combustion ratio of methane to air is 1 : 9.57. Therefore the air flow rate to reactor for CQ combustion can be calculated as: 0.06 rnl/min x 9.57 = 0.57 mumin With the additional air flow rate shown in Table 3, the total gas flow rate is calculated as 10.28 mYmin. .. The residence time for 0.4 cm i.d. x 8 cm effective length quartz tubing at 600C is calculated as: I 0.22x 3.14 x 8 (ml) / [10.28 (mumin) / 60 (s/min) x (600 + 273) (K) / 298 (K) = 2.00 s. The excess air ratio is the ratio of additional air to stoichiometric air. For FC-S07A, 7.5 mumin additional air flow will be introduced while 1.94 ml/min is the air flow rate for stoichiometric combustion (sample + CHJ). The excess air ratio is calculated as: 7.5 (mVmin) / 1.94 (mVmin) x 100 = 387 % 6. Effective Length of Reactor The effective length of the reactor was determined based on measured temperature profiles at - 600 and 900C. The temperatures of reactor wall (outside) were measured by thermocouples I (Chromel-Alumel Type K, 304 SS Sheath, OMEGA) wrapped with quartz tape to prevent radiation effects from the heater. For the reactor temperature of 6000C, the temperature was set at 613C. The effective length of 8 cm was obtained by allowing a deviation from the desired temperature (600C) by k 20C, which is 5 3.3 % of desired temperahue. The measured temperatures at the center of the reactor and at a distance of 1,2, 3,4, and 5 cm from the center are shown in Figure 7. For the reactor temperature of 9OO"C, temperature was set at 928C. The 8 cm effective length was obtained by allowing a deviation fiom the desired temperature (900C) by k 3092, which is also i:3.3 % of desired temperature. The measured temperatures at the center of the reactor and at a distance of 1,2, 3,4, and 5 cm fiom the center are also shown in Figure 7. 11 +- 900 c Reactor Temperature Profile -gGLI 2 cE" 0 1 2 3 4 5 Distance from Center (cm) Figure 7. Reactor Temperature Profile for 600 and 900C. The profiles are roughly symmetrical about the center of the reactor. 7. Experimental Procedure (Gas Phase Sample Analvsis and Collection) Helium will be used initially to purge both air and methane lines to the pyroprobe and - reactodtransfer line. The experiments start with setting the flow rate of air and methane and the temperatures of GC1 (260"C), furnace (600 or 900aC), and the GC2 (-60C). After the temperature is appropriately set, air and methane, if necessary, will be introduced into the pyroprobe, and air will be introduced into the reactor. The exhaust gas will be vented without pressurization by setting the switching valve 1 to (2) position. The pyroprobe will not be mounted initially in the system, instead the top of pyroprobe chamber will be capped. The sample will be carehlly loaded into capillary quartz tubing, lmm (id.) x 2mm (0.d.) x 2.0 cm (length) or 2rnm (id.) x 4 m (0.d.) x 1.5 cm (length), the net weight of sample measured, and the tubing carefully inserted into the pyroprobe. After the flow rate and temperature are properly set and sample preparation is completed, the system will be held for 1 minutes to allow the flow to stabilize. The cap for the pyroprobe chamber will then be removed and the pyroprobe quickly inserted into its chamber. Immediately afterwards, the pyroprobe will be ignited to gasify the sample. M e r the appropriate amount of time to sweep the gasified sample from the pyroprobe chamber (1.2 times of sweeping time shown in Table 3 and 4), the air flow for the pyroprobe will be maximized ( 5 rnl/min at room temperature, 8.9 mVmin at 260C) and held for 10 s. The switchmg valve for both the pyroprobe and reactor will then be switched to helium. After approximately 20 sec, switching valve 1 will be tumed to (1) position to pressurize the GC 12 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 PTJF cartridges will be secured, labeled, and appropriately packaged for next business day delivery to 3M Envlronmental 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 fiom the previous analysis. The exhaust gas will be vented to a laboratory hood following each test (as shown in Figure 5 ) to minimize m y cross contamination during Phase I11 study. 8. Experimental Procedure (Condensed Phase Sample Extraction) After gas-phase and PUF sample collection and analysis are completed, condensed phase sample extraction will be performed. This process will be identical to Section 2 - Laboratory Spike Analysis, as illustrated in Figure 2. The collected samples will be secured, labeled, and appropriately packaged for next business day delivery to 3M Environmental Laboratory with one blank vial (40 ml) containing 5.5 ml methanol. The sample probe (capillary quarts tubing) used for sample loading will be weighed after the combustion test to determine the net amount of sample gasified. 5 . Transfer Efficiency Test for and c ~ F ~ ~ s o ~ - K + Figure 8 shows schematic diagram of transfer efficiency test for C s g s03' K', and C8F17SO3-K'. The starting materials will be collected using two PUF cartridges in the same manner as described earlier for the combustion tests, however, in these tests, the furnace temperature will be held at 260C. The helium flow rate will be set as 20 ml/min and the temperature in the GC oven will be set as 260C. The sample preparation and loading processes are the same as the combustion off-gas collection. The switching valve, which is originally set to (2) position in Figure 8, will be switched to (1) positionjust before the pyroprobe/sample insertion. The sample will be collected for two minutes after gasification begins. The collected samples will be secured, labeled, and appropriately packaged for next business day delivery to 3M Environmental Laboratory with one blank PUF. 13 Ventilation fSyst m I Figure 8. Transfer Efficiency Test for GCI C4F9SO3-Kf,and C ~ F I ~ S O ~ - K + 6. Cross Contarnination Prevention and Examination Extensive precautions will be applied to minimize any PFOSPFBS cross-contamination due to the release of these environmentally persistent materials into the immediate laboratory environment following each combustion test. The effluent exhaust line has been connected to a laboratory hood in KL 112 following the results of the phase I1 study to mitigate the release of PFOSRFBS into the immediate laboratory environment associated with the off-line PUF sample collection. Prior to Phase IIIstudy, the laboratory tabletop and STDS combustion apparatus will be completely cleaned using reagent grade methanol and acetone and only the cleaned tabletop will be used for sample preparation and system assembly and disassembly. After the first cleanup of the desktop, the surface will be wiped using 3M Scotch-Brite High Performance Cloths with HPLC grade methanol that is used for sample extraction. The cloth will be soaked with methanol and squeezed before each wipe test. The wiping methods will follow 3M's instruction given at previous laboratory wipe test. The wiped cloth will be stored in the I-CHEM 40 ml vial provided by 3M. The vial will be stored outside of the KL 112 where the Phase 111 study will be conducted. The cleaning and wip-etests will be conducted following the completion of each subsection task and between each sample if the section involved multiple sample analysis. 14 7 . Samples to be sent to 3M The following samples will be sent to 3M Environmental Laboratory for each test shown in . Figure 1 excluding test 1. Blanks for PUF, solvent, and wipe test will be included in each shipment whenever these analyses/collection are performed. Next business day delivery will be used for all shipments. Eleven total shipments are scheduled. The contents for each shipment to be delivered are as follows: Test 2 ----- Two extracts (5.5 ml) for each test compound (PFOSand PFBS), one solvent blank (5.5 ml), one wipe test, and one wipe test blank Test 3 ----- Two sampled PUF cartridges, one blank PUF cartridge, two extracts (5.5 ml), one solvent blank (5.5ml), two wipe test, and one wipe test blank Test 4 ----- Four sampled-PUF cartridges [two for 600C (Istand Znd collections) and two for 850C (lstand 2"d collections)], one blank PUF, two extracts (5.5 ml) (lstand 2nd), one solvent blank (5.5 ml), two wipe tests, and one wipe test blank [Samples listed above are for each test compound. There are seven test compounds in Test 4.1 Test 5 ----- Two sampled PUF cartridges, one blank PUF cartridge, two extracts (5.5 ml), one solvent blank (5.5ml), two wipe test, and one wipe test blank Test 6 ----- Two sampled PUF cartridges (Ist and 2nd)for each test compounds . C$$O3-K+, and C X F ~ $ ~ O ~on-eKb~lan, k PUF'cartridge, two wipe tests, and one wipe test blank 8. Changes in Original Protocol Three significant changes have been made as the experimental approach has evolved after the original proposed protocol was approved by EPA. They are outlined below. 