Document G3R8yxMbZRO7jkjVb9bY8rgx

AR226-2713 35 AR226-2713 UDR-TR-2004-00025 FINAL REPORT Laboratory-Scale Thermal Degradation ofFluorocarbon Materials July 2004 Final Report - July 6,2004 Laboratory-Scale Thermal Degradation ofFluorocarbon Materials Takahiro Yamada, Ph.D. Philip H. Taylor, Ph.D. Environmental Engineering Group Energy and Environmental Engineering Division University of Dayton Research Institute 300 College Park Dayton, OH 45469-0114 Prepared for: Robert C. Buck, Ph.D. DuPont Chemical Solutions Enterprise Barley Mill Plaza 23/1324 Lancaster Pike and Route 141 Wilmington, DE 19880-0023 TABLE OF CONTENTS SECTION_________________________________________PAGE . List of Figures iv List of Tables viii Abbreviations x Executive Summary xi 1 Introduction 1 2 Experimental Protocol 2 2.1 Introduction/Objectives 2 2.2 Overall Experimental Approach 2 2.3 Samples 2 2.3.1 Atomic Composition 2 2.3.2 Thermogravimetric Analysis (TGA) Results 3 2.4 In-line GC/MS Analysis and 99.9% Destruction Temperature Determination 4 2.4.1 Experimental Setup and Procedure of In-line GC/MS Analysis of Combustion Byproducts 4 2.4.2 ATRS Experimental Conditions 6 2.4.3 GC/MS Chemical Calibration 8 2.4.4 GC/MC Determination of Major Ions for Construction of Thermal Decomposition Profile 10 2.5 Treated and Untreated Articles: PFOA, Fluoride, and Chloride Analysis at1000C 14 2.6 Treated and Untreated Articles: Off-line GC/MS Analysis of Volatile Organic Compound (VOC) Analysis at 1000C 15 2.7 Treated and Untreated Articles: CO and C02 Analyses at 1000C 16 2.8 XPS Analysis of Pyroprobe Cartridge 17 2.9 Telomer B Alcohol Combustion: GC/MS Analysis 17 2.10 Perfluorooctanoic Acid (PFOA) Absorption Study 18 2.10.1 PFOA Absorption Study 18 TABLE OF CONTENTS (continued) SECTION 2.11 PFOA Transport Studies 2.11.1 PFOA Transport Study 2.11.2 PFOA Transport Study - Aqueous Sampling Gas Phase Sampling 2.12 PFOA Calibration Curve and Detection Limit Study 2.13 Test Matrix and Quality Assurance Procedures 2.14 Quality Assurance Narrative Statement 3 Experimental Results , 3.1 In-line GC/MS Analysis and 99.9% Destruction Temperature Determination 3.1.1 Untreated Article 3.1.2 Treated Article 3.1.3 Fluorinated Acrylic Polymer 3.2 Treated and Untreated Articles: PFOA, Fluoride, and Chloride Analyses at 1000C 3.3 SiF4 Analysis from Fluorinated Acrylic Polymer Combustion 3.4 Treated Article Gasification: XPS Analysis ofPyroprobe Cartridge 3.5 Telomer B Alcohol Combustion GC/MS Analysis 3.6 Treated & Untreated Articles: Off-line GC/MS VOC Analysis at 1000C 3.7 Treated & Untreated Articles: CO and CO; Analyses at 1000C 3.8. PFOA Absorption Study 3.8.1 PFOA in Aqueous Solution 3.9 PFOA Transport Studies 3.9.1 PFOA Transport Study - Aqueous Sampling 3.9.2 PFOA Transport Study - Gas phase Sampling 3.10 PFOA Calibration curve and Detection Limit Studies 3.11 PFOA Analysis from Combustion Tests of the Treated & Untreated Articles and the Fluorinated Acrylic polymer Using In-line GC/MS Analysis 11 TABLE OF CONTENTS (continued) SECTION 4 Discussion 5 Conclusions 6 References Appendix A Experimental Condition (Temperature, Flow Rate, and Pressure) and Total Ion Chromatogram for DuPont Sample In-line GC/MS Analysis Appendix B Experimental Condition (Temperature and Flow Rate) and Results for PFOA, F, and Cl Aqueous Solution Analysis Appendix C Experimental Condition (Temperature, Flow Rate, and Pressure) and Total Ion Chromatogram for Telomer In-line GC/MS Analysis Appendix D Experimental Condition (Temperature and Flow Rate) for VOC, CO and C02 Off-line GC/MS Analysis Appendix E Experimental Condition (Temperature and Flow Rate) for PFOA Transport Efficiency Test and System Steam Extraction Appendix F Experimental Condition (Temperature and Flow Rate) for PFOA Calibration and Detection Limit Study Appendix G General Description ofATRS Standard Procedure, Wickbold Torch Methods for Total Fluorine, and QuikChemMethod for Fluoride and Chloride in Water 111 LIST OF FIGURES FIGURE 1.1 Fluorotelomer-based Polymer Description 2.1 TGA Result for Untreated Article 2.2 TGA Result for Treated Article 2.3 TGA Result for Fluorinated Acrylic Polymer 2.4 General Schematic of the Advanced Thermal Reactor System (ATRS) 2.5 Position of Thermocouples in Reactor Assembly 2.6 CFsH Calibration Curve 2.7 CiFg Calibration Curve 2.8 CgFig Calibration Curve 2.9 Total Ion Chromatogram and Peak Identification for Untreated Article at 600C 2.10 Mass Spectra at 13.4 min for Untreated Article at 600C 2.11 Total Ion Chromatogram Peak Identification for Treated Article at 600C 2.12 Mass Spectra at 13.5 min for Treated Article at 600C 2.13 Total Ion Chromatogram and Peak Identification for Fluorinated Acrylic Polymerat 600C 2.14 Extracted Ions (69 and 77) for Fluorinated Acrylic Polymer at 2.16 Off-Line Aqueous Sampling for Fluoride and PFOA CO Calibration Curve 600C 2.15 2.17 COz Calibration Curve 2.18 Schematicfor PFOA Absorption Test 2.19 Schematic for PFOA Steam Extraction of the ATRS 2.20 Schematic of PFOA TransportEfficiency Test Through the ATRS Schematic of PFOA Direct Injection to GC Injection Port System 2.21 LIST OF FIGURES (continued) FIGURE__________________________________________PAGE 3.1 Untreated Article Destruction Profile Normalized by Sample Mass 26 3.2 Extracted Ion 122 (benzoic acid) for Untreated Article at 600, 650, 700and725C 26 3.3 Extracted Ion 149 (terephthalic acid derivative) for Untreated Article at 600, 650,700,and725C 27 3.4 Extracted Ion 122 (benzoic acid) and 149 (terephthalic acid derivative) for Untreated Article Combustion at 1000C 27 3.5 Treated Article Destruction Profile Normalized by Sample Mass 28 3.6 Extracted Ion 122 (benzoic acid) for Treated Article at 600,650, 700, and 725C 29 3.7 Extracted 149 (terephthalic acid derivative) for Treated Article at 600, 650, 700, and 725C 29 3.8 Extracted Ion Count 69 ('CFs) for Treated Article at 600, 650,700, and725C 30 3.9 Extracted Ion 119 (-CFzCFa) for Treated Article at 600,650,700, and 725C 30 3.10 Extracted Ion 131 ('CFzCF^Fz) for Treated Article at 600,650,700, and 725C 31 3.11 Extracted Ion Count 122 (benzoic acid) and 149 (terephthalic acid derivative) for Treated Article Combustion at 1000C 31 3.12 Fluorinated Acrylic Polymer Destruction Profile 33 3.13 Extracted Ion 69 (*CFa) for Fluorinated Acrylic Polymer at 600,650, 700,750, and 800C 33 3.14 Extracted Ion 69 ('CFa) for Fluorinated Acrylic Polymer at 850, 900,950, and 1000C 34 3.15 Extracted Ion 77 ('CFzCH^Hz) for Fluorinated Acrylic Polymer at 600,650,700, 750, and 800C 34 3.16 Extracted Ion 77 ('CFzCH^CHz) for Fluorinated Acrylic Polymer at 850, 900,950 and 1000C 35 v LIST OF FIGURES (continued) FIGURE__________________________________________PAGE 3.17 Extracted Ion 119(*CF2CF3) for Fluorinated Acrylic Polymer at 600, 650, 700,750, and 800C 35 3.18 Extracted Ion 119('CF2CF3) for Fluorinated Acrylic Polymer at 800, 850, 900, 950, and 1000C 36 3.19 Extracted Ion 131(-CF2CF=CF2) for Fluorinated Acrylic Polymer at 600,650, 700, 750, and 800C 36 3.20 Extracted Ion 169(*CF2CF2CF3) for Fluorinated Acrylic Polymer at 600, 650, 700,750,and800C 37 3.21 Extracted Ion 85 (SiFa) for Untreated Article at 600,650,700, 725, and750C 38 3.22 Extracted Ion 85 (SiFs) for Treated Article at 600, 650, 700,725, and 750C 39 3.23 Extracted Ion 85 (SiFa) for Fluorinated Acrylic Polymer at 600, 650, 700, 750, and 800C 39 3.24 Extracted Ion 85 (SiFa) for Fluorinated Acrylic Polymer at 850, 900, 950 and 1000C 40 3.25 Temperature vs. Integrated Normalized Peak Area of Ion 85 (SiFs) 41 3.26 XPS Result for Blank Cartridge 42 3.27 XPS Result for Sample Cartridge (First Analysis) 42 3.28 XPS Result for Sample Cartridge (Second Analysis) 43 3.29 Extracted Ion 77 (-CFzCIK^) for Telomer Alcohol Combustion at200and600C 44 3.30 VOC Analysis for Untreated Article Combustion at 1000C 45 3.31 VOC Analysis for Treated Article Combustion at 1000C 45 3.32 Total Ion Chromatograms Obtained from PFOA Transport Test .Through ATRS 50 3.33 Total Ion Chromatograms Obtained from Direct Injection 51 VI LIST OF FIGURES (continued) FIGURE__________________________________________PAGE 3.34 PFOA Calibration Curve 52 3.35 PFOA Extracted Ion m^CFzCF^Fa) for 1.10,5.50,10.16,50.80, and 100.40 p,g 53 3.36 PFOA Reference Spectra Obtained from NIST129K Library 54 3.37 PFOA Full Scan Spectra for 100.40,50.80,10.16, 5.50, and 1.10 p.g Injection 55 3.38 PFOA Full Scan Spectra at 16.2 and 16.6 min for 100.40 p,g Injection 56 3.39 Extracted Ion 131 for Treated Article from 14 to 18 min Retention Time 57 at 600,650, 700,725, and 1000C 3.40 Extracted Ion 131 for Untreated Article from 14 to 18 min Retention Time 57 at 600, 650, 700,725, and 1000C 3.41 Extracted Ion 131 for Fluorinated Acrylic Polymer from 14 to 18 min 58 Retention Time at 600,650,700,750, and 800C 3.42 Extracted Ion 131 for Fluorinated Acrylic Polymer from 14 to 18 min 58 Retention Time at 850, 900,950, and 1000C 3.43 Spectra for the Peaks 16.35,17.10,17.70, and 17.95 min at 600C in 59 Figure 3.41 vn LIST OF TABLES TABLE 2.1 Weight Composition (%) ofDuPont Samples 2.2 Atomic Composition ofDuPont Samples 2.3 Pyroprobe Gasification Temperature (C) 2.4 Linear Fit Equations for Standard Calibration Curve and Detection Limits 2.5 Linear Fit Equations for CO and C02 Calibration Curves 2.6 Telomer B Alcohol Characterization 2.7 Solution Concentration (PFOA in Methanol) and Volume Required to Produce 1,5,10,50, and 100 |Xg injection into ATRS 3.1 Major Ion Counts of the Untreated Article 3.2 Major Ion Counts of the Treated