1. Significant changes were made to the sample inlet and gasification system. To satisfy the analytical requirements for PFOSPFBS detection by LCMS analysis by 3M, we determined that relatively large amounts of sample, 0.5 to several mg, had to be gasified in the actual experiments. This amount of sample is much larger than initially estimated (ca. 10 to 100 pg) and could not be gasified with the inlet available with the Advanced ThermalPhotolytic Reactor System (ATPRS). Preliminary experiments in phase u[ also demonstrated that higher gasification temperatures (> 400C) were necessary to rapidly gasify the fluorocarbon-based samples. As such, the System for Thermal Diagnostic Studies (STDS), equipped with a hightemperature pyroprobe that can gasify milligram quantities of material, is proposed for the phase 111combustion tests. The STDS is very similar to the ATPRS with regard to its incineratiodanalytical capabilities and is a satisfactory substitute for the ATPRS. 15 2. In the approved protocol, we had originally planned sample combustion with hydrocarbon fuels (e.g., 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 deficient and requires hydrogen source to convert F to HF, otherwise fuel will not be introduced to the reactor. 3. In the approved protocol, we also proposed to conduct combustion tests at three temperatures (600, 750, and 900OC). Preliminary combustion tests with several samples indicates that many combustion byproducts were formed at 600"C, but those combustion byproducts were not observed at higher temperature (750 and 9 0 0 T ) and the GC-MS total ion chromatograms for these higher temperatures were very similar. Therefore it is proposed that two temperatures are sufficient to analyze the combustion phenomena of the selected samples (600 and 900OC). . .. 16 November 4,2002 Addenda for Phase 111 Protocol 9. 2ndTransfer Efficiency Test for > C4F9S03-K+(PFBS), and CgFl+03-Kf (PFOS) In addition to the transfer efficiency tests specified in phase IItprotocol, direct transfer efficiency tests where the gasified samples are collected without passing through the combustion reactor will also be performed. Samples will be collected using two PUF cartridges. Extraction of the entire system @yoprobe chamber and transfer tubing) will be performed using methanol as the solvent. This additional study will provide information concerning how much PFBS and PFOS is transported f?om the pyroprobe through the transfer lines to the reactor entrance. The transfer efficiency tests in the phase I11protocol address sample transport from the pyroprobe to the combustion reactor exit. Figure 9 shows a schematic diagram of the direct transfer efficiency test for PFBS, and PFOS. The gasified samples-will be collected using two PUF cartridges in the similar manner as described in Section 5 of the phase I11protocol. The PUF cartridges will be directly connected to the pyroprobe chamber by 19.5 cm long, U S " 0.d. Silcosteel tubing (Silcosteel, Restec, Inc.). The GC oven temperature will be held at 260C through the entire analysis. The detailed flow profiles are shown in Table 3. Helium will be used as a carrier gas. The flow will be set as 0.63 mumin and held for one minute before the sample is inserted and gasified. After the sample is placed in the pyroprobe, the flow will remain at 0.63 d m i n for 94 seconds w h l e the sample is gasified at 1250C for 40 seconds. The flow rate will then be maximized to 4.53 mumin and held for 30 seconds to purge the sample from the pyroprobe chamber and transfer line. The I conditions and operational procedures were determined to simulate gas-phase combustion of , PFBS, and PFOS at 600C. The calculated entire volume is 3.79 ml as shown the detail below: ._ Pyroprobe chamber: Transfer line: Total: (0.35)' (cm') x 3.14 x 8 (cm) (0.108)* (crn2)x 3.14 x 19.5 (crn) = 3.08 ml = 0.71 ml 3.79 ml The system will be extra.ctedwith methanol using five 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 Profile for Direct Transfer Efficiency Test Time Period Pyroprobe Flow Volume (sec) Rate (mumin) (dl 0-60 0.63 0.63 60 - 85 0.00" 0.00 85 - 179 0.63 0.99 179 - 189 0.63 3 4.53b 0.43 189 - 219 4.53 2.27 Total Volume (ml) 4.32 a No flow due to open system to insert the sample. Linear increase (approximate) Ventilation System i High Voltage DC Power Supply Pyroprobe and Sample Cartridge GCf Figure 9. Direct Transfer Efficiency Test for ,PFBS, and PFOS. 2 November 4,2002 10. Additional Extraction Analysis of Unheated Sample Transport Lines In addition to the extractions specified in the phase IDprotocol, the unheated sample transport lines downstream of the combustion furnace (switching valve and the transfer line between switchmg valve and PLT cartridge) will be extracted using methanol. This analysis will be performed for FC-807A and PFOS after the combustion tests at 600C. This analysis will determine if PFOSPFBS condensation occurs whde the effluent is being collected using ambient temperature PUT 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 900C Combustion Test. After combustion tests of the fEst three samples were completed, we decided to perform another blank combustion analysis using a single PUF after the combustion test at 600C but before the combustion test at 900C for the rest of the samples (FC-807AY ,PFBS, and PFOS). The temperature of the GC oven and reactor will be set at 260 and 600C, respectively. Table 4 shows the flow profile that will be performed for this analysis. Table 4. Flow Rate Profile for PUF Collection (Blank Analysis between 600 and 900OC) Time Period 0 - 120 Reactor Flow Rate ( d r n i n ) Air 9.70 Pyroprobe Flow Rate (mllmin) Air 0.84 Total Flow Rate (ml/min) 10.54 Volume 21.08 120 - 130 130- 140 140 - 160 9.70 9.70 8.89 (He)b 0.84 3 4.63' 4.63 4.53 (He)' 10.54 14.33 14.33 13.42 Total Volume (ml) 2.07 2.39 4.47 30.01 aLinearincrease (approximate). b7cSwitched to helium for sweep Air and helium will be used for the sample collection. The flow rate for the reactor and the pyroprobe will be same as the actual combustion test at 600C. Air will flow for 120 seconds and then increased to the maximum flow rate and held for 10 seconds. Air will be replaced by helium to purge all the air from the system for 20 seconds. The collected samples will be secured, labeled, imd appropriately packaged for the delivery to 3M Environmental Laboratory with the other PUFs and methanol extractions. 3 November 4,2002 12. 3rdTransfer Efficiency Test for PFBS and PFOS (Sample in Reactor) Another transfer efficiency test where PFBS and PFOS are directly placed in the reactor and gasified will also be conducted. This analysis will demonstrate the PFBSRFOS transport efficiency of the overall system downstream of the combustion reactor. It will also demonstrate how efficiently the PUTScapture the PFBS and PFOS that exits the reactor in the vapor/aerosol phase. Figure 10 shows a schematic diagram of 3rdtransfer efficiency test. G C M S in-line analysis, sample collection using PUF, off-line G C M S analysis using Tedlar bag, and reactodtransfer line, valve extraction using methanol will be performed in t h s study using air and helium as camer gases. A detailed analytical procedure follows. 1. PUF collection and in-line GCMS analysis for PFBS gasification with air. 2. Tedlar Bag Collection.a. nd off-line GCMS analysis for PFBS gasification with air 3. Methanol extraction for PFBS gasification with air. I 4. PUF collection and in-line GCMS analysis for PFBS gasification with He. 5. Tedlar Bag Collection and off-line GCMS analysis for PFBS gasification with He. 6. Methanol extraction for PFBS gasification with He. 7. PUF collection and in-line GCMS analysis for PFOS gasification with air. 8. Tedlar Bag Collection and off-line GCMS analysis for PFOS gasification with air. 9. Methanol extraction for PFOS gasification with air. _- - IO. PUF collection and in-line G C M S analysis for PFOS gasification with He. 11. Tedlar Bag Collection and off-line GCMS analysis for PFOS gasification with He. 12. Methanol extraction for PFOS gasification with He. The sample will be loaded into a sample probe and placed in the middle of the reactor. The gasification temperature will be determined based on the TGAs conducted in the development of the Phase I test protocol. The transfer lines will be heated to 260C and then the reactor will be heated to the appropriate temperature. The reactor temperature will be between 525 and 575C depending on the sample and camer gas. The temperahire will be held for 5 minutes for sample collection and in-line G C M S analysis. The PUF collection, in-line G C M S analysis and off-line GC/R/IS analysis will be performed the similar manner as described in Section 5 of the phase IIIprotocol. The flow rate will be set as 10.8 d m i n to maintain the sample retention time in the reactor at approximately 2 seconds. 4 November 4,2002 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. Ventilation System Switching Valve 2 u Flow Controller GUMS <- 1 I SampIe Probe GC1 1 Figure 10.. Schematic Diagram of 3'd Transfer Efficiency Test 5 ... November 4,2002 13. Sulfur Recovery Analysis Sulfur recovery rate as SO2 using the in-line GCMS system was not quantitatively repeatable. T h s was due primarily to the low SO2 peak resolution using the cryogenic focusing method at -60C with a holding time of ca. 4 min. Because the SO2 peaks using the off-line G C M S system were much sharper than those observed using in-line G C M S , we decided to use off-line GC/MS analytical result-sto quantitatively analyze the sulfur recovery analysis as SO^. his section describes the overall protocol for these tests. 13.1 Calibration Curve Pure sulfur dioxide (Aldnch 99.9+ %) will be diluted to 100, 400, 700, 1000 ppm using the Tedlar bag (SKC Inc., 0.5 L) to construct the calibration curve. The column and the GC/MS operating conditions will be same as used for off-line G C N S analysis of the actual combustion tests. Each concentration will be performed twice and the average will be taken. 13.2 SO2 Transfer Effic'i'encyAnalysis Known amount of SO2 standard will be injected into reactor and collected along with camer gas (air) flow by 0.5 L Tedlar bag. 1 ml of collected sample will be injected to off-line GCMS system and recovery rate will be calculated using the calibration established above. Figure 11 shows the schematic diagram of SO2 transfer efficiency test. The reactorkransfer line system will be heated at 260C throughout the SO2 transfer efficiency test. Dry air will be used as a carrier flow. The flow rate for the reactor and pyroprobe will be 8.0 and 0.75 mumin, respectively. After the switching valve is turned to (1) position, 1 ml of 4.0% concentration SO2 will be injected to the reactor. The sample will be collected for 2.5 min, then the switching valve will be turned to (2)position and the bag will be closed. The sampled bag will be brought to offline GCMS 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. 6 ._ Veri tilation Systgm November 4,2002 n 9r Valve 1 Flow Control1 Cham\ ber l r x c , . I L G- C_ 1 . I Figure 11. Schematic Diagram of SO2 Transfer Efficiency Test 7 Appendix 4 The 3M Analytical Report Analytical Results for the University of Dayton Research institute Study Titled "Laboratory-Scale Thermal Degradation of Perf1u oroa I kyI Su Ifonates and Perflu oroa I kyl Su Ifonami des" Combined Laboratory Report for E02-0820,E02-0821, E02-0822, 1 i E02-0839,E02-0840,E02-0867,E02-0895,E02-0896, E02-0898,E02-0899,E02-0916,E02-0917,E02-0926, E02-0968,E02-0969,E02-0970,and E02-0971 Testing Laboratory 3M EnvironmentalTechnology & Safety Services 3M EnvironmentalLaboratory 2-3E-09 935 Bush Avenue, St. Paul, MN 55106 Laboratory Contact Ph.D Bldg. 2-3E-09 P.O. Box 3331 St. Paul, MN 55133-3331 Phone FAX: Requester 3M Environmental Technology & Safety Services Bldg. 2-3E-09 P.O. Box 3331 St. Paul, MN 55133-3331 Page 1of 37 3M Environmental Laboratory I i I: University of Dayton IncinerationStudy I . .. .. Solvent e,utracts and polyurethane foam (PUF) cartridges (Supelco, ORBOTM-lOOO,22mm OD PUF Sampler) were submitted to the 3M Environmental lab to determine at what levels PFOS, PFBS, and were present in the samples generated at the University of Dayton Research Institute, URDI, during the study titled "Laboratory-Scale Thermal Degradation of Perhoroalkyl Sulfonates and Perfluoroalkyl Sulfonamides". Sample results presented here were generated at 3M using LC/MS instrumentation to detect and quantitate the anions of PFOS (CBFI~SO~P')F, BS (C4FgSO3'), Individual study samples and quality control samples are presented in Appendix A, which contains both the measured anion concentrations and the concentration of the compounds uncorrected for purity and the contribution of the potassium cation to the mass used allowing URD1 to calculate percent recoveries. The interpretation of results is beyond the scope of this report and will be completed by URD1 study personnel and the 3M requester and presented in the URD1final report. Reported samples were received at the 3M Environmental Laboratory from URD1 between August 20 and September23,2002 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 refrigeratorat approximately4%. Dates of receipt of all samples are documented in the raw data. Samples E02-089943014 and 02-0899-43012 were not located with the associated samples in sample check-in. These samples were associated with the extraction blank and first extraction for the second heated blank combustion. There are no results reported for these samples. Three sample containers, I-Chem vials, were received not labeled. It is assumed that these samples correspond to the blank, first and second extraction samples (EO2-084042716,E020840-42714, and E02-0840-42715) for the FC-1395 incineration test, since they were received with the other FC-I395 samples. The individual I-Chem vials associated with these samples were consequently labeled as 02-0840-A, 8, and C and were identified as such in the raw data and report. The wipe samples that arrived with each set of samples were not analyzed but are retained for possible future analysis. All study samples collected but not analyzed will be retained until permissionis provided by the requester to discard them in an appropriatemanner. I I I I r .f I i Holding times for analysis were not assigned prior to sample receipt. Sampling dates, receipt dates and analysis dates are all documented in the raw data. It is not expected that sample storage conditions at the laboratory would contribute to analyte degradation, especially since study samples were subjected to the thermal degradation study conditions. It is also expected that the fluorochemicais measured are stable in methanol over the time period of this study. Page 2 of 37 3M Environmental Laboratory University of Dayton Incineration Study Preparatory and analytical methods were not validated for this project but are processed with quality control spikes and blanks to assess method performance. For this project, methanol extracts and polyurethane foam (PUF) cartridges were analyzed via LC/MS. Most of the methanol extracts did not require any further preparation prior to analysis. However, some extracts did require a simple dilution in methanol prior to analysis. These samples (extracts and dilutions) were aliquoted into sample vials and analyzed. The PUF samples, lab control blanks, and lab control spikes required extraction prior to analysis. In summary, the PUF was extracted by removing the large plastic endcap at the wide end of the cartridge ana 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 cartidge was vortex mixed for at least fifteen seconds and then inverted five times to ensure proper mixing. Then the sample was allowed to sit for fifteen minutes to allow for desorption of the analytes of interest. After fifteen minutes, the sample was drained and washed again with the same twenty milliliters an additional four times for a total of five washes. After the fifth wash, the methanol was collected and aliquoted into a sample vial for analysis via LC/MS. Analysis of samples was conducted based on ETS-8-155.1 "Analysis of Waste Stream, Water Extracts or Other Systems Using HPLC-Electrospray/Mass Spectrometry." This method is not written specifically for the extraction of PUF cartridges,just for the analysis of the analytes of interest via LC/MS. The method was modified (documented as deviations) to strengthen the data quality for these analyses by the following: standard curves are to be injected only prior to the samples, CCVs are injected at least every ten samples, the coefficient of determination is to be greater than 0.990, CCVs must be within +25%, the system suitability must be 4 . 