Article 3.3 Major Ion Counts of Fluorinated Acrylic Polymers 3.4 Gasified Sample Masses 3.5 Integrated Peak Area of Ion 85 (SiFs) Normalized by Mass for the Fluorinated Acrylic polymer 3.6 Approximate Atom % Surface Compositions 3.7 Sample Gasified and Normalized Integrated Peak Area of Ion 77 (CF2CH=CH2) 3.8 Net Mass of Sample Gasified 3.9 Flow Rate Monitored for CO and CO; Analysis 3.10 Carbon Recovery Rate for Untreated and Treated Article Combustion at1000C 3.11 3.12 3.13 3.14 Summary of PFOA Absorption Tests PFOA Recovery as Fluorine (Wickbold Torch Analysis) Summary of PFOA Transport Studies Wichbold Torch Determination of Total Fluorine vni TABLE LIST OF TABLES (continued) 3.15 3.16 3.17 3.18 PFOA Recovered from Steam Extraction PFOA Recovered from Pyroprobe Rinsing PFOA Peak Area PFOA Mass vs. Corresponding Peak Area IX LIST OF ABBREVIATIONS Abbreviation ATRS d EPA Eqn ft GC/MS He HPLC i.d. LOD LOQ min NIST o.d. PFOA QA QAPP S/N sec SOP TCD TGA UDRI VOC XPS Explanation Advanced Thermal Reactor System Diameter Environmental Protection Agency Equation foot, feet Gas Chromatography / Mass Spectrometry Helium High Performance Liquid Chromatography Internal Diameter Limit of Detection Limit of Quantitation minute(s) National Institute of Standards and Technology Outer Diameter Perfluorooctanoic acid Quality Assurance Quality Assurance Program Plans Signal to Noise second(s) Standard Operating Protocol Thermal Conductivity Detector Thermogravimetric Analysis University of Dayton Research Institute Volatile Organic Carbon X-ray Photoelectron Spectroscopy Executive Summary This study reports the first known studies to investigate the thermal degradation of a polyester/cellulose fabric substrate ("article") treated with a fluorotelomer-based acrylic polymer under laboratory conditions conservatively representing typical municipal incineration conditions of time, temperature, and excess air level. The studies emulated typical municipal waste incinerator combustion conditions with an average temperature of 1000C or greater over approximately 2 sec residence time. The results demonstrate that the polyester/cellulose fabric treated with a fluorotelomer-based acrylic polymer is destroyed and no detectable amount ofPFOA is formed under typical municipal incineration conditions. Therefore, textiles and paper treated with such a fluorotelomer-based acrylic polymer disposed of in municipal waste and incinerated are expected to be destroyed and not be a significant source ofperfluorooctanoic acid (PFOA) in the environment. Fluorotelomer-based acrylic polymers (Banks, et al., 1994; Kissa, 2001) are applied to the surface of textiles and paper to impart oil and water repellency to them. Textile fabrics are made from natural (i.e. cotton, wool) and synthetic (i.e. poly-ester, -amide, -propylene) fibers and their blends. Paper is comprised mainly ofcellulosic fiber, principally wood pulp. Some paper may also contain fibers such as cotton. The environmental fate ofperiluorinated chemicals, such as fluorotelomer-based substances is of growing interest (Hekster, et al., 2003; Schultz, et al., 2003; Dimitrov, et al., 2004; Stock, et al., 2004). Textiles and paper are often incinerated when they are disposed. No information regarding emissions from incineration of textiles or paper treated with fluorotelomer-based products is available. This study reports the first known studies to investigate the thermal degradation of a polyester/cellulose fabric substrate ("article") treated with a fluorotelomer-based acrylic polymer under laboratory conditions conservatively representing typical municipal incineration conditions of time, temperature, and excess air level. The treated article is reasonably expected to be present in municipal waste as discarded textile or paper. Therefore, the principal focus of this work was to determine the environmental fate of the treated article when it is incinerated. The test substrate was a fabric comprised of a blend of polyester (ethylene glycol, terephthalic acid) and cellulose fibers. Fabrics with and without a fluorotelomer-based acrylic polymer treatment were tested. The substrate was chosen to be representative of both synthetic and natural fibers that are used in textiles and cellulosic fibers (cotton, wood pulp) used in paper. Fluorotelomer-based acrylic polymers are most commonly used for treating textiles and paper. The fluorotelomer based polymer used was a proprietary DuPont formulation whose composition has been generally described. (US 4742140 and US 5344903) The test protocols used were similar to those developed for recent testing offluorinated materials (Yamada and Taylor, 2003; Graham, 2002). Thermogravimetric analysis was used to define the gasification conditions. Thermal experiments were then conducted at non-flame reactor temperatures from 600 to 1000C for a mean, gas-phase residence time of 2.0 sec. 85% excess air was used for all experiments. The studies emulated typical municipal waste incinerator combustion conditions with an average temperature of 1000C or greater over approximately 2 sec residence time (Giraud, 2004). Combustion tests for the treated article, the untreated article, and the fluorotelomer-based acrylic polymer were completed. The following objectives were addressed: 1) determination of the temperature for 99.9% conversion, 2) determination of major products of incomplete combustion at 1000C for the treated and untreated article, 3) determination of carbon mass balances at 1000C for the treated and untreated article, 4) determination of the concentration of PFOA in the effluent from all tests, and 5) XI determination of the concentration offluoride ion in the 1000C tests for the treated and untreated articles. The temperature for 99.9% destruction of the treated and untreated articles was 725C. This temperature regime (700-750C) for 99.9% conversion is consistent with the results of prior tests of hydrocarbonbased materials using UDRI thermal instrumentation systems (Dellinger, et al. 1984; Dellinger, 1989; Taylor, et al. 1990). The temperature for 99.9% destruction ^99.9) of the fluorotelomer-based acrylic polymer was 1000C. The T99.9 value for the fluorotelomer-based acrylic polymer was slightly higher than that measured for other fluorinated materials using the same experimental apparatus (Graham, 2002). The difference may be related to the levels of excess air present in the respective combustion tests. Combustion tests with the fluorotelomer-based acrylic polymer used 85% excess air, while previous tests with other fluorinated materials employed considerably higher excess air levels. Excellent carbon mass balances were obtained from the combustion tests of the untreated and treated articles (101.9 and 103.6%, respectively) at 1000C. The only product of incomplete combustion that was observed under these conditions was carbon monoxide. Fluorinated organic byproducts were not observed via GC/MS in the combustion tests of the treated and untreated articles. In-line GC/MS was employed to determine the presence of heavier, less volatile fluorinated byproducts. No peaks were detected. Additionally, off-line GC/MS was employed to determine the presence of volatile fluorinated byproducts in the gas exhaust from the 1000C tests of the treated and untreated articles. No peaks were detected. Combustion tests of the fluorotelomer-based acrylic polymer were conducted to facilitate interpretation of the treated article combustion results. At 1000C, 99.9% destruction of the polymer was observed. Based upon this result, the fluorotelomer-based acrylic polymer would be destroyed under typical municipal incinerator conditions. Analysis of the reactor effluent from additional combustion tests of the fluorotelomer-based acrylic polymer indicated the formation of a variety of compounds at temperatures below 1000C. Many of these compounds could not be identified using either the NIST mass spectral library or manual mass spectral interpretation. As a result, a limited number of combustion experiments were conducted on the Telomer B Alcohol raw material to try to determine me origin of these unidentifiable peaks. The experiments confirmed that selected ions were the same for the polymer and alcohol indicating their origin was indeed from the telomer functionality. Potential volatile combustion byproducts from the combustion of the fluorotelomer-based acrylic polymer were not studied. Of additional interest was to determine whether PFOA was formed as a result of combustion of the treated article to determine if incineration of treated articles may be a source of PFOA in the environment. Analysis for PFOA in combustion tests of the treated and untreated article at 1000C using both HPLC/MS/MS and in-line GC/MS were conducted. No detectable level of PFOA was determined. It can therefore be concluded that under typical municipal waste incineration conditions no significant quantity of PFOA would be formed from the incineration of a textile or paper substrate treated with a fluorotelomer-based acrylic polymer. In addition, transport efficiency tests for PFOA using aqueous sampling (followed by HPLC/MS/MS) and gas-phase sampling (followed by in-line GC/MS analysis) were conducted. Aqueous sampling with HPLC/MS/MS analysis produced transport efficiencies of less than 20% using ATRS reactor and transfer line temperatures of 170C. Alternatively, in-line GC/MS tests using ATRS reactor and transfer line temperatures of235C produced transport efficiencies of