0 % relative standard deviation (RSD) for area counts and <2.5% RSD far retention times, and the standards should be within Q5% (lower limit of quantitation (LLOQ) ?30%) 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 LC/MSD in the negative ion mode. Approximate instrument conditions are presented below. Actual conditions are documented in the raw data. LC CONDITIONS: Column Flow: Injection Volume: Column Temperature: Column: Column Size: 0.300 mUmin 3-5 pL 30% Betasil C18 2x50 mm, 5 p Solvent A: Solvent B: Gradient: 2 mM Ammonium Acetate Methanol Time 0.00 0.50 3.00 5.50 6.00 9.00 %A %E 85 15 85 15 0 100 0 100 85 15 85 15 Page 3 of 37 3M Environmental Laboratory University of Dayton Incineration Study 1 MS CONDITIOEIS: Mode: SIM Polarity: Negative V Cap: 4000 V SIM Ions: Compound Ion PFOS 499 PFBS 299 . sis 5.1 Calibration Calibrations curves were constructed using at least five concentrationswith quadratic fitting. All coefficients of determination were greater than 0.990 and all calibration standards used in the calibration curves'were within +25%,the LOQ within 530%. Calibration standards outside this range that were excluded are documented in the raw data along with technical justification for deactivationof curve points. Continuingcalibrationverification standards (CCVs) were analyzed after no more than 10 samples. All CCV recoveries were within +25% as specified by the method. 5.2 System Suitability Out of the ten analytical runs where three compounds in each were evaluated (30 total) all system suitabilities passed for the analytes of interest except for on 9/26/02 (PFBS), 10/04/02 (PFOS), and 10/08/02 (PFBS). The system suitabilities were 5.2%, 5.2%, and 5.3% RSD respectively,exceeding the 5.0% RSD criterion typically allowed. Since all calibration curves and CCVs all passed for each analysis, the data were accepted. 5.3 Blanks All solvent blanks were less than one half the area counts of the lower limit of quantitation with two exceptions. On 9/30/02, a methanol blank contained approximately 9.4 pg/pL of PFOS. This methanol blank was followed by E02-089542975 (PFOS-BLK-PUF), which had PFOS levels below the LLOQ ( 4 . 0 0 pg/pL). Since the next sample following the blank was cLLOQ, this one time occurrence did not affectthe data. Also, on 9/23/02. all of the methanol blanks contained apprclxirnately 8-9 pg/pL of Since the instrument blank and many of the samples were below the LLOQ (4.96 pg/pL) it was deemed that the methanal blanks were contamtnated, not the instrument. Based on this fact and that none of the samples were from tests specifically for fthis run consisted of the 3rdtransfer efficiency tests for PFOS and PFBS), the results for were accepted. 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. Ii Page 4 of 37 3M Environmental Laboratory University of Dayton Incineration Study 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, 80% and 90% respectively for PFBS, and 62% and 73% respectively for Sample results are not corrected for this recovery information. Summaries of each analysis of the LCSs are presented in Appendix B. 5.5 Sample Calculations Sample Calculation: Final'Result(ug) = Instrument Result (ug/L)xDilution Factorx Extraction Volume (L) So for E02496843362 (TE3-EX-PFOS-R-3) Final Result (ug) = 270-uxg 50 x 0.0102 L = 138 ug L Polyurethane Foam (PUF) Cartridge spike recoveries: Instrument Result (ug/L) x 0.02 L Percent Recovery = Spiked Amount (ug) XlOO SOfor 020923LCS-1 (PFOS): 38.2-uxg 0.02 L Percent Recovery = L x 100 = 76% 1 .oo ug Individual sample results are presented in appendix A. Each sample is identified with its respective LlMS number and the code that was associated with the sample upon arrival at 3M Environmental Laboratory. Sample results are given as pg/pL (or ng/mL or parts per billion) and in pg (if applicable) for each analyte of interest. Samples that were not detected above the lower limit of quantitation (LLOQ) are reported a s less than quantities ("c")with the numerical value being the LLOQ for the analysis of that particular sample. Laboratory Control Spikes are presented in appendix B and are reported in pg/pL and the percent recovery is given. Averages and standard deviations are only calculated for each spiking level of the Laboratory Control Spikes. Individual samples were not corrected for recovery. Page 5 of 37 3M Environmental Laboratory University of Dayton Incineration Study The final report and raw data will be retained according to 3M Environmental Lab standard operating procedures. 8 Appendices Appendix A: IndividualSample Results Appendix 8 : Laboratory Control Spikes Appendix C: Example Chromatograms Page 6 of 37 3M Environmental Laboratory University of Dayton incineration Study Ph.D., Technical Manager QualtyAssur&xx?Representative Senior Research Chemist /'&/ o> Date Date ., Date 3M Environmental Laboratory University of Dayton Incineration Study Appendix A: Individual Sample Results Page 8 of 37 3M Environmental Laboratory University of Dayton Incineration Study _. Sample E02-082042500 600- I E02-082042502 900-1 E02-082042504 -BLK-PUF E02-082042505 ,-I E02-OS2042507 BLK E02-0821425 19 PFOS I E02-082142520 PFOS 2 E02-082 1-42521 PFBS I E02-0821-42522 PFBS 2 E02-082 1-42523 PFS-ELK E02-0822-42526 -600-1 EO2-082242927 -600-2 E02-0822-42528 -900-1 E02-0822-42529 -900-2 E02-0822-42530 C-PW E02-0822-4253 I -I E02-0822-42532 L -2 802-0922-42533 ILK LIQ , E02-0839-42697 -600-1 E02-083942698 -600-2 E02-083942699 ,900-1 E02-0839-42700 1900-2 E02-08394270 1 LK-PUF E02-083942702 .I E02-083942703 ,-2 E02-083942704 LB LK E02-0840-42708 FC1395-600-1 E02-0840-42709 FC1395-600-2 E02-0840-427 IO FC1395-900- 1 E02-084042711 FC1195-900-2 E02-084042712 FCI 395-BLK-PUF E02-0840-A FC1395 EXTRACT E02-0840-8 FC1395 EXTRACT E02-0840-C FC1395 EXTRACT E02-086742903 FC807-600- I E02-0867-42904 FC807-600-2 E02-086742905 FC807-69BLK 802-08674906 FCSO7-900-1 E02-086742907 FC807-900-2 E02-086742908 FC807-BLK-PUF E02-086742909 FC807-0 E02-0867-42910 FCSO7- I E02-0867-429I I FCS07-2 E02-0867129 12 FCS07-BLK E02-089542970 PFOS-600-1 E02-08954297 I PFOS-600-2 E02-089342972 PFOS-69BLK 202-0895-42973 PFOS-900-1 E02-0895-42974 PFOS-900-2 E02-089542975 PFOS-BLK-PUF E02-089542976 PFOS-0 01-089542977 PFOS- I E02-0895-42978 PFOS-2 E02-0895-42979 PFOS-BLK E02-0896-42983 PFBS-600-1 E02-0896-42984 PFBS-600-2 EO2-0896-42985 PIBS-69BLK E02-089642986 PFBS-900-1 E02-0896-42987 PFBS-900-2 E02-089642988 PFRS-ELK-PW E02-089642989 PFBS-I E02-0896422990 PFBS-2 c 10.0 <10.0 s10.0 14.9 XlO.0 212 40.5 14.7 c10.0 <IO.O c5.00 c5.00 <5.00 6.00 G.00 c5.00 4.00 4.00 4.00 G.00 ~5.00 <5.00 c5.00 c5.00 6.00 C5.00 45.00 4.00 <5,00 C5.00 G.00 4.w <5.00 -3.00 -3.00 cs.00 <5.00 <s.oo 6.00 cs.00 c5.00 cs.00 C5.00 4.00 25.1 64.0 6.32 4.31 9.01 c5.00 25.5 15.4 8.61 6.06 <5.00 c5.00 4.00 6.00 6.00 -3.00 C5.00 cs.00 <0.20 <o 20 <0.20 0.082 c0.55 1 .I 0.22 0.081 <OS5 <OS <0.10 co.10 <0.10 co. 10 <0.10 <0.028 <0.028 <0.028 so.10 co.10 co.10 <o. IO <o. IO ~0.028 <0.028 <0.028 <0.10 co. 10 co.10 <0.10 <0.10 c0.028 <0.028 ~0.028 co.10 <O.IO <0.10 <o. 10 <0.10 <o. 10 <0.014 <0.025 <0.029 c0.028 0.50 I .3 0.13 0.086 0.18 <O.lO 0.070 0.085 0.047 0.033 co.10 co.10 co.10 <0.10 <o. IO <0.10 40.028 <0.025 0 PFOS Corrected** (us) c0.25 <0.25 <0.25 0.10 C0.68 1.6 0.28 0.10 ~0.68 c0.68 <o. I 2 <0.12 <0.12 c0.12 c0.12 <0.035 <0.015 <0.015 ' co.12 <0.12 <o. I2 <0.12 co.12 <0.015 <0.035 <0.015 c0.12 c0.12 c0.12 GO.12 <0.12 <O.OIS C0.035 C0.035 co. I2 <0.12 <o. 12 q0.12 <o. 12 c0.12 C0.017 <0.035 <0.035 C0.035 0.62 I .6 0.16 0.11 0.22 c0.12 0.09 0.1 I 0.059 0.041 c0.12 c0.12 c0.12 co.12 CO.12 co.12 C0.035 C0.035 PFBS' PFBS* (PdW (us) c10.1 <0.20 c10.1 co.20 <10.1 c0.20 G10.1 C0.056 CIO.1 C0.056 c10.1 <0.056 <10.1 <0.056 146 0.90 10.2 0.056 c10.1 c0.056 6 . 