greater than 70% (determined by dividing the ATRS PFOA response by the response obtained by direct injection of PFOA into the gas chromatograph). A plausible PFOA loss mechanism during the aqueous sampling transport tests may have involved absorption onto the unheated silicone transfer line tubing between the ATRS vent and the bubblers (see Y11 Fig. 2.15). The basis for this hypothesis was the strong interaction observed between PFOA and the DB5 capillary column support (phenyl-methyl siloxane) during the in-line GC/MS analysis and the evidence for PFOA condensation in the absorption and transport tests. Cryogenic temperatures were not required to trap PFOA. PFOA was effectively trapped using this column at a temperature of40C, thus indicating a strong interaction between the capillary column support and the analyte of interest. Based upon the combustion product analyses, it was clear that carbon-fluorine bonds were severed at 1000C. This would result in the formation of fluorine atoms [F]. Fluorine atoms are highly reactive and would be expected to form hydrogen fluoride [HF] by reaction with hydrogen available in the combustion matrix. Analysis for fluoride ion (indicative ofHF formation) in combustion tests of the treated and untreated article at 1000C by trapping the gaseous effluent in aqueous bubblers followed by sampling and ion chromatography indicated fluoride [F'] below analytical detection limits. Subsequent examination of different sections of the experimental apparatus provided clues as to what happened to the fluoride generated from combustion. XPS analysis of the pyroprobe cartridges used to contain the test sample did not indicate the presence of fluorine on the surface. Removal and visible examination of the high-temperature reactor did, however, indicate significant etching of the reactor surface, most notably downstream of the midpoint of the reactor. This is very likely due to the reaction of hydrogen fluoride (HF) with the silica groups (SiOz, SiOH) of the reactor surface. Strong evidence confirming this interpretation was obtained from in-line GC/MS total ion chromatograms from the combustion of the fluorotelomer-based acrylic polymer at temperatures between 600 and 1000C. Silicon tetrafluoride (SiF4) was observed as a byproduct in these tests. The signal response for SiF4 showed a near-linear increase with increasing temperature, consistent with increasing yields ofHF at higher temperature arising from carbon-fluorine bond breaking. SiF4 has been observed in previous combustion tests of highly fluorinated materials using high-temperature fused silica reactors (Yamada and Taylor, 2003, Graham, 2002). To summarize, these results demonstrate that the polyester/cellulose fabric treated with a fluorotelomer- based acrylic polymer is destroyed and no detectable amount of PFOA is formed under typical municipal incineration conditions. Therefore, textiles and paper treated with such a fluorotelomer-based acrylic polymer disposed of in municipal waste and incinerated are expected to be destroyed and not be a significant source of PFOA in the environment. xm 1. Introduction Fluorotelomer-based acrylic polymers (Banks, et al., 1994; Kissa, 2001) are applied to the surface of textiles and paper to impart oil and water repellency to them. Textile fabrics are made from natural (i.e. cotton, wool) and synthetic (i.e. poly-ester, -amide, -propylene) fibers and their blends. Paper is comprised mainly ofcellulosic fiber, principally wood pulp. Some paper may also contain fibers such as cotton. The environmental fate ofperfluorinated chemicals, such as fluorotelomer-based substances is of growing interest (Hekster, et al., 2003; Schultz, et al., 2003; Dimitrov, et al., 2004; Stock, et al., 2004). Textiles and paper are often incinerated when they are disposed. No information regarding emission from incineration of textiles or paper treated with fluorotelomer-based products is available. This study reports the first known studies to investigate the thermal degradation of a polyester/cellulose fabric substrate ("article") treated with a fluorotelomer-based acrylic polymer under laboratory conditions conservatively representing typical municipal incineration conditions of time, temperature, and excess air level. The treated article is reasonably expected to be present in municipal waste as discarded textile or paper. Therefore, the principal focus of this work was to determine the environmental fate of the treated article when it is incinerated. The test substrate was a fabric comprised of a blend of polyester (ethylene glycol, terephthalic acid) and cellulose fibers. Fabrics with and without a fluorotelomer-based acrylic polymer treatment were tested. The substrate was chosen to be representative of both synthetic and natural fibers that are used in textiles and cellulosic fibers (cotton, wood pulp) used in paper. Fluorotelomer-based acrylic polymers are most commonly used for treating textiles and paper. The fluorotelomer based polymer used was a proprietary DuPont formulation whose composition has been generally described. (US 4742140 and US 5344903) "Fluorotelomer" Functionality F- (Cf--2CF-z^)niC-Hin2CuM2n0 HtorCHa) I I Polymerize ----------------------------------^ with other acrylic monomers Fluorotelomer-based Acrylate Polymer Fluorotelomer Acrylic Monomer Figure 1.1 Fluorotelomer-based Polymer Description. 2. Experimental Protocol 2.1 Introduction/Objectives The incineration study was conducted for three samples provided by DuPont: a fluorinated acrylic polymer, untreated articles, and articles treated with the polymer. One major goal of the work was to determine the thermal stability profile of each sample from the sample gasification temperature to a temperature of 99.9% conversion at 50C increments. Quantitative analysis was also performed for the combustion byproducts CO, CO^, CFaH, CA, and CgFig at a specified level of conversion. Fluoride and chloride ion were also sampled in aqueous solution and determined. Perfluorooctanoic acid (PFOA) was also sampled using two independent methods and determined. The advanced thermal reactor system (ATRS) with various sampling and analytical techniques was used for the study. The ATRS has been widely used for incineration studies and has been described elsewhere (see Appendix G). The detailed experimental setup, test procedures, analytical methods, and a quality assurance (QA) statement will be discussed in this section. 2.2 Overall Experimental Approach Sample gasification behavior was investigated using thermogravimetric analysis (TGA) and results are shown in Section 2.4. TGA results were used to determine the sample gasification temperature. The sample materials were fed to the ATRS to incinerate them and analyze their combustion byproducts. An in-line gas chromatography/mass spectrometry (GC/MS) system was used to generate the thermal decomposition profile of each sample and identify major combustion byproducts. Quantitative CO, COz, and volatile organic carbon (VOC) determination were performed in separate experiments by collecting effluent from the exhaust line and using off-line GC/thermal conductivity detector (TCD) and GC/MS systems. PFOA, fluoride, and chloride samples were collected in aqueous solution and determined by HPLC/MS/MS and ion chromatagraphy using Exygen, me., an analytical laboratory selected by DuPont. 2.3 Samples 2 J.I Atomic Composition Tables 2.1 and 2.2 show the weight and atomic compositions of the samples as provided by DuPont. ______Table 2.1 Weight Composition (%) of DuPont Samples.______ H F 0 Cl N _______Sample_________C Untreated article 49.1 5.1 45.8 Treated article 49.7 4.9 0.2 45.2 Fluorinated acrylic polymer____40.5 4.0 35.5 6.5 13.1 0.3 ________Table 2.2 Atomic Composition of DuPont Samples._______ H F 0 Cl N ______Sample________C Untreated article 0.340 0.422 0.238 Treated article 0.350 0.410 0.001* 0.239 Fluorinated acrylic polymer 0.334 0.401 0.185 0.040 0.037 0.002* ''' Number is neglected for the stoichiometric reaction shown below. The untreated and treated articles were prepared using a one-hole punch with a diameter of 6 mm (d = 6 mm) purchased specifically for this project. The fluorinated acrylic polymer was prepared using our hand-made metal template which gives "hockey-puck" shaped polymer samples (d " 1.6 mm). Relatively uniform dimensions and mass were obtained using these approaches for each sample. Based on the atomic composition, the stoichiometric oxidation reaction can be written as follows. * Untreated article Co.34Ho.420o.24 + 0.3902 -> 0.34C02 + 0.21H20 -- (Equation 1) * Treated article Co.35Ho.4iOo.24 + 0.390z -> 0.35C02 + 0.2 IHzO ----- (Equation 2) * Fluorinated acrylic polymer Coj3Ho.4oOo.o4Fo.i9Clo.o4 + 0.3502 -> 0.33C02 + 0.19HF + 0.04HC1 + 0.085H20 (Equation 3) The amount of oxygen necessary for complete oxidation was used for the gasification time calculation, which is explained in Section 2.4.2. 2.3.2 Thermogravimetric Analysis (TGA) Results A TGA study was conducted prior to development of the test protocol in order to establish the temperature for complete gasification of each test material. TGA was performed in flowing air using a CSI Model 1050 TGA (Stone-Premco Analytical Instruments) programmed at a heating rate of25C/min from room temperature to the point where there is no further weight loss. Approximately 4 mg of sample was gasified with air and the weight % remaining was recorded as function of temperature. Figures 2.1 and 2.2 show TGA results for untreated and treated articles, respectively. Similar gasification behavior was observed for both samples. Gasification started at 380 and 350C and ended at 600 and 550C for untreated and treated articles, respectively. Weight remaining after gasification was 7 and 2.5% for untreated and treated articles, respectively. Figure 2.3 shows TGA results for the fluormated acrylic polymer. The gasification of the polymer started at around 100C. Continuous weight loss was observed until 600C, where nearly 100% gasification was observed. 100-1 I0) a EC. g 4^ C01. 40 S -i--------r 0 100 200 300 400 500 Temperature, C Figure 2.1 TGA Result for Untreated Article. 10(M -^ 80- I 60- 5? 40- o 20- -T 100 200 300 400 500 600 Temperature, C Figure 2.2 TGA Result for Treated Article. . 0) 5 u-l--------i--------i--------i--------r 0 100 200 300 400 500 600 Temperature, C Figure 2.3 TGA Result for Fluorinated Acrylic Polymer. 2.4 In-line GC/MS Analysis and 99.9% Destruction Temperature Determination 2.4.1 Experimental Setup and Procedure for In-line GC/MS Analysis of Combustion Byproducts Figure 2.4 shows the ATRS, which consists of a sample inlet, reactor, cold trap, and in-line GC/MS system. The sample was placed into a sample cartridge (2 x 2.5 mm (i.d.xo.d.), 12.5 mm length quartz capillary tube, CDS Analytical Inc., Oxford, PA) and the cartridge was inserted into a pyroprobe (CDS- 2000). The pyroprobe was placed into Inlet 1 and gasified with synthetic air (21% 0; and 79% Nz, Airgas me.) at 85% excess air to conservatively represent municipal waste combustion conditions (Giraud, 2004). All experiments were performed using synthetic air. The reactor dimensions are 4 x 6 mm (Ld.xo.cl.) with an effective length of 15 cm. The gas residence time was 2.0 sec. All transfer lines were maintained at approximately 300C for all experiments. Figure 2.5 shows thermocouple locations in the reactor assembly. The temperature at these locations was monitored and recorded before and after the incineration test. Inlet 2 for Supplemental Gas Flow Inlet 1 for Pyroprobe & Main Gas Flow Figure 2.4 General Schematic of the Advanced Thermal Reactor System (ATRS). Figure 2.5 Position of Thermocouples in Reactor Assembly. GC/MS Analysis Method The gasified sample was incinerated in the reactor, and the combustion byproducts were condensed in the cold trap maintained at -125C using liquid nitrogen. After combustion was completed, the condensed materials were released when the cold trap was heated to 280C (with ramping of approximately 45C/min) and introduced to the GC/MS system for analysis. An HP5890A/5970B series GC-MS with DB-5 GC capillary column (30 m length, 0.25 mm i.d., 0.25 (l film thickness, Agilent Technologies, me. Folsom, CA) was used for in-line combustion byproduct analysis. The split ratio was 1 to 24. While the condensed materials were released from the cold trap, the materials were cryogenically trapped at the head of the GC column at -60C. Following the cryogenic focusing, the oven temperature was held at 60C for 1 min, then increased to 280C (with ramping of20C/min) and held for 10 min at 280C. The mass scan range was 12 - 450 m/z to allow analysis of a wide range of compounds including water. The actual sample combustion procedure was performed in sequence as follows: 1. Set air flow rate to obtain residence time of 2 sec at the reactor. Two thirds of the flow is introduced to Inlet 1 where the pyroprobe is inserted and one third of the flow is introduced to Inlet 2. 2. Record ATRS inlet flow rates. 3. Set cold trap temperature to -125C using liquid nitrogen. 4. Record temperature at the 7 points shown in Figure 2.4. 5. Insert pyroprobe into Inlet 1. 6. Stabilize the system for 2 min. 7. Start pyroprobe temperature programming. 8. Remove pyroprobe. 9. Sweep entire system with helium (He) for 3 min. 10. Record ATRS inlet flow rates. 11. Record temperature at 7 points shown in Figure 2.5. 12. Set GC column temperature to -60C using liquid nitrogen. 13. Start GC/MS analysis. 14. Heat cold trap to 280C to release condensed materials from the trap and transfer them to GC/MS. 2.4.2 ATRS Experimental Conditions Flow Rate The reactor volume of 1.88 cm3 (0.2 cm i.d., 15 cm effective length) and residence time of 2.0 sec gives a fixed flow rate of 0.94 mL/sec at 25C. This flow rate was corrected with the reactor temperature as shown below: 0.94 mL/sec x 298 / (T + 273) (T: Reactor Temperature in C) ------- (Equation 4) Gasification Temperature and Duration Table 2.3 shows initial and final temperatures of the pyroprobe. Based on the TGA results, the initial and final temperature of the untreated and treated articles were set at 350 and 650C, respectively. Although the TGA results indicated that the final gasification temperature for the untreated article is 50C higher than the treated article, the pyroprobe final gasification temperatures for both materials were set at the same level for consistency and to facilitate comparison of results. The temperatures for both materials were identical for consistency. The initial and final temperatures for the fluorinated acrylic polymer were set at 250 and 650C, respectively. The temperature ramping rates between the initial and final temperatures were varied to adjust gasification time and obtain appropriate stoichiometric conditions as described in more detail below. The temperature of Inlet 1 was set at 300C for the untreated and treated articles and 250C for the fluorinated acrylic polymer. The inlet temperature for the fluorinated acrylic polymer was reduced to prevent significant weight loss during system stabilization after sample insertion and before gasification. __________Table 2.3 Pyroprobe Gasification Temperature (C).__________ _______Sample_________Initial_____Final_____Inlet 1 Temperature Untreated article 350 650 300 Treated article 350 650 300 Fluorinated acrylic polymer_____250______650_________250______ Because the reactor volume and residence time are fixed parameters, the flow rate cannot be changed to set the excess air level. Therefore, the gasification time and amount of sample are the two adjustable parameters to obtain 85% excess air. Since it is not practical with existing equipment to prepare the desired amount of samples with 10 ng precision, the gasification time is the only parameter that can be varied to obtain the desired ratio. The calculation below shows how the gasification time for the fluorinated acrylic polymer was determined. Suppose the weight of the fluorinated acrylic polymer used for combustion at 600C is 2.25 mg. The molecular weight of the hypothetical polymer shown in Eqn 3 is 9.88. The molar amount of polymer in this sample is 2.25/1000(g)/9.88(g/mol) = 2.28 x 10"4moles. From the stoichiometric reaction for the polymer (Eqn 3 in Section 2.3.1), the oxygen required can be calculated as: 2.28 xlO^moIX 0.35 The volume of air (21% oxygen and 79% nitrogen) in units ofmL with 85% excess air (85% x 0.21 = 17.85% excess oxygen) at 1 atm and 298C can be calculated as: [2.28 x lO^mol) x 0.35 x 1.1785 x 0.082 l(atm-'/mol-K) x 298(K) / l(atm)] / 0.21 x 1000(mL/l) = 11.0 mL The flow rate at 600C is 0.94(mL/sec) x 298 (K) / (600 + 273) (K) = 0.32 mL/sec. The gasification time can then be calculated as follows: 11.0 mL/0.32(mL/sec) = 34.4 sec Since the initial and final gasification temperatures for the polymer are 250 and 650C, respectively, as discussed above, the pyroprobe temperature was linearly increased from 250 to 650C with a ramping rate of: (650-250)C/34.4 sec x 60 sec/min = 698C/min The key assumptions are that gasification starts when the pyroprobe temperature programming for the polymer starts (250C) and ends at the final temperature (650C), and sample weight loss is linear with time. 2.4.3 GC/MS Calibration Calibration curves were created for the compounds of interest based on prior work: CFsH (98+%, Lot #: 22912MI, Aldrich, Milwaukee, WI), C+Fg (98% minimum. Lot #: 8B-110, SynQuest Labs., Inc., Alachua, PL), and CgFig (98%, Batch #: 17024MA, Aldrich, Milwaukee, WI). The results are shown in Figures 2.6 through 2.8. The detection limit was determined based on EPA's detection limit criteria for identifying an unknown (EPA Method 8260B, pages 23 - 24). In this analysis, we chose the most abundant ion (target ion) and major ions whose intensities were greater than ca. 20% of the target ion. The detection limit was the lowest concentration that had the target ions and all of major ions whose relative intensity also agreed with the reference spectra within ca. 20%. Calibration and detection limit determination were consistent with prior thermal decomposition studies conducted in this laboratory (Taylor, et al., 1995, 1996,; Tirey, et al., 1990; Wehrmeier, et al., 1998). The following procedure was used to construct each calibration curve. A known amount of each standard was introduced into Inlet 1 in the reactor assembly. All transfer lines and the reactor was heated at 300C. Standards were condensed at the cold trap at -125C, and then transferred to the GC/MS system for analysis. The procedure was exactly the same as in the combustion tests of samples. The major ion from each standard was extracted (69 for CFsH and CgFig, and 131 for C4Fg) and plotted as the function of the injected molar quantity. Figures 2.6 - 2.8 shows calibration curves for CFsH, C<Fg, and CgFig, respectively. The linear fit equation and detection limit for each standard are summarized in Table 2.4. The detection limit improves with molecular size. This is probably due to an increased MS response factor and better peak shape obtained from the DB-5 GC capillary column (30 m length, 0.25 mm i.d., Agilent Technologies, me. Folsom, CA) with increased molecular size. & Injected Quantity (Mol) Figure 2.6 CF3H Calibration Curve. 