0 5 c0 10 G.05 ~0.10 ~5.05 ~0.10 <5.05 <0.10 ~5.05 ~0.10 25.05 <0.028 <5.05 C0.028 G . 0 5 <0.028 c5.05 <0.10 ~5.05 <0.10 -3.05 cO.10 -3.05 <O.IO c5.05 CO.10 6 . 0 5 <0.028 <5.05 cO.023 C5.05 c0.028 G.05 <0.10 ~ 5 . 0 5 <0.10 -3.05 <0.10 C5.05 SO.10 -3.05 <0.10 -3.05 <0.028 c5.05 <0.028 G.05 (0.025 G.05 cO.10 6 . 0 5 cO.10 <5.05 co.10 -3.05 <0.10 -3.05 GO.10 G . 0 5 cO.10 -3.0s C0.014 6 0 5 c0.028 '3.05 CO.029 G5.05 <0.028 <5.05 co.10 ~ 5 . 0 5 qO.10 G . 0 5 <0.10 c5.05 CO.10 25.3 0.52 -3.05 CO.10 17.0 0.047 7.11 0.039 4.05 <0.028 G.05 ~0.02s 34.5 1.7 85.6 1.7 19.3 0.39 120 6.4 9.63 0.19 c5.05 CO.10 169 0.93 60.3 0.33 PFBS Corrected** (us) <0.21 c0.21 <0.21 <0.065 <0.065 c0.065 <0.065 0.93 0.065 G0.065 <0.12 c0.12 <0.12 c0.12 CO. 12 c0.032 <0.012 <0.032 <0.12 c0.12 <o. 12 <0.12 c0.12 c0.012 c0.012 <0.032 c0.12 10.12 eo. I2 co.12 c0.12 c0.032 c0.012 c0.032 so.12 <0.12 <O.I2 co.12 co. 12 <O.IZ c0.016 <0.03? G0.032 <0.012 c0.12 <0.12 co.12 c0.12 0.64 4.12 0.054 0.045 c0.012 <om2 2.0 2.0 0.45 7.4 0.22 <0.12 1.1 0.39 (PW-) <4.96 <4.96 <4.96 C4.96 <4.96 c4.96 c4.96 <4.96 <4.96 <4.96 S4.96 C4.96 <4.96 c4.96 <4.96 c4.96 <4.96 <4.96 c4.96 <4.96 c4.96 4.96 C4.96 <4.96 c4.96 <4.96 4.96 S4.96 <4.96 <4.96 c4.96 C4.96 <4.96 <4.96 c4.96 C4.96 4.96 <4.96 <4.96 <4..96 C4.96 C4.96 <4.96 <4.96 <4.96 G4.96 C4.96 c4.96 c4.96 C4.96 C4.96 c4.96 4.96 <4.96 C4.96 c4.96 26.2 c4.96 <4.96 C4.96 15.4 <4.96 (UP) <0.099 <o.a99 co.099 c0.027 c0.027 <0.027 C0.027 c0.027 <0.027 <0.027 <0.099 <0.099 co.099 <0.099 co.099 c0.027 <0.027 c0.027 <0.099 <0.099 <0.099 <0.099 -=0.099 <0.027 <0.027 C0.027 co.099 <0.099 <0.099 <0.099 c0.099 <0.027 C0.027 <0.027 <0.099 co.099 <0.099 co.099 <0.099 <0.099 4.014 C0.027 C0.027 <0.027 <0.099 <0.099 <om9 co.099 <0.099 <0.099 <0.014 <0.027 c0.027 c0.027 co.099 co.099 0.52 co.099 <0.099 <0.099 0.085 c0.027 (us) <0.10 <0.10 c0.10 <0.028 <0.028 <0.025 <0.02% <0.028 <0.028 <0.029 <0.10 <0.10 <0.10 c0.10 CO. IO <0.02% <0.025 <0.028 <o. 10 c0.10 <0.10 <0.10 c0.10 C0.028 <0.028 c0.028 c0.10 <0.10 c0.10 <o. 10 <0.10 S0.028 <0.028 <0.028 c0.10 c0.10 <0.10 CO. IO co. 10 <0.10 4.014 <0.028 ~0.028 c0.025 c0.10 <o. 10 <0.10 <0.10 c0.10 c0.10 <0.014 <0.028 4,028 co.025 <O.IO c0.10 0.54 c0.10 <O.IO <0.10 0.087 c0.023 Page 9 of 37 3ibd Environmental Laboratory University of Dayton Incineration Study _. ~ Sample E02-0896-4299 I PFBS-ELI: E02-0898-42995 ,600-1 E02-0898-42996 -600-2 E02-089842997 69BLK E02-0898-42998 900-1 E02-089542999 ,900-2 E02-0898-43000 LK-PIE E02-0898-4300 I 1- I E02-089843002 -2 E02-0898-43003 -ELK E02-089943007 HB2-600-1 02-0899-43009 HB2-900-1 602-0899-4301 I HB2-BLK-PUF E02-0916-J3081 TE-I 802-0916-43082 rE-2 E02-091643083 PFBS-TE- I E0249 16-43084 PFBS-TE-2 02-09 16-43085 PFOS-TE-I , E02-09 16-43086 PFOS-TE-2 E02-09I643087 TE-BLK E02-0917-43090 TE2-1 E02-0917-4309 I TE?-2 E02-09 1743092 PFBS-TEZ- 1 E02-091743093 PFBS-TE2-2 02-09 I743094 PFOS-TE2-I E02-0917-43095 PFOS-TE2-2 E02-091743096 TE2-ELK E02-091743 100 ,TE2x- I E02-09 17-4310I TE2x-2 E02-0917-43 102 -TE2X-BLK E02-09 17-43103 PFBS-TEZX-1 E02-0917-43 104 PFBS-TELK-2 E02-0917-43 IO5 PFBS-TE2X-BLK EM-0917-43 106 PFOS-TE2X-I EO2-09 1743107 PFOS-TE2X-2 E02491743 108 PFOS-TE2X-BLK E02492643141 "B-I E02-0926-43 142 NHB-2 E02-092643 143 NHB-BLK E02-096843 360 302-0968-43361 PFOS-HE-TE3-1 PFOS-HE-TE3-2 E02496843362 TE3.EX-PFOS-P.-3 E02.096843 363 TE343-PFOS-A.4 E02-096843364 TE3. EX-PFOS-V-3 E02-0968-43365 TE3-EX-PFOS-'4-4 E02-096843366 TE3-EX-BLK-2 ~02-096843370 E02-09694337 1 PFOS-ELK-TE3 PFOS-AIR-TW..1 E02-096943372 PFOS-AIR-TE3-2 E02-0969-43373 TE3-EX-PFOS-R1- 202-096943374 TE3-EX-PFOS-R-2 E02-096943375 TE3-EX-PFOS-V-I EO?-0969-43376 TE-13-PFOS-V.2 802-0970-43377 PFBS-AIR-TE3- 1 E02-0970-43378 PFES-AIR-TE3-2 E02-097043379 TE3-EX-R-I E02-0970-43380 TS3-EX-R-2 E02-0970-4338 1 E3-EX-V-1 E02-097033382 TE3-EX-V-2 E02-097043383 PFBS-HE-TU- I E02-0970433 84 PFBS-HE-TE3-2 E02-097043385 TE3-EX-R-3 ~5.00 CJ.00 4.00 c5.00 600 C5.00 <s.oo c5.00 <s.oo 6.00 <10.0 c10.0 c10.0 c5.00 a.00 <5.00 cs.oa G.00 <LOO <5.00 <lO.O 40.0 119 c10.0 s10.0 <10.0 < 10.0 35.0 c10.0 c10.0 23 3 40.0 c10.0 897 <LO.O <IO.O C5.00 <5.00 c5.00 2330 44.0 13530 I50 2218 I02 c10.0 <lO.O 997 c10.0 1908 35.4 696 22.9 <10.0 c10.0 <10.0 c10.0 <10.0 <10.0 s10.0 s10.0 <IO.O ~0.028 <O.lO co.10 <0.10 co.10 co.10 co.10 c0.028 <0.028 <0.029 c0.20 co.20 <0.20 <0.10 <0.10 c0.10 co.10 CO. 10 <0.10 <O.IO co.20 <0.20 2.4 <0.20 <0.20 <0.20 q0.20 0.66 GO. 19 <o. 19 4.4 <0.19 co.19 17 co.19 <o. 19 CO.028 <0.028 C0.028 47 0.88 138 I .5 6.2 0.29 ..I <0.20 20 <O.lO 19 0.16 I .9 0.064 <a20 <0.20 co.10 <0.10 C0.028 C0.028 co.20 c0.20 <o. IO PFOS Corrected-' (UP) <0.035 <0.12 co.12 c0.12 <0.12 c0.12 <0.12 C0.035 <0.015 ~0.035 c0.25 ~0.25 C0.25 <0.12 <o. I2 <o. 12 c0.12 c0.12 <o. I2 <0.12 <0.2s x0.25 3.0 e0.25 <0.25 <0.25 C0.25 0.82 40.24 <0.24 5.5 4.24 s0.24 21 C0.24 <0.24 <0.035 C0.035 S0.035 58 !.I 171 1.9 7.7 0.35 ..I co.25 25 c0.12 24 0.45 2.4 0.079 c0.25 C0.25 <0.12 <O.l2 C0.035 C0.035 c0.2s <0.2s <o. I2 PFBS' PFBS' (PdUL) (UP) 35.4 0.19 6 0 5 <0.10 45.05 C0.10 C5.05 <0.10 4 . 0 5 c0.10 C5.05 c0.10 <5.05 <0.10 ~ 5 . 0 5 <0.028 ~ 5 . 0 5 <0.028 G . 0 5 CO.018 c10.1 ao.1 c0.20 c0.20 <IO.] c0.20 C5.05 co.10 ~ 5 . 0 5 <0.10 <5.05 co.10 cs.05 a 1 0 <5.05 <0.10 4 . 0 5 <0.10 cS.05 co.10 c25.2 <0.20 11.2 0.22 c25.2 <0.20 c10.1 <0.20 c25.2 <0.20 <10.1 CO.20 c10.1 <0.20 c25.2 C0.48 4 0 . 1 C0.LY <10.1 co.19 805 15 <10.1 <10.1 <63.0 co.19 -=o. 19 < 1.20 <10.1 co.19 <10.1 co.19 -4.05 CO.028 i5.05 C0.028 cs.05 <0.028 37.4 cs.05 0.75 -=o.ia 237 cS.05 2.4 <O.OS? 47.4 c5.05 <5.05 CS.05 ...0.13 <0.014 co.10 14.7 0.29 C5.05 co.10 81.4 0.83 5.79 0.059 52.0 0. I5 cS.05 C0.014 1255 25 15.9 0.32 883 9.0 12.8 0.13 3824 I1 69.9 0.20 51 1 IO C5.05 <O.lO 10484 I07 PFBS Corrected" (%I 0.23 <0.12 c0.12 GO.12 c0.12 <0.12 c0.12 <0.032 <0.032 c0.032 C0.23 <0.23 <0.23 co.12 c0.12 <o. 12 <0.12 c0.12 c0.12co.12 c0.23 0.26 <0.23 <0.23 <0.23 <0.23 <0.23 COS6 c0.22 <0.22 18 <0.22 <0.22 x1.19 <OX <0.22 C0.032 C0.032 C0.032 0.87 co.12 2.8 <0.060 0.15 <0.016 *** -=O.l2 0.34 e0.12 0.96 0.069 0.17 e0.016 29 0.37 IO 0.15 I2 0.23 12 4.12 124 (PdUL) <4.96 ~4.96 c4.96 <4.96 C4.96 c4.96 <4.96 <4.96 <4.96 4.96 <4.96 <4.96 c1.96 4.96 4.96 <4.96 ~4.96 <4.96 C4.96 c4.96 <4.96 <4.96 C4.96 <4.96 ~4.96 <4.96 <4.96 6.89 c4.96 ~4.96 c12.4 <4.96 <4.96 C12.4 c4.96 <4.96 C4.96 4.96 <4.96 c1.96 C4.96 ~4.96 <4.96 <4.96 <4.96 <4.96 4.96 e4.96 C4.96 <4.96 C4.96 <4 96 4.96 <4.96 c4.96 <4.96 c4.96 8.17 <4.96 s4.96 <4.96 <4.96 (UP) c0.027 <0.099 <0.099 co.099 XO.099 <0.099 <0.099 C0.027 C0.027 C0.027 co.099 co.099 <0.099 <0.099 co.099 co.099 ~0.099 <0.099 <0.099 co.099 <0.099 <0.099 <0.099 co.099 <0.099 <0.099 co.099 0.13 C0.094 <0.094 <0.24 c0.094 C0.094 <0.24 C0.094 C0.094 c0.027 c0.027 <0.027 co.099 cO.099 <0.050 co.050 sO.014 <0.014 *.* co.99 co.99 <0.99 <os0 <OS0 C0.014 <O.OlJ co.99 <0.99 C0.050 <O.OJO 0.023 <0.014 <0.99 co.99 <O.OjO (UP) <0.028 <0.10 c0.10 c0.10 <0.10 <o. 10 a10 <0.028 <0.028 <0.028 c0.10 <o. I0 <o. IO 50.10 <0.10 <0.10 c0.10 <o. 10 c0.10 <0.10 CO.10 <0.10 <0.10 c0.10 <0.10 <0.10 c0.10 ' 0.13 <0.097 c0.097 <0.25 e0.097 C0.097 c0.25 <0.097 <0.097 q0.028 4.028 <0.029 <o. I O <O.lO 4.052 c0.052 ...C0.014 <0.014 <1.0 c1.0 51.0 <052 <052 e0.014 <0.014 c1.0 <1.0 <0.052 co.052 0.024 <0.014 <1.0 c1.0 x0.052 Page 10 of 37 3M Environmental Laboratory University of Dayton Incineration Study Sample E02-097043386 TE3-EX-R-4 E02-0971-43387 TE3-EX-V-3 E02-0971-43388 TE3-EX-V.4 E02-097143392 PFBS-ELK-TE3 02-0971-43393 TE3-EX-BLK-I PFOS' (PglUL) c10.0 c10.0 c10.0 c10.0 c10.0 PFOS' (ug) co.10 ~11.02s c0.028 co.20 *** PFOS Corrected'* (UP) <0.12 co.03~ co.035 <0.25 .** PFBS' (PwJ 420 2510 71.6 cs.05 C5.05 PFBS' (UP) 4.3 70 0.20 co.10 *** PFBS Corrected" (W) 5.0 8.2 0.23 co.12 *** (PgiUL) 11.9 C4.96 ~4.96 ~4.96 <4.96 (ud 0.12 C0.014 ..