0 1 10'8 210'8 310"8 410"' Injected Quantity (Mol) Figure 2.7 CiFg CaKbration Curve. 510'8 Injected Quantity (Mol) Figure 2.8 CgFis Calibration Curve. Table 2.4 Linear Fit Equations for Standard Calibration Curves and Detection Limits. Sample Name Linear Fit R Detection Limit CFsH (x: vioi,y: peak area)_______________(mol) x=(y+1.69E6)/2.07E14 0.997 1.01E-8 C4Fg ;c= (y-2.56E5)/1.38E15 0.999 1.01E-9 CgFig_________^=(y-3.94E5)/6.32E15_______0.999 2.34E-10 2.4.4 GC/MS Determination of Major Ions for Construction of Thermal Decomposition Profile Preliminary tests were conducted to identify the chemical species associated with the major peaks and determine major ions that could be used for construction of the thermal decomposition profile. The ions used were 122 (benzoic acid) and 149 (terephthalic acid derivative) for the untreated and treated article, and 69 (CFs) and 77 ^FzHs) for the fluorinated acrylic polymer. Treated and Untreated Articles Thermal testing was initiated at 600C. The total ion chromatogram obtained at this temperature was presumably from simple gasification products with minimal oxidation. Preliminary tests indicated that benzoic acid was the largest peak for untreated and treated articles at 600C. Figure 2.9 shows a total ion chromatogram of the untreated article at 600C, and Figure 2.10 shows the mass spectrum at 13.4 min, where the largest signal is located. Comparison of the sample and library spectra indicates benzoic acid with 91% match quality. The first large peak at 8 min is due to the formation of water. The peak at 16 min has strong ion of 149 and is most likely a terephthalic acid derivative. Figure 2.11 shows a total ion chromatogram of the treated article combustion at 600C and Figure 2.12 shows mass spectra at 13.5 min, where the largest peak is located. Similar results were obtained for bom treated and untreated articles. Benzoic acid and terephthalic acid are expected thermal decomposition products of polyester (Ohtani, et al., Radlein, et al., 1991). The areas of all peaks were integrated within a mass range between 35 and 450 m/z to eliminate the peak associated with water from the analysis, and the ratio of these two peaks were calculated. The results showed that the benzoic acid peak consists of 33 and 36% of total peak area for untreated and treated articles, respectively, and the terphthalic acid derivative peak consists of 13% of the total peak area for both samples. The total integrated peak area of these extracted ions (122 and 149) was used for constructing the thermal decomposition profiles for the treated and untreated articles. The results are summarized in Section 3.1.1 and 3.1.2. m Atoundancss 2.00 4.00 0.00 S.OO 10.0012.0014.0010.0013.00:20.0022.0024.0026.00 TD# I 2 Compound Name Benzene Toluene1' Quality (%)' 96 94 3 1 -Phenyl-1,2-propanedione 91 4 Benzoic acid 91 5 Terephthalic acid derivative" 78 a Match quality from NIST129K standard spectra library, obtained by data analysis software (G1701BA Version B03.00, Agilent Technologies). b Toluene is located on top of the large water peak. This compound could not specifically be identified, but is most likely a terephthalic acid derivative based on manual mass spectral analysis. Figure 2.9 Total Ion Chromatogram and Peak Identification for Untreated Article at 600C. Abundance 1800000- Scan 1321 (13.288 mln>; 1-)-TB-25.D 1600000 1400000' 1200000. 1000000 800000 800000 400000 200000 ..YUi.. Hf^ '^eiTte'e,,^; 26^0 32a^,3-i'd3^,4i2^.A Figure 2.10 Mass Spectra at 13.4 min for Untreated Article at 600C. n Abundance Time--v 2.00 4.00 6.00 8.00 10.0012.0014-0016.0018.0020.0022.0024.0026.00 ro# 1 Compound Name Water" Quality (%)" 1 2 Benzene 96 3 Toluene" 91 4 l-Phenyl-l,2-propanedione 91 5 Benzoic acid 81 6_____Terephthalic acid derivative'1________64 a Match quality from NIST129K standard spectra library, obtained by data analysis software (G1701BA Version BOS.00, Agilent Technologies). b The low matching quality is due to number of small background ions in the spectrum. The major ions clearly indicate water. c Toluene is located on top of the large water peak. d The compound could not specifically be identified, but is most likely a terephthalic acid derivative based on manual mass spectral analysis. Figure 2.11 Total Ion Chromatogram and Peak Identification for Treated Article at 600C. /<.t>t^rctanc=o 2000000 1346 <13.SSO mn>: TKa-StSS.O iaooooo I 600000 1400000' 1200000 t 000000' 800000 600000 4000001 A 5:00000 o' zo^oBO Vo'^SmX^e^SSaoSi^X^^B^a^Sc^t&a^SStQ^y' Figure 2.12 Mass Spectra at 13.5 min for Treated Article at 600C. 17 Fluorinated Acrylic Polymer Figure 2.13 shows the total ion chromatogram of the fluorinated acrylic polymer combustion at 600C. The baseline elevation at 8 min is due to formation of water. The baseline also indicates the presence of ion 85 which is indicative of the formation of silicon tetrafluoride (Sil'4). This product is associated with oxidation of the polymer and subsequent reaction of hydrogen fluoride with test system materials. The extent of formation ofSiF4 was monitored in each run to determine its potential impact on the fluorine recoveries. Several peaks were identified as fluorinated and chlorinated hydrocarbons. Figure 2.14 shows extracted ions 69 and 77, which are the major ions for the major peaks identified. The structures of these ions were suggested by the NIST library and are plausible combustion byproducts. The total peak area of these extracted ions (69 and 77) was used as reference ions for constructing the thermal decomposition profile for the polymer. The combustion byproducts of interest were quantified at each reactor temperature. The results are summarized in Section 3.1.3. Abundance 1.4e+07 < TIC:PM8-29-1.D 1.2e+07 1e+07 8000000 6000000 4000000 2000000 Time--> ^ A 2.00 4.00 6.00 8.00 10.0012.0014.0016.0018.0020.0022.0024.0026.00 ID# 1 Compound Name Not identifiable" Quality (%)' 2 3,3,4,4,-tetrafluoro-l ,5-hexadiene0 45 3 Not identifiable" 4 Not identifiable' 5 1,1,3 -trichloro-2-Propanone'5 47 6 Perfluoro-n-pentanoic acid 90 7 Not identifiable8' a Match quality fromNIST129K standard spectra library, obtained by data analysis software (G1701BA Version B03.00, Agilent Technologies). b Not identifiable due to low match quality. c The compound showed is the best match to the library, but not reliable because of the low match quality. Figure 2.13 Total Ion Chromatogram and Peak Identification for Fluorinated Acrylic polymer at 600C. 13 4000000 3000000 3EOOOOOO <eo.TO to ea.7o>: F*IWIS Ion 69 1000000 AtM-*nd aariCf ^^..L.I^JflWlAAj^ _2.0^0. A^. 4.00 F e ^lJ .oo ^ a ^^ -oo U 1 Wy 0.00 U^ 122..00 ., 0 . 1 4 ..0.0.1. 8. ..0. 0. .1.8.. .0.0.2.0...0.0.2. : ; 2 . 0 0 5 4 . 0 0 2 6 . 0 0 Ion 77 loo 77.00 (7S.70 to 77-70); F-MB-JBS-I .0 4000000' 3000000 saoooooo 1000000 .2..)0^0. , i 4 . 0^0:\ ,8.^.0w0, . .8, . 'Y.^ 00 .'y-^r^-'- 10.001 '"'! Sf. .;.'. 0014 .i0.0.1. . Q .iO..O. i i a .i 0.0.2.0. . i 0 Q..2.S. . i O Q..2. i 4 . i 0 0. 2..Q.. i O O.. Figure 2.14 Extracted Ions (69 and 77) for Fluorinated Acrylic Polymer at 600C. 2.5 Treated and Untreated Articles: PFOA, Fluoride, and Chloride Determination at 1000C The reactor effluent from the combustion of the treated and untreated articles was sampled and PFOA, fluoride, and chloride were determined. The samples were gasified and incinerated in a similar manner to the procedure described in section 2.4.1. The entire system, including cold trap, was heated to 300C. As shown in Figure 2.15, the effluent was taken from the exhaust vent and passed through an aqueous solution bubbler system to collect the analyte of interest. The bubbler system consisted of two bubblers (120 mL amber glass jar, I-CHEM, New Castle, DE ) with 1x3 mm i.d. x o.d., 4 in length quartz stem filled with 60 mL HPLC grade water (HPLC Grade Ultrapure Water, Stock #22934, Lot #L1 ON39, Alfa Aeser, Ward Hill, MA) as shown in Figure 2.15. The silicone tubing (0.063 in i.d., 0.125 in o.d., 12 in length. Cole Farmer Instrument Co., Vemon Hills, IL) was used as a transport line between the exhaust vent and first bubbler. The same tubing, approximately 2 in in length, was used to connect the two bubblers. An additional thermocouple was placed downstream of the bubblers as shown in Figure 2.15 and the temperature monitored and recorded. Following each experiment, the silicone tube that connects the exhaust line and the first bubbler was rinsed with 5 mL HPLC grade water (Alfa Aesar) and the extracts added to the first bubbler. The sample was sealed with an aluminum foil sealer, labeled, and sent to Exygen with chain of custody form for the analyses. The actual sampling was performed as follows: 1. Set airflow rate to obtain residence time of 2 sec at the reactor. Two thirds of the flow was introduced to Inlet 1 where the pyroprobe is inserted and one third of the flow was introduced to Inlet 2. 2. Record ATRS inlet flow rates. 3. Set cold trap temperature to 300C (no condensation step). 4. Record temperatures at the 8 points shown in Figure 2.4 and 2.15. 5. Connect bubblers to exhaust line. 6. Insert pyroprobe into Inlet 1. 7. Stabilize the system for 1 min. 8. Start pyroprobe temperature programming. 9. Sweep entire system with helium for 3 min. 10. Record temperature downstream of second bubbler. 