*<O.OM ~0.99 * PFOS and PFBS results are presented as corrected for purity as the anion. is corrected for punty and presented as the ** PFOS. PFBS and are presented uncorrected for purity and as the Corrections used as follows: PFOS: 0.8060 (0.869 purity x 0.9275 correction for potassium. PFBS: 0.8607 (0.971 purity x 0.8846 correction for potassium. j '** 'These samples are just bl& of the methanol used in the study. 'There is no associated volume to calculate ug for these samples. (UP) 0.12 c0.014 <a011 C1.0 .** Page 11 of 37 3M Environmental Laboratory University of Dayton Incineration Study Appendix B: Laboratory Control Spikes Page 12 of 37 ,..... 3M Environmental Laboratory University of Dayton Incineration Study Table'l: 1 ug Laboratory Control Spikes Sample 020913LCS-1 PFOS percent PFBS percent (pg/uL) recovery RPD (pghL) recovery RPD 43.4 87% 4.9% 43.5 86% 5.0% 020913LCS-2 02091 3LCS-1 45.6 91% 45.7 91% 45.6 91% 4.0% 43.9 87% 3.4% 020913LCS-2 020923LCS-1 47.4 95% 45.4 90% 35.2 76% 14% 35.4 70% 16% 020923LCS-2 020923LCS-1 44.0 85% 41.7 83% 37.1 74% 19% 35.1 75% 15% 020923LCS-2 02093OLCS- 1 44.8 90% 44.4 88% 35.3 71% 3.3% 35.6 71% 2.9% 02093OLCS-2 02100 1LCS- 1 36.5 73% 36.7 73% 34.7 69% 10% 34.6 68% 11% 021001LCS-2 020927LCS-1 38.4 77% 38.4 76% 41.5 83% 2.0% 39.7 79% 9.7% 020927LCS-2 42.3 85% 43.7 87% Average 41.0 82% 40.5 80% 1StandardDeviation 4.27 RSD 10% 8.5% 4.02 8.0% 10% True values of the LCS samples are: PFOS 50.0 p & L (1.00 ug), PFBS 50.5 pghL (1.01 ug). and RPD-Relative Percent Difference @g/uL) 34.5 36.0 35.4 36.3 25.5 31.1 26.8 33.0 25.5 25.8 24.6 27.1 32.3 35.5 30.7 4.55 15% percent recovery 69% 73% 71% 73% 51% 63 % 54% 66% 51% 52% 50% 55% 65% 72% 62% 9.2% RPD 4.4% 2.5% 20% 21% 1.2% 9.5% 9.4% Table 2: 10 ug Laboratory Control Spikes PFOS percent Sample (pgluL) recovery RPD 020913LCS-3 464 93% 6.8% PFBS percent @g/uL) recovery 450 89% RPD 9.3% - percent @g/uL) recovery 357 72% RPD 14.1% 0209 13LCS-4 497 99% 495 98% 41 1 83 % 0209 13LCS-3 489 98% 5.9% 473 94% 7.0% 372 75% 13.1% 020913LCS-4 519 104% 507 100% 424 86% .- 020923LCS-3 .414 83% 4.6% * * 320 65% 6.8% 020923LCS-4 433 57% * * 343 69% 020923LCS-3 434 87% 4.3% 405 80% 3.9% 331 61% 6.3% 020923LCS-4 02092SLCS-3 02092:iLCs-4 453 91% 421 83% 425 85% 4.6% * * 445 89% * * 353 71% 337 68% 8.1% 365 74% 02092:iLCs-3 458 92% 3.7% 437 87% 4.8% 352 71% 6.5% 476 95% 459 91% 376 76% 459 92% 456 90% 362 73% Standard Deviation 31.6 RSD 7% 6.3% 34.9 6.9% 8% 31.0 6.3% 9% True values of the LCS samples we: PFOS 500 pg/uL (10.0 up), PFBS 505 pg/uL (10.1 up). and Valuer were above the upper limit of qwtitation for that analysis (nominal concentration of 250 pg/uL). For that analysis the high calibrationpoint (nominal concentration of 500 pg/uL) WM excluded in order to quantitatesamples at a lower LLOQ (lower limit of quantitation). In other words, the 500 p g / L standard was excluded to make the lowest standard within the +/- 30% criteria. These spikes were run again at a later date and all results for all analytes are presented here. Page 13 of 37 3M Environmental Laboratory University of Dayton Incineration Study Appendix C: Example Chromatograms Page 14 of 37 3M Environmental Laboratory University of Dayton Incineration Study I L *.'.* I-. ..ai ..+. ..I. Page 15 of 37 3M Environmental Laboratory I .'& ..L ..- ..I. .A. ..I. University of Dayton Incineration S t u I xi.= Info : Page 16 of 37 3M Environmental Laboratory .." I University of Dayton hckneration Sh 1 - 1 ...: 7.i Page 17 of 37 3M Environmental Laboratow c-nc . University of Dayton Incineration Stud -.--.- L M I,", I u.n, ,..I - 8 I..., ................................ . ............. ..,.. .... -_- .... 3.. .'...Ut., ,.a .I... . . ......I I..., 1.S/", a*.,* -oc Flag lpgcnd I Compound response c+mually i n r e q r a c d . Page 18 of 37 3M Environmental Laboratory ... '.+ 8.9 ..i g :.J{ ..-J ..C .... ,.I. I I ... .a. ..I. '. .A.. .. .. .......... . i.' .,..................................... ....,.......,...................... University of Dayton Incineration Stuc ..".6 . 7 .a; ,.. a.. . . . . . .,..'. . . 9 ..1 . .. I.. . . Page 19 of 37 3M Environmental Laboratory University of Dayton Incineration Study I _- - -- _ ._.._._____ M I, -.-u . . .". .." ............ ............ 1 ,1..I ...... .... ............................... I unrt I,., -n----n U" __.I- .,.., -.- ---,_u I-, I." *I" .Y,1. 1 14.w a_") "I., 111.c. -PC Flag Legend M C o m v o d reawnse mually lncograccd. Page 20 of 37 jN1 knmronmental Laboratory i..: I.& 3.4. U. L.: z.: ..e I.*. 1.1- . . : 2.. j I... , I... ...L %.I. ...L *.a. ..I. a,.. .z. University of Dayton Incineration Study 1 \.'..-.-,...: Page 21 of 37 3M Environmental Laboratory University of Dayton Incineration Stu I ..*i 'A. . . .?!..,. ... ,.I .. 1. . .. . 1 . . *,:. ... ... ......................... . 1 I., ..I I'. L .. ':, ........... '.I I.. I.' 1.1 , , , q ;..* L.? L. : ..a. , , ,.a .:i' X i ' .:i.'is Page 22 of 37 3M Environmental Laboratory ..P 1 University of Dayton Incineration St ....._....,L.r. 3 ,111 ,I", 11.1. ... .............. ........................ ................... 1" I.". ...us r,.x 14%. 11.1.s. "3.W ..,., I,..,* Y Page 23 of 37 3M Environmental Laboratory University of Dayton Incineration stul -.-........ .N I..., I L.11,1 1-1 I I.., _.- -M ..I .I. ...1.1 I.. -.I _.U ...." .....-7.. ............. ..,n ..Ill .*.I. ... ... *.I, L, . L - .. -.o. __Y.- .,l Y l (-1 ,,..... 1..11 .....o... 21.1.11 ".l.l Y,.,., I.",., U",", -PC n Flag Ccw w mu en nd d re.pan=.e onnually inzcgraced. .. Wlh ..e .... & :p 'ai I... ..a2 ..d .... .:. ...................... . . \\Kt~c~rge~\c~~~c\c~m\it~hy.i\IOllOO~.b\I~~X~K3.D 801-0840-41710 0 3 - O m - 1 0 0 1 02:37 k3 e FCl195-900-1 liuc ID, i c c h y . i - ... ."_. - ............................ --,-" ._,.1I____^._w..a..,_...........r-.n...,..".."..-.n..u...--.....-.....0 ....-.....-Y .-.U .... I VUIt ,I..# ""U Page 24 of37 3Ivf Environmental Laboratorv University o f Dayton Incineration s h ....*., I" ..a ._."as. ., .I ," , ...I ,,,,." ,,"<-", Y .* a,,. ..a, *_".*..,, I........... L ,111. YlY ..111., ...,a, Page 25 of 37 .. 3M Environmental Laboratory University of Dayton Incineration Study D l l P.EC0.: 1.00000 ... . . , " . . I ....1. b . A l " 1 . I " ,., Page 26 of 37 3M Environmental Laboratory University of Dayton Incineration Study .- ................................. ,&..I..,..,L .............. , I.." ..... .I a" ..... .I a". ,_/" I.". *.I., ,.,.,., 7" n. I ....' . , ..I;i :1: L I d. ' i i ' 1:. /I ,;,....:.. *:, ........ ......... ..Y"U.IL............... u ..._"."...........-.....-... ...................... w ._U. I...". .."I ..... ._.. I,." ,...,.I "I ......I<., Page 27 of37 3M Environmental Laboratory University of Dayton Incineration Stuc 2.q I&.7*< 5;z.c .%...a.!................ - -- --- t !.I L I Y..ll ,.",I.", - I--.- .-.- - - . . I - ......................... Y. 6.") ..1.1 18.. .**." I..,., ....,.I .."mu .......... ........... 1U ..I. a. . . . I.9 I 1 A1:L-,>...:...I.,....!'-...... Page 28 of 37 E! 3M Environmental Laboratory 4.- - ..Y 1 r.2 . . 2.2 I... +:.4':; . ,;,' .>' ' I:' University of Dayton Incineration S t u ~ P.0 I co-IC . Page 29 of 37 3M Environmental Laboratow .. ..... .."..... UU.1 ._I ,.I, -SI.I" "I.......*.-...wU......-.4...--................................................................................................,.I../.," ..,. I..." University of Dayton Incineration Study r,..!y 2 .1?..2:;.': .." .a: .:. *. L. ... I.1 I.,. I I#. " I.", ......................._.."..............................,.,-... Page 30 of 37 3M Environmental Laboratory University of Dayton Incineration Study I 1 Page 3 1 of 37 3M Environmental Laboratow University of Dayton Incineration Study .. j3 l :;:.... >....e . 1 1.6 IL.*.. *-I. ..I. ..Li I... I_II...& i 3.02 2 2 . ,L.a.i l ..I. ..*e. ,i '6:. ' .A ' i:i I:. Kl " I.? - "- 1. 2.c ...... *.I ..... ..I .2. . . .. ,A Page 32 of 37 3M Environmental Laboratow University of Dayton Incineration Study 1 z m .,'. -:'i ..': *.'I *..; .a; . .,......,....., . , . , . .a . I : . .u....I--...,....; .$ :c" z.+ ... *.$ ... .., ?..L 6.. . . , . .,.,, . Misc Info z .- ..... I- I US," I,.* 1 (.", ..%" ....................,1 .."."....... ..I .. 1..11.."..........".............,,." ..".< ,.".",I.. ..#" I Page 33 of 37 31M Environmental Laboratory ..- I.- ..a. University of Dayton Incineration Sh Page 34 of 37 I - 1 I.". s.n p ;:: ;2.d * ::i ,.a, ...L ... ...... 1 .*..... . . . . . . . .. IJ . ... 1.1 University of Dayton Incineration Study ...&. ..,. .. ..I . . .L. . . . e. . . . ,..... .,.??-z-- Page 35 of 37 3M Environmental Laboratory c-ne . University of Dayton Incineration S t u ~ I ::q \, J ,.(. . . . . . . . . . .,, .a 4.- .a.. 9. .."...... ---0-L I Y". 1.11 I I on.., -aC F l a g L q m d n caqound zc.pon.e -." -. ---.- -- -.-. .--- .-- Y " _ " e" ................ I" .."U '.*- ,,nu (1- Y.L... .... ." ......................... ........ .I ..,.". ..Y, ....'.l *,,A.. .,3 WLY ia:w.cd. 1 Page36of37 3M Environmental Laboraton 'r/** p.e: .;; - ..e .+ ................. ..a 4.6. 4." +.II. University of Dayton Incineration S t u Page 37 of 37 Appendix 5 Spreadsheet Linking the UDN Combustion Tests with the 3M Analytical Results Spreadsheet linking UDRl Thermal Testing and 3 M Analytical Results 3M Sample Number E02-082 1-425 16 E02-0821-42517 E02-0821-42518 E02-082 1-42519 E02-0821-42520 E02-0821-4252 I E02-0821-42522 E02-0821-42523 E02-082 1-42524 E02-0821-42525 E02-0820-42500 E02-0820-42501 E02-0820-42502 E02-0820-42503 E02-0820-42504 E02-0820-42505 E02-0820-42506 E02-0820-42507 E02-0820-42508 E02-0820-42509 E02-0820-42510 E02-0822-42526 E02-0822-42527 E02-0822-42528 E02-0822-42529 E02-0822-42530 E02-0822-4253 I E02-0822-42532 E02-0822-42533 E02-0822-42534 E02-0822-42535 E02-0822-42536 E02-0839-42697 E02-0839-42698 E02-0839-42699 EO2-083942700 E02-0839-42701 E02-0839-42702 E02-0839-42703 Date Saiiipled 7/30/2002 7/30/2002 7/30/2002 7/30/2002 ?!30!2002 7/30/2002 7/30/2002 7/30/2002 7/30/2002 7/30/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/2/2002 8/5/2002 8/5/2002 8/5/2002 8/5/2002 8/5/2002 8/5/2002 8/5/2002 8/5/2002 8/5/2002 8/5/2002 8/5/2002 8/7/2002 8/7/2002 8/7/2002 8/7/2002 8/7/2002 8/7/2002 8/7/2002 UDIU Sample Description WT-DT-I WT-BT-1 WT-ELK-1 PFOS 1 ?';OS 2 PPBS 1 PFBS 2 PFS - RLK WT-BT-2 WT-BLK-2 HB 1-600-I HB 1-600-2 HB 1-900-1 HB 1-900-2 kIB 1-BLK-PUF HB1-l I-IB 1-2 HB 1-BLK WT-BT-3 WT-DT-3 WT-B LK-3 '-600-1 -600-2 -900-1 -900-2 -BLK PUF -I -2 -BLK LIQ WT-BT-4-1 WT-DT-4-1 VT-BLK-4 -1 -600-1 -600-2 -900-1 -900-2 -BLK-PUF -1 -2 Test* 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5.2 5:2 5.2 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.1 5.4.2 5.4.2 5.4.2 5.4.2 5.4.2 5.4.2 5.4.2 Detailed Sample Description Desktop wipe test before Test 2 Bench top wipe test before Test 2 Wipe test blank for before Test 2 1st extraction of PFOS spike 2nd extraction a i PFOS spike 1st extraction of PFBS spike 2nd extraction of PFBS spike Solvent Blank for PFOS and PFBS extractions Bench top wipe test after Test 2 Wipe test blank for after Test 2 1st PLJF for heated blank Combustion at 600C 2nd PUF for heated blank Combustion at 600C 1st PUF for heated blank Combustion at 900'C 2nd PUF for heated blank Conibustion at 900C PUF blank for heated blank Combustion 1st extraction for heated blank Combustion 2nd extraction for heated blank Combustion Extraction blank for heated blank Combustion Wipe test for bench top after heated blank Combustion Wipe test for desktop after heated blank Combustion Wipe test blank after heated blank Combustion 1st PUF for Combustion at 600C 2nd PUF for Combustion at 600C IstPUFfor. Combustion at 900C 2nd PUF for Combustion at 900C PUF blank 6 r - I Combustion 1st extraction for- Combustion 2nd extraction for Combustion Extraction blank io; Combustion Wipe test for bench top after Combustion Wipe test for desktop after Combustion Wipe test blank after :ombustion I St PUF fOT Combustion at 600C .. 2nd PUF for - Combustion at 600C 1st PUF for Combustion at 900C 2nd PUF fo; Combustion at 900C PUF blank for - Combustion 1st extraction for Combustion 2nd extraction for Combustion Spreadsheet linking UDRl Thermal Testing and 3M Analytical Results E02-0839-42704 E02-0839-42705 EO2-0839-42706 E02-0839-42707 E02-0840-42708 E02-0840-42709 E02-0840-42710 E02-0840-4271 I E02-0840-42712 E02-0840-427 14 E02-0840-42715 E02-0840-42716 EO2-0840-427 17 E02-0840-42718 E02-0840-42719 EO2-0867-42903 E02-0867-42904 E02-0867-42905 E02-0867-42906 E02-0867-42907 E02-0867-42908 E02-0867-42909 E02-0867-429 IO E02-0867-42911 E02-0867-42912 E02-0867-42913 E02-0867-429 14 E02-0867-42915 E02-0898-42995 E02-0898-42996 E02-0898-42997 ~02-0898-4299a E02-0898-42999 E02-0898-43000 E02-0898-43001 E02-0898-43002 E02-0898-43003 EOI-089a-43004 EO?-0898-43005 E02-0898-43006 E02-0896-42983 E02-0896-42984 8/7/2002 8/7/2002 8/7/2002 8/7/2002 8/9/2002 8/9/2002 8/9/2002 R!912002 8/9/2002 8/9/2002 8/9/2002 8/9/2002 a1912002 8/9/2002 8/9/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 8/20/2002 812 112002 8/21/2002 8/2112002 8/21/2002 812 112002 8/21/2002 812 I 12002 812 112002 X I 2 112002 8/21/2002 812 112002 812 V2002 8/22/2002 8/22/2002 J-BLK WT-BT-4-2 WT-DT-4-2 WT-B LK-4-2 FCI 395-600-1 FCI 395-600-2 FC1395-900-1 FC1395 900-2 FCI 395-BLK-PUF FCl395-I FC1195-2 FC1395-BLK , WT-BT-4-3 WT-DT-4-3 WT-B LK-4 -3 FC807-600-1 FC807-600-2 FC807-69BLK FC807-900-1 FC807-900-2 FC807-BLK-PUF FC807-0 FC807-1 FC807-2 FC807-BLK WT-BT-4-4 WT-DT-4 -4 WT-BLK-4-4 -600-1 -600-2 -69BLK -900-1 -900-2 -BLK-PUF -1 -2 -BLK WT-BT-4-5 WT-DT-4-5 WT-ELK-4-5 PFBS-600-1 PFBS-600-2 5.4.2 5.4.2 5.4.2 5.4.2 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 5.4.3 5.4.4 5.4.4 5.4.4 5.4.4 5.4.4 5.4.4 5.4.4 5.4.4 5.4.4 5.4.4 5.4.4 5.4.4 5.4.4 5.4.5 5.4.5 5.4.5 5.4.5 5.4.5 5.4.5 5.4.5 5.4.5 5.4.5 5.4.5 5.4.5 5.4.5 5.4.6 5.4.6 Extraction blank for. Combustion Wipe test for bench top after Combustion Wipe test far desktap after Combustion Wipe test blank after Combustion 1st PUF for FC-1395 Combustion at 600C 2nd PUF for FC-1395 Combustion at 600C 1st PLJF for FC-1395 Combustion at 900C 2nd PUF for FC-1395 Combustion at 9 0 0 T PUF blank for FC-1395 Combustion 1st extraction for FC-1395 Combustion 2nd extraction fur FC-1395 Combustion Extraction blank for FC-1395 Combustion Wipe test for bench top after FC-1395 Combustion Wipe test for desktop after FC-1395 Combustion Wipe test blank after FC-1395 Combustion - 1st PUF for FC-807 Combustion at 600C 2nd PUF for FC-807 Combustion at 600C Blank Combustion between 600 and 900C Is1 PUF for FC-807 Combustion at 900C 2nd PUF for FC-807 Combustion at 900C PUT: blank for FC-807 Combustion Valve and Extended Tubing Extraction after 600C FC-807 Combustion 1st extraction for FC-807 Combustion 2nd extraction for FC-807 Combustion Extraction blank for FC-807 Conibustion Wipe test for bench top after FC-807 Combustion Wipe test for desktop after FC-E07 Combustion Wipe test blank after FC-807 Combustion 1st PUF for ?ombustion at 600C 2nd PUF for Combustion at 6000C Blank Combustion between 600 and 900C Is1 PUF for Combustion at 900C 2nd PUF for lombustion at 900C ' PUF blank for Ir . Combustion 1st extraction for Combustion 2nd extraction for Combustion Extraction blank for :ombustion Wipe test for bench top after :ombustion Wipe test for desktop after Combustion Wipe test blank after Combustion 1st PUF for PFBS Combustion at 600C 2nd PUF for PFBS Combustion at 600C I Spreadsheet linking UDRl Thermal Testing and 3M Analytical Results EO2-0896-42985 EO2-0896-42986 EO2-0396-42987 E02-0896-42988 E02-0896-42989 E02-0896-42990 E02-0896-42991 E02-089642992 E02-0896-42993 E02-0896-42994 E02-0895-42970 E02-0895-42971 E02-0895-42972 EO2-0895-42973 E02-0895-42974 E02-0895-42975 E02-0895-42976 E02-0895-42977 E02-0895-42978 E02-0895-42979 E02-0895-42980 E02-0895-42981 E02-0895-42982 E02-0899-43007 ~02-08994300a E02-0899-43009 E02-0899-43010 E02-0899-43011 E02-0899-43012 E02-0899-43013 E02-0899-43014 E02-0899-43015 E02-0899-43016 E02-0899-43017 E02-0916-43081 E02-0916-43082 E02-0916-43083 E02-091643084 E02-0916-43085 E02-0916-43086 E02-09 16-43087 E02-0916-43088 8/22/2002 8/22/2002 8/22/2002 8/22/2002 8/22/2002 8/22/2002 8/22/2002 Rf22!2002 ai2212002 812212002 812612002 812612002 812612002 812612002 8/26/2002 8/26/2002 812612002 812612002 812612002 812612002 812612002 a/2612002 812612002 a/27/2002 8/27/2002 8/27/2002 8/2 712002 8/27/2002 8/27/2002 8/27/2002 812 712002 ai2712002 812712002 8127l2002 812 812002 8/28/2002 8/28/2002 8/28/2002 