11. Disconnect bubblers 12. Record ATRS inlet flow rates. 13. Record temperatures at the 8 points shown in Figure 2.4 and 2.15. 14 The results are summarized in Section 3.2. Exhaust Line Bubbler w/60ml HPLC Grade Water Thermocouple 8 From ATRS Exhaust Line Figure 2.15 Off-Line Aqueous Sampling for Fhioride and PFOA. 2.6 Treated and Untreated Articles: Off-line GC/MS Analysis of Volatile Organic Compound (VOC) Analysis at 1000C The reactor effluent from the combustion of the treated and untreated articles was analyzed for volatile organic compounds at 1000C using a gas sampling bag and off-line GC/MS analysis. The sample was taken from the exhaust line shown in Figure 2.4 using a 0.5 L Tedlar bag (SKC Inc., Eighty Four, PA). Silicone tubing (0.063 in i.d., 0.125 in o.d., 30 cm length. Cole Farmer Instrument Co., Vemon Hills, DL) was used for the transfer line. The collected sample was used for both VOC and fixed gas (CO, COz) analyses (see Section 2.7). The sample was gasified and incinerated in a manner similar to me in-line GC/MS analysis. The entire system, including cold trap, was heated at 300C for this analysis. The detailed procedure is shown below. A Supeico Q PLOT column (30 m x 0.53 mm ID, SUPELCO Inc., Bellefonte, PA) was used for analysis and the injection volume was 0.5 mL. The GC oven temperature was held at -60C for 1 min, then increased to 280C with ramping of20C/min and held 5 min at 280C. The mass scan range was 12 - 450 m/z to allow analysis of a wide range of compounds including water. The sampling procedure is shown below: 1. Set air flow rate to obtain residence time of 2 sec at the reactor. Two thirds of the flow is introduced to Inlet 1 where the pyroprobe is inserted and one-third of the flow is introduced to Inlet 2. 2. Record inlet flow rate. 3. Set cold trap temperature to 300C (no condensation step). 4. Record temperatures at 7 points shown in Figure 2.4. 5. Insert pyroprobe into Inlet 1. 6. Stabilize the system for 1 min. 7. Connect Tedlar bag to exhaust line and open valve. 8. Start pyroprobe temperature programming. 15 9. Sweep entire line with He for 3 min. 10. Close Tedlar bag valve and disconnect a bag. 11. Record inlet flow rate. 12. Record temperatures at 7 points shown in Figure-2.4. The results are summarized in Section 3.6. 2.7 Treated & Untreated Articles: CO and COz Analyses at 1000C The samples collected for VOC analysis were also used for CO and CO; analyses. The CO and CO; were analyzed using a GC/TCD (8610C gas chromatograph, SRI Instruments, Torrance, CA). CO and COz were separated from other compounds using a 6 ft molecular sieve packed column and silica gel column, respectively, which were preinstalled by the manufacturer (SRI Instruments). A standard calibration was conducted prior to the analyses; results are shown in Figures 2.16 and 2.17. Table 2.5 shows the linear fit equation of CO and COz calibration. Carbon mass balance was calculated based on the sample gasified and the amounts of VOC, CO, and COz measured. The results are summarized in Section 3.7 0 500 1000 1500 2000 2500 3000 3500 4000 Cone. (ppm) Figure 2.16 CO Calibration Curve. 16 510' 410' 310' 2104 < 1 10 010' -1 10' Cone. (ppm) Figure 2.17 COz Calibration Curve. Table 2.5 Linear Fit Equations for CO and COi Calibration Curves. Sample Name Linear Fit R (x: mol, y: peak area) CO ;c=(y+3.04E2)/8.13E-l 0.992 COz x= (y + 8.57ED/1.37EO 0.999 2.8 XPS Analysis ofPyroprobe Cartridge The surface of the sample cartridge used for treated article gasification was analyzed by x-ray photoelectron spectroscopy (XPS) to investigate fluoride deposition on the cartridge surface. The results are summarized in Section 3.4 2.9 Telomer B Alcohol Combustion: GC/MS Analysis In-line GC/MS analysis was conducted for Telomer B Alcohol combustion at 200 and 600C to investigate if the 77 ion observed in the combustion tests of the fluorinated acrylic polymer is formed. Ion 77 is the most abundant ion of the fluorinated acrylic polymer combustion byproduct effluent according to the preliminary combustion tests (see Section 2.4.4). The Telomer B Alcohol is a multicomponent mixture whose formula and concentration range are shown in Table 2.6. The generic formula is estimated based on the average concentration of each constituent and can be expressed as: Co.3oFo.52Ho.l50o.03 Due to a scarcity of hydrogen in the test substance, methane was also supplied as a hydrogen source to convert excess fluorine to HF. Methane was supplied at twice the stoichiometric amount to ensure fluorine conversion to HF. A 10 mL gas tight syringe (SGE, Austin, TX) and syringe pump (Kd Scientific, Holliston, MA) was used to supply methane. The stoichiometric oxidation can be expressed as follows: 17 Co.3oFo.52Ho.i50o.o3 + 0.185CH4 + 0.562502 -> 0.485COz + 0.52HF + 0.185HzO ------- (Equation 5) The sample inlet and transfer lines were kept at 150C. Pyroprobe initial and final temperatures were set at 150 and 200C, respectively, and the final temperature was held for 1 min to ensure complete gasification. Two tests were conducted at reactor temperatures of 200C and 600C. The results are summarized in Section 3.5. Table 2.6 Telomer B Alcohol Characterization. Name Formula Cone. (%) _1_,1_,2_,2_-_Te_tr_ah_y_d_ro_p_er_flu_o_ro_-__C_H_20_H_C_H_z(_C_F2_)3_C_F_3 __Rang1e-2 1-Hexanol 1,1,2,2-Tetrahydroperfluoro- CH20HCHz(CF2)5CF3 27-34 1-Octanol 1,1,2,2-Tetrahydroperfluoro- CH20HCH2(CF2)7CF3 29-34 1-Decanol 1,1,2,2-Tetrahydroperfluoro- CH20HCH2(CF2)9CF3 17-21 1-Dodecanol 1,1,2,2-Tetrahydroperfluoro1-tetradecanol CH20HCH2(CF2)nCF3 6-9 1,1,2,2-Tetrahydroperfluoro1-Hexadecanol CH20HCH2(CF2)i3CF3 2-5 1,1,2,2-Tetrahydroperfluoro- CH20HCH2(CF2)i5CF3 1-2 Average Cone. (%) 1.5 30.5 31.5 19 7.5 3.5 1.5 1-Octadecanol_______________________________________ 2.10 Perfluorooctanoic Acid (PFOA) Absorption Study An independent system was built to study PFOA absorption. The purpose of the absorption test was to study how much PFOA can be transferred from the gas phase to the aqueous solution. This set of experiments examined the absorption efficiency of PFOA into aqueous solution and sought to examine the propensity in which PFOA may condense in the test system. 2.10.1 PFOA Absorption Study Figure 2.18 shows a schematic of the PFOA absorption study apparatus. PFOA was weighed and placed into a sample container (2x2.5mm (i.d-Xo.d.), 25 mm length quartz capillary tube, CDS Analytical me., Oxford, PA), which was also weighed prior to sample loading. The sample container was placed into a heating tube (4x6 mm (i.d.xo.d.), 20 cm length). The aqueous absorption system consisted of two 120 mL glass jars, each containing 60 mL HPLC grade water (HPLC Grade Ultrapure Water, Stock #22934, Lot #L10N39, Alfa Aeser, Ward Hill, MA). Silcosteel tubing (1/8 in) (RESTEC Co., Bellefonte, PA) was used as a transfer line between the heating tube and bubbler. The heating tube and transfer line was heated from room temperature to 170C with a temperature ramping rate of approximately 25C/min and held at 200C for 5 min. The vaporized PFOA was swept using carrier flow (synthetic air) at 19.2 mL/min flow rate and bubbled through the aqueous solution. The sample container was weighed again after heating. The molar amount of PFOA available for absorption was calculated from the difference in weight before and after heating. This amount was compared to PFOA determined in aqueous solutions to calculate the absorption efficiency. 18 The heating tube and Silcosteel (RESTEC Co., BeUefonte, PA) transfer line were rinsed with 60 mL HPLC grade water (Alfa Aeser) and collected into jar 3. This was to facilitate capture ofPFOA condensed on heating tube and transfer line walls. Each aqueous sampling jar was labeled, secured, and sent to Exygen with a chain of custody form for PFOA determination. The results of these studies are summarized in Section 3.8. Bubbler w/60rri HPLC Grade Water Figure 2.18 Schematic for PFOA Absorption Test 2.11 PFOA Transport Studies In order to evaluate the transport of PFOA through the ATRS, two independent experiments were conducted. First, PFOA in the ATRS effluent was sampled in an aqueous solution bubbler system for HPLC7MS/MS analysis. Second, PFOA in the ATRS effluent was sampled and analyzed using in-line GC/MS analysis. 2.11.1 PFOA Transport Study - Aqueous Sampling Two tests were conducted using the same ATRS setup used for PFOA, fluoride, and chloride sampling and analyses described in Section 2.5. The temperature for the first test was 170C, and the temperature for the second test was 300C. All transfer lines, reactor, and cold trap were maintained at the same temperature to prevent sample condensation and decomposition. The injection ports were kept at 170C for both 170 and 300C transport tests. The sample was placed into a sample cartridge (2 x 2.5 mm (Ld.xo.d-), 12.5 mm length quartz capillary tube, CDS Analytical Inc., Oxford, PA) and the cartridge inserted into Inlet 1 using the pyroprobe and gasified at 170C. The pyroprobe temperature was increased from 100C to 170C at the rate of70C/min and held 170C for 4 min giving a total of 5 min. The ATRS effluent was passed through two aqueous solution bubblers connected in series to collect PFOA as shown in Figure 2.15. The transfer line (12 in silicone tubing (0.063 in i.d., 0.125 in o.d.. Cole Farmer Co., Vemon Hills, IL)), was rinsed with 5 mL HPLC grade water (HPLC Grade Ultrapure Water, Stock #22934, Lot #L10N39, Alfa Aeser, Ward Hill, MA), and added to Jar 1. After PFOA was collected in the aqueous solutions, a low pressure steam extraction procedure was performed to extract any possible PFOA condensate remaining in the ATRS system. The steam was collected from the ATRS exhaust line and condensed into two glass vials (40 mL Vial, Amber, Wheaton, Millville, NJ) which were connected in series and immersed in an ice bath as shown in Figure 2.19. The following procedure was used for steam extraction. 19 The entire ATRS system (inlet, reactor, transport line, and cold trap) was heated to 300C prior to steam extraction. 5 mL ofHPLC grade water (Alfa Aeser) was injected into inlet 1 using a syringe pump (Model 101, Kd Scientific Inc., Holliston, MA) and a 5 mL syringe. Steam was generated by injection to inlet 1 heated to 300C. The syringe pump was used to inject water at a constant rate. The steam was collected as condensate using two 40 mL vials which were placed in the ice bath. The steam injection flow rate was limited to 200 mL/min at 300C. Five mL ofHPLC grade water (Alfa Aesar) was injected at a rate of 4 mL/hr, generating 174 mL/min steam flow through the system. The extraction procedure was performed five times consecutively. Vial 1 was weighed before and after the steam extraction procedure to measure the amount of water condensed. Vial 2 was not weighed because there was no visible condensation in this vial. Following each steam extraction, the silicone tubing connects the ATRS exhaust line and the first vial was rinsed with 5 mL HPLC grade water (Alfa Aeser) and added to vial 1. Vial 1 was sealed with aluminum foil, labeled, and sent to Exygen with a chain of custody form for PFOA determination. A HPLC grade water (Alfa Aeser) blank and a second blank of HPLC water injected through the syringe were also provided for background PFOA determination. The pyroprobe used to hold the sample cartridge for gasification was also rinsed using 100 mL HPLC grade water (Alfa Aeser). This water sample was placed in a glass jar, sealed with aluminum foil, labeled, and sent to Exygen with a chain of custody form for PFOA determination. The results of these studies are summarized in Section 3.9.1 40 mL Vials in Ic&Bath Silicone Tubing ToGC (Plugged) Figure 2.19 Schematic for PFOA Steam Extraction of the ATRS. 20 2.11.2 PFOA Transport Study - Gas Phase Sampling Solid PFOA samples were obtained from Oakwood Products, Inc. (West Columbia, SC, Lot No.: 210002) PFOA transport efficiency was determined by comparing the total PFOA ion peak area obtained by direct PFOA injection into the GC/MS with PFOA introduction into Inlet 1 of the ATRS followed by in-line GC/MS analysis. Operational conditions for these two studies were identical and are described in detail below. ^ For the ATRS tests, the temperature (inlets, transport lines, reactor and the cold trap) were set at 235C. Synthetic air was used as carrier gas. The total flow rate was set at 33 mL/min (22 mL/min to inlet 1 and 11 mL/min to inlet 2) to maintain the sample residence time in the reactor at 2 sec at 235C. The same type of sample container used for the previous study (see Section 2.10.1) was used to load PFOA. The pyroprobe temperature was increased from 100 to 300C at the rate of200C/min and held at 300C for 2 min. After gasification, the system was swept with He for 3 min and the GC temperature programming was started. The GC initial temperature was set at 40C and held for 1 min. The temperature was increased to 280C at the rate of20C/min and held for 5 min at 280C. For the direct GC injection tests. He was used as the carrier flow and the flow rate through the injector was also 33 mL/min. The sample was introduced into the GC injection port using the sample cartridge used for the pyroprobe sample gasification, while the injection port was kept at 40C. The injection port temperature was then increased to 235C at a rate of approximately 20C/min and held for 1 min at 235C. Then me GC temperature programming was started using the same temperature programming rate used for the ATRS tests. The PFOA total ion chromatogram peak areas for the two methods were integrated, and the ratio of the peak areas was used as the PFOA transport efficiency through the ATRS. The results are summarized in Section 3.9.2. Exhaust ATRS GC Cold Trap 2^1 Inlet I' 5Figure 2.20 Schematic of PFOA Transport Efficiency Test Through the ATRS System. 21 Cartridge in Injection Port Figure 2.21 Schematic ofPFOA Direct Injection to GC Injection Port 2.12 PFOA Calibration Curve and Detection Limit Study This study was conducted to identify the actual retention time of PFOA in the GC/MS total ion chromatogram, quantify PFOA if it is formed, and determine the PFOA detection limit using the ATRS with same experimental procedure used for the sample combustion tests. The sample container (2 x 2.5 mm (i.d.xo.d.), 12.5 mm length quartz tubing, CDS Analytical me., Oxford, MA) was loaded with 1,5,10,50, and 100 u,g PFOA. To load these minute amounts of PFOA, three PFOA solutions with different concentrations were prepared as shown in Table 2.7. The preparation conditions are also summarized in Table 2.7. The results are summarized in Section 3.10. Table 2.7 Solution Concentration (PFOA in Methanol) and Volume Required to Produce 1,5,10,50, and 100 u,g PFOA Injection into ATRS. Dried Sample Solution Used Solution Drying Time Mass(ng) (Concentration) Loaded (pi) (hr) (mgPFOA/mL ______1 _________MeO1 H')_________1_________3_____ 5 1 5 15 10 10 1 3 50 10 5 '15 100 100 1 3 ' MeOH: Methanol The ATRS, inlets, transport lines, and reactor temperatures were set at 300C. The total gas flow was set at 29.4 mL/min (19.6 mL/min to inlet 1 and 9.8 mL/min to inlet 2) to maintain a sample residence time in the reactor at 2 sec at 300C. The pyroprobe temperature was increased from 100 to 300C at a rate of 200C/min and held at 300C for 2 min to gasify PFOA. After gasification, the system was swept with He for 3 min. The gasified PFOA was condensed at the cold trap and released for in-line GC/MS by heating the cold trap to 280C. The GC conditions were the same as the actual combustion tests in Section 2.4.1. In order to determine if PFOA was lost during solvent evaporation (drying), similarly prepared 500u,g samples were weighed before and after drying. Results showed that more than 90% of the PFOA remained during drying. This ca. 10% difference is within the uncertainty of the analytical balance used for the Weight measurements. 22 2.13 Test Matrix and Quality Assurance Procedures A thermal decomposition profile for each sample was generated from 600C to 799.9. A blank analysis was performed before each combustion test to examine any carryover from previous tests. If any carryover was observed, the reactor assembly, cold trap, and GC column was cleaned at elevated temperature with air (for reactor assembly and trap) and He (for GC column) and a second blank analysis was performed. The cleaning process was continued until no carryover was observed. Blank runs were performed using the same procedure, but without sample insertion. Upon completion of thermal decomposition profiles for each sample, temperatures to perform CO, COz, fluoride, and PFOA analyses were determined following a discussion between UDRI and DuPont. CO, CO;, fluoride, and PFOA sampling and analyses were performed in triplicate at the specified temperature. The test matrices are shown below. (1) In-line GC/MS Analysis: All three samples, untreated and treated articles, and fluorinated acrylic polymer were analyzed using the in-line GC/MS system at temperatures from 600C to T99.9 at 50C increments. (2) VOC, CO and CO; Analyses: Untreated and treated articles were analyzed using off-line GC/MS for VOC and GC/TCD for CO and C02 at the specified temperatures. (3) PFOA, Fluoride and Chloride Analysis: Untreated and treated articles were analyzed using ion chromatography and HPLC/MS/MS for PFOA, fluoride, and chloride at specified temperatures. (4) Additional Study i) XPS Analysis: Sample cartridge used for treated article combustion. ii) Telomer B Alcohol Analysis: Telomer B Alcohol combustion at 200 and 600C. iii) PFOA Absorption Test at 170C. iv) PFOA Transport Test at 170 and 300C. v) PFOA Steam Extraction at 300C vi) PFOA Calibration Curve and Detection Limit Study at 300C 2.14 Quality Assurance Narrative Statement This program involved conducting thermal decomposition tests on a fluorinated acrylic polymer, an article treated with the polymer, and an untreated article provided by DuPont. All analysis and handling of data fully conformed to ANSI/ASQC E4 requirements (ASQ, 1994). All analysis techniques were performed with the appropriate ASTM or US-EPA standard methods. Any specialized, non-standard analytical techniques used fully developed SOPs which have been incorporated into prior EPA-approved Quality Assurance Project Plans (US-EPA, 2000). 1. Study Design: The overall study design is described in Section 2 of this report. 2. Sample Handling and Custody: Chain of custody procedures previously developed under USEPA Quality Assurance Program Plans (QAPPs) were followed during this program. All samples were composed of purchased chemicals of known purity or samples provided by DuPont. All samples, including any hazardous chemicals, were received, labeled and logged, with hazardous materials placed into a pre-existing Hazardous Materials Handling Facility. Samples were not removed from storage except as labeled prepared samples for immediate study. 3. Sample Analysis: Only samples of known purity were purchased. All analysis techniques were performed in compliance with appropriate standard methods. Any specialized, non-standard 23 analytical techniques have fully developed SOPs that were followed and which have been incorporated into prior EPA-approved QAPPs. 4. Calibration and Performance Analysis of Sampling and Analytical Methods: All of the measurement and analytical equipment used in this program are commercially available and calibrated and maintained in accordance with the manufacturer's SOPs. Quantitative analysis of samples was performed using established GC/MS methods including the use of certified internal standards as needed. 5. ATRS Operation: Known amounts of the samples were gasified with 85% excess air. The mean gas-phase residence time in the reactor was maintained at 2 sec. The reactor and transport line temperature and carrier flow rate were monitored and logged before and after the experiments. The reactor temperature was kept within 1C of the set temperature for most cases and 2C for few cases. The flow rate was kept within 0.2 mL/min of the set flow for all cases. 6. Data Reduction and Reporting: Tables of calibration data were furnished, along with graphs of reduced data. Standard deviations, regression coefficients, and other statistical measures of data quality were calculated from linear or nonlinear regression analyses of data. All data are subject to internal review by the project leader 7. Intended Use of the Data: The data generated in this study were used to provide guidance as to the temperature required to destroy the parent material with an efficiency of>99.9% and all organic products to an equivalent level with a mean exposure time of 2 sec and a level of excess air of no lower than 85%. The data also provided guidance as to the identification of organic products and the temperature required to destroy them. 8. Evaluation of the Success of the Project: The success of the project will be indicated by our ability to determine the temperature required to destroy the parent material with an efficiency of >99.9% and all organic products to an equivalent level with a mean exposure time of 2 sec and a level of excess air of no lower than 85%. 9. Reviews of the Study Plan: The study plan and the proposed analytical methods were prepared by the project leader and his research team within the Environmental Engineering Group. It is common practice for external review by the sponsor's technical representative or designated alternate. 24 3. Experimental Results 3.1 In-line GC/MS Analysis and 99.9% Destruction Temperature Determination Thermal decomposition profiles for the untreated and treated articles and fluormated acrylic polymer were generated using the ATRS with in-line GC/MS analysis. The thermal decomposition profile and extracted ion chromatograms at each temperature for each sample are presented in this section. Raw data for all experiments are presented in Appendix A. 3.1.1 Untreated Article Ions 122 (benzoic acid) and 149 (terephthalic acid derivative), which are the major ions of the untreated article at the temperature of complete gasification, were used to determine the thermal decomposition profile. Table 3.1 shows total ion counts and summation of ions 122 and 149. Both ions disappear at 725 and 700C, respectively. The analysis was repeated at 750C to ensure complete sample destruction. The total ion counts were also normalized by gasified sample mass and the relative degradation was calculated. Tg9.9 was obtained at 725C. Figure 3.1 shows the degradation profile of the untreated article. Figures 3.2 and 3.3 show extracted ions 122 and 149 for the untreated article at 600,650,700, and 725C, respectively. Ions 122 and 149 were also extracted for combustion at 1000C to ensure that these compounds were not reformed at higher temperature. Figure 3.4 shows the results. Only a background signal was observed, and there is no indication of reformation of these compounds. Temp (C) 600 650 700 725 750 750 Table 3.1 Ion 122 2.31E+08 1.82E+08 4.53E+07 O.OOE+00 O.OOE+00 O.OOE+00 Major Ion Counts of the Untreated Article. Ion 149 Total Mass (mg) Normalized By Mass 4.48E+07 2.76E+08 1.11 2.48E+08 1.31E+06 1.83E+08 1.01 1.81E+08 O.OOE+00 4.53E+07 1.02 4.44E+07 O.OOE+00 O.OOE+00 1.00 O.OOE+00 O.OOE+00 O.OOE+00 0.97 O.OOE+00 O.OOE+00 O.OOE+00 1.04 O.OOE+00 Relative % 100 72.95 17.86 0.00 0.00 0.00 25 100 10 6S .E Untreated Article 0.1 0.01 550 600 650 700 750 800 Temperature (C) Figure 3.1 Untreated Article Thermal Destruction Profile Normalized by Sample Mass. Afc> L* nd SB rice -I 0000001 &ooooo| 400000J aooooo| 0 Ion 122.00 <121-70 to 122.'7'0>: L1~T0-2-D 5.00 1 0.00 IS.00 20.00 25.00 30.00 3S.OO 1000000 aooooo eooooo -l-OOOOO 200000 lor-* 122.00 <121-'7'0 to I 22.7'0>: l-IT'QS-2-D .4. B.bd'loloois.oo 20.00 zs.oo 30.00 700C aooooo GOOOOO -4.00000 200000 0 Ion 12:3.00 <12:1.70 t3 122--7-0): LJT-7-0-3.C3 5.00 10.00 15.00 20.00 25.00 30.00 35.00 725C 1000000 lor* 122.00 <121-yo to 122.-7-0): OT'73.0 6000001 toooool 2000 S.OO 10.00 15.00 20.00 25.00 30-00 35.00 Figure 3.2 Extracted Ion 122 (benzoic acid) for Untreated Article at 600,650,700, and 725t>C. 26 ^o>-*ndanQ a.00000 300000 200000 100000 0 Ion 1AS-00 <148.70 to 1AS.70): -l-reO-2.D S.OO 10.00 1S.OO 20.00 2S.OO 30.00 3S.OO -t.00000 300000 200000 100000 0 AoLjncjanCQ 400000 300000 200000 100000 0 AA3i-inc!ancse "*00000 300000 200000 1 00000 0 Ion l.d.9.00 <-14S.7'0 to 1-*Q.7-0>: UT-SS.O 5.00 10.00 1S.OO 20.00 2S.OO 30.00 3B.OO Ion 14.9.00 <11S-70 to K9.7-0>: l-tT-70-3.0 5.00 10.00 1S.OO 20.00 2S.OO 30.00 3S.OO Ion 1-4.9.00 <14.S.7'0 to 1AS.7'0>: >_l-r-7"3.0 5.00 10.00 1S.OO 20.00 2S.OO 30.00 3S.OO Figure 3.3 Extracted Ion 149 (terphthalic acid derivative) for Untreated Article at 600,650,700,and725C. ^bLjndeinc:^ lor 122.00 <iai.7-0 to 12a.7'0}: UTI 00-1 .D Figure 3.4 Extracted Ion 122 (benzoic acid) and 149 (terephthalic acid derivative) for Untreated Article Combustion at 1000C. 27 3.1.2 Treated Article Ions 122 and 149 were also used to determine the thermal decomposition profile of the treated article. Table 3.2 shows total ion counts and a summation of ions 122 and 149. Ions 122 and 149 disappear at 700 and 725C, respectively. The analysis was repeated at 750C to ensure complete sample destruction. T99.9 was obtained at 725C. Figure 3.5 shows the degradation profile of the treated article. Figures 3.6 and 3.7 show the extracted ions 122 and 149 for the treated article at 600,650,700, and 725C, respectively. Ions for fluorinated species fragments (69 for 'CFs, 119 for 'CF2CF3, and 131 for CFzCF=CF2) were also extracted and are shown in Figures 3.8,3.9, and 3.10, respectively. Ion 69 was observed even at 725C, but the amount was very small. Ions 119 and 131 were destroyed at 725C. No other fluorinated species fragment was observed for the treated article combustion test. Ions 122 and 149 were extracted for the combustion at 1000C to ensure these compounds were not reformed at higher temperature. Figure 3.11 shows the results. Only a background signal was observed. Temp ( C ) 600 650 700 725 750 750 Table 3.2 Major Ion Counts of the Treated Article. Ion 122 Ion 149 Total Mass (mg) Normalized by Mass 2.80E+08 5.43E+07 3.34E+08 1.22 2.74E+08 2.38E+08 6.15E+06 2.44E+08 1.25 1.95E+08 1.49E+06 O.OOE+00 1.49E+06 1.22 1.22E+06 O.OOE+00 O.OOE+00 O.OOE+00 1.23 O.OOE+00 O.OOE+00 O.OOE+00 O.OOE+00 1.24 O.OOE+00 O.OOE+00 O.OOE+00 O.OOE+00 1.23 O.OOE+00 Relati've% 100 71.27 0.45 0.00 0.00 0.00 Treated Article 550 600 650 700 750 800 Temperature (C) Figure 3.5 Treated Article Thermal Destruction Profile Normalized by Sample Mass. 28 ^kDUrtdfixincG Ion 122.00 (.121 .70 to 122.7-0): -TReo-2.0 6000004 40oooo| aoooool .AkbLinclaxricQ 1200000 1000000 eooooo eooooo 4.00000 A.fc>ur*oarioo 1200000 1000000 800000 eooooo 400000 11200000000000 600000 400000 200000 .00 10.00 15.00 20.00 25.00 30.00 36.00 122.00 <121.7'0 to 122.7"0>1 T*=lS.D '.00 10.00 15.00 20.00 25.00 30.00 35.00 lor* 122.00 <121 .'TO to 122-'7-05: ~rF%7-0-I=> .00 10.00 IS.00 20.00 25.00 30-00 3S.OO Ion 122.00 <121.-7-0 to 122. TO): TR-7-3.0 S.OO 10.00 I^S.OO 20.00 2S.OO 30.00 3S.OO Figure 3.6 Extracted Ion 122 (benzole acid) for Treated Article at 600,650,700, and 725C At>j ncia nc 400000 300000 200000 100000 0 ^k>'u nd e r-c 400000 300000 200000 100000 -Tli-no--- .Abcindsince ior* 1.4.0.00 <-i-*e.70 to -i -<.&.7'o>; T-Reo-a.o S.OO 10-00 15.00 20.00 2S.OO 30.00 3S.OO Ion 148.00 <-I-*e.7-0 to 1-*Q.70>: T-RSS-0 i.OO 10.00 1 S.OO 20.00 2S.OO 30.00 3S,00 600C 650C 700C 400000 300000 200000 100000 0 Ion 14.8.00 C14.S.7-0 to l-l.S.T'O): -rRT-O.O S.OO 10.00 1S.OO 20.00 2S.OO 30.00 3S.OO 725C 400000 300000 200000 100000 0 Ion 14&.00 <14S.7"0 to 14Q-7'0>: "TR7';3-D .00 10.00 1S.OO 20.00 2S.OO 30.00 3S.OO Figure 3.7 Extracted 149 (terphthalic acid derivative) for Treated Article at 600,650,700, and 725C. 29 aoooo 60000 40000 2000001 Tirr^------ ,Afcii-i n dan co aoooo 60000 40000 20000 0 *c< 80000 60000 40000 20000 80000 eoooo 40000 20000 39.00 <S.7 .70>: -TR.60-2.D .00 10.00 IS.00 20.00 25.00 30.00 35.00 ion ee-oo <ee.70 to e&.'7'o>: TRSS.O [HA. .00 10,00 15.00 20.00 25.00 30.00 35.00 *on ea.oo <ss-70 to SQ.TO>; TRTO.D 5.00 10.00 15.00 20.00 25-00 30.00 35.00 Ion GQ.OO <sa-70 to S.7'0>: -TR73.D 5.00 1 0.00 1 5.00 20.00 25.00 30.00 35.00 600C 650C 700C 725QC Figure 3.8 Extracted Ion Count 69 (CFs) for Treated Article at 600,650,700, and 725C 2SOOOO < 200000 ieoooo 100000 50000 2600001 1SOOOO| 100000| 50000| 0 250000 200000 1SOOOO 100000 50000 