8/28/2002 8/28/2002 8/28/2002 8/28/2002 PFBS-69BLK PFBS-900-1 PFBS-900-2 PFBS-ELK-PUF PFES-I PFBS-2 PFBS-ELK WT-BT-4-6 WT-DT-4-6 WT-ELK-4-6 PFOF-600-1 PFOS-600-2 PFOS-69BLK PFOS-900-1 PFOS-900-2 PFOS-BLK-PUF PFOS-0 PFOS-I PFOS-2 PFOS-BLK WT-BT-4-7 WT-DT-4-7 WT-B LK-4-7 HB2-600-1 HB2-600-2 HB2-900-1 HB2-900-2 HB2-BLK-PUF HB2-1 HB2-2 HB2-BLK WT-BT-HB2 WT-DT-HE2 WT-BLK-HB2 TE-1 TE-2 PFBS-TE- 1 PFBS-TE-2 PFOS-TE-1 PFOS-TE-2 TE-ELK WT-DT-6 5.4.6 5.4.6 5.4.6 5.4.6 5.4.6 5.4.6 5.4.6 5.4.6 5.4.6 5.4.6 5.4.7 5.4.7 5.4.7 5.4.7 5.4.7 5.4.7 5.4.7 5.4.7 5.4.7 5.4.7 5.4.7 5.4.7 5.4.7 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.6 5.7.1 5.7.1 5.7.1 5.7.1 5.7.1 5.7.1 5.7.1 5.7.1 Blank Combustion behveen 600 and 900C 1st PUF for PFBS Combustion at 900C 2nd PUF for PFBS Combustion at 900C PUF blank for PFBS Combustion 1st exkaction for PFBS Conibustion 2nd extraction for PFBS Combustion Extraction blank for PFBS Combustion Wipe trsl for bench top after PFBS Combustion Wipe test for desktop after PFBS Combustion Wipe test blank after PFBS Combustion 1st PUF for PFOS Combustion at 6 0 0 T 2nd PUF for PFOS Combustion at 600C Blank Combustion behveen 600 and 900C 1st PUF for PFOS Combustion at 900C 2nd PUF for PFOS Combustion at 900C PUF blank for PFOS Combustion Valve and Extended Tubing Extraction after 600C PFOS COmI bustion 1st exkaction for PFOS Combustion 2nd extraction for PFOS Combustion Exh-actionblank for PFOS Combustion Wipe test for bench top after PFOS Combustion Wipe test for desktop after PFOS Combustion Wipe test blank after PFOS Combustion 1st PUF for 2nd heated blank Combustion at 600C 2nd PUI; for 2nd heated blank Combustion at 600C 1st PUF for 2nd heated blank Combustion at 900C 2nd PUF for 2nd heated blank Combustion at 900C PUF blank for 2nd heated blank Combustion 1st extraction for 2nd heated blank Combustion 2nd extraction for 2nd heated blank Combustion Extraction blank for 2nd heated blank Combustion Wipe test for bench top after 2nd heated blank Combustion Wipe test for desktop after 2nd heated blank Conibustion Wipe test blank after 2nd heated blank Combustion 1st PUF 1st Transfer Efficiency 2nd PUF . : 1st Transfer Efficiency 1st PUF PFBS 1st Transfer Efficiency 2nd PUF PFBS 1st Transfer Efficiency 1st PUF PFOS 1st Transfer Efficiency 2nd PUT; PFOS 1st Transfer Efiiciency PUF Blank for 1st Transfer Efficiency Wipe Test Desktop 1st Transfer Efficiency S p r e a d s h e e t linking UDRl Thermal Testing and 3M Analylicai Results E02-091643089 E02-091743090 EO?.-09174309 1 E02-0917-43092 E02-0917-43093 E02-091743094 E02-0917-43095 ~02-n917-43096 E02-0917-43097 E02-0917-43098 E02-0917-43099 E02-09 17-43100 E02-09l7-43IOl E02-0917-43102 E02-0917-43 103 EO2-0917-43104 E02-0917-43 105 E02-0917-43106 E02-0917-43 107 E02-09 17-43I08 E02-0926-43141 E02-0926-43142 E02-0926-43143 E02-0926-43 144 E02-0926-43145 E02-0970-43377 E02-0970-43378 E02-0970-43379 E02-0970-43380 EO2-0970-43381 E02-0970-43382 E02-0970-43383 E02-0970-43384 E02-0970-43385 E02-0970-43386 E02-097 1-43387 E02-0971-43388 E02-0971-43389 E02-0971-43390 E02-0971-43391 E02-0971-43392 E02-0971-43393 8/28/2002 8/30/2002 8/30/2002 8/30/2002 8/3012002 8/30/2002 8/30/2002 a,130!2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 8/30/2002 9/6/2002 9/6/2002 9/6/2002 9/6/2002 9/6/2002 9/20/2002 9/20/2002 9/20/2002 9f 2012002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 WT-BLK-6 fE2-1 TE2-2 PFBS-TE2-I PFBS-TE2-2 PFOS-TE2-I PFOS-TE2-2 TE2-BLK WT-BT-TE2 WT-DT-TE2 WT-RLK-TE2 -TE2X-I , -TE2X-2 -TEZX-BLK kI'BS-TE2X-1 PFBS-TE2X-2 PFBS-TE2X-BLK PFOS-TE2X-1 PFOS-TE2X-2 PFOS-TE2X-ELK NHB-I NMB-2 NIIB-BLK WT-BT-NHB WT-BLK-"B PFBS-AIR-TE3-1 P FBS-AI R-TE3-2 TE3-EX-R- 1 TE3-EX-R-2 TE3-EX-V-1 TE3-EX-V-2 PFBS-HE-TE3-1 PFBS-HE-TE3-2 TE3-EX-R-3 TE3-EX-R-4 TE3-EX-V-3 TE3-EX-V-4 WT-BT-TE3-PFBS WT-DT-TE3-PFBS WT-BLK-TE3-PFB S PFBS-BLK-TE3 TE3-EX-BLK-I 5.7.1 5.7.2 5.7.2 5.1.2 5.7.2 5.1.2 5.7.2 5.1.2 5.7 :2 5.1.2 5.7.2 5.7.2 5.7.2 5.7.2 5.7.2 5.1.2 5.7.2 5.1.2 5.7.2 5.1.2 5.7.3 5.7.3 5.7.3 5.1.3 5.1.3 5.7.3 5.7.3 5.7.3 5.1.3 5.1.3 5.1.3 5.7.3 5.7.3 5.7.3 5.1.3 5.7.3 5.7.3 Wipe Test Blank 1st Transfer Efficiency 1st PUF 2nd PUT ~ 2nd Transfer Efficiency 2nd Transfer Efficiency 1st PUF PFBS 2nd Transfer Efficiency 2nd PUF PFBS 2nd Transfer Efficiency 1st PUF PFOS 2nd Transfer Efficiency 2nd PUF PFOS 2nd Transfer Efficiency PUF Blank for 2nd Transfer Efficiency Wipe Test Bench top 2nd Transfer Efficiency Wipe Test Desktop 2nd Transfer Efficiency Wipe Ttst Blank 2nd Transfer Efficiency 1st extraction 2nd Transfer Efficiency 2nd extractior- 2nd Transfer Efficiency Blank extraction- 2nd Transfer Efficiency 1st extraction PFBS 2nd Transfer Efficiency 2nd extraction PFBS 2nd Transfer Efficiency Blank extraction PFBS 2nd Transfer Efficiency 1st extraction PFOS 2nd Transfer Efficiency 2nd extraction PFOS 2nd Transfer Efficiency Blank extraction PFOS 2nd Transfer Efficiency 1st extraction for non-heated blank 2nd extraction for non-heated blank Extraction blank for non-heated blank Wipe test on bench top after non-heated blank Wipe test blank after non-heated blank 1st PUF for PFBS in air 3rd Transfer Efficiency 2nd PUF for PFBS in air 3rd Transfer Efficiency 1st Extraction of Reactor and Transfer line for 3rd Transfer Efficiency of PFBS in air 2nd Extraction of Reactor and Transfer line far 3rd Transfer Efficiency of PFBS in air 1st Extraction of Valve & Short Transfer line for 3rd Transfer Efficiency of PFBS in air 2nd Extraction of Valve & Short Transfer line for 3rd Transfer Efficiency of PFBS in air 1st PUF for PFBS in He 3rd Transfer Efficiency 2nd PUF for PFBS in He 3rd Transfer Efficiency 1st Extraction of Reactor and Transfer line for 3rd Transfer Efficiency of PFBS in He 2nd Extraction of Reactor and Transfer line for 3rd Transfer Efficiency of PFBS in He 1st Extraction of Valve & Short Transfer line for 3rd Transfer Efficiency of PFBS in He 2nd Extraction of Valve & Short Transfer line for 3rd Transfer Efficiency of PFBS in He Wipe Test Bench top PFBS 3rd Transfer Efficiency Wipe Test Desktop PFBS 3rd Transfer Efficiency Wipe Test Blank PFBS 3rd Transfer Efficiency PUF Blank for PFBS in air 3rd Transfer Efficiency 1st Blank extraction for 3rd Transfer Efficiency I Spreadsheet linking UDRl Thermal Testing and 3M Analytical Results EO2-0969-4337 1 E02-0969-43372 E02-0969-43373 EQ2-0969-43374 E02-0969-43375 E02-0969-43376 E02-0968-43360 E02-0968-4336 1 . E02-0968-43362 E02-0968-43363 E02-0968-43364 E02-0968-43365 E02-0968-43366 E02-0968-43367 E02-0968-43368 E02-0968-43369 E02-0968-43370 9/20/2002 9/20/2002 9/20/2002 9/2012002 9/2012002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 9/20/2002 912012002 9/20/2002 9/20/2002 9/20/2002 9/2012002 9/20/2002 9/20/2002 PFOS-AIR-TE3-1 PFOS-AIR-TE3-2 TE3-EX-PFOS-R-1 TE3-EX-PFOS-R-2 TE3-EX-PFOS-V-I TE3-EX-PFOS-V-2 PFOS-HE-TE3-I PFOS-HE-TE3-2 TE3-EX-PFOS-R-3 TE3-EX-PFOS-R-4 TE3-EX-PFOS-V-3 TE3-EX-PFOS-V-4, TE3-EX-BLK-2 WT-BT-TE3-PFOS WT-DT-TE3-PFOS WT-BLK-TE3-PFOS PFOS-BLK-TE3 * conesponds to section number in final report 5.1.3 5.7.3 5.7.3 5.1.3 5.7.3 5.7.3 5.7.3 5.7.3 5.1.3 5.1.3 5.7.3 5.7.3 5.7.3 5.7.3 5.7.3 5.1.3 5.13 1st PUF for PFOS in air 3rd Transfer Efficiency 2nd PUF for PFOS in air 3rd Transfer Efficiency 1st Extraction of Reactor and Transfer line for 3rd Transfer Efficiency of PFOS in air 2nd Extraction of Reactor and Transfer line for 3rd Transfer Efficiency of PFOS in air 1st Extraction of Valve & Short Transfer line for 3rd Transfer Efficiency of PFOS in air 2nd Extraction of Valve 8:Short Transfer line for 3rd Transfer Efficiency of PFBS in air 1st PUF for PFOS in We 3rd Transfer Efficiency 2nd PUF for PFOS in Hc 3rd Transfer Efficiency1st Extraction of Reactor and Transfer line for 3rd Transfer Efficiency of PFOS in He 2nd Extraction of Reactor and Transfer line for 3rd Transfer Efficiency of PFOS in He 1st Extraction of Valve 8:Short Transfer line for 3rd Transfer Eficiency of PFOS in Ile 2nd Extraction of Valve & Short Transfer line for 3rd Transfer Efficiency of PFOS in He 2nd Blank extraction for 3rd Transfer Efficiency Wipe Test Bench top PFOS 3rd Transfer Efficiency Wipe Test Desktop PFOS 3rd Transfer Efticiency Wipe Test Blank PFOS 3id Transfer Efficiency PUF Blank for PFOS in air 3rd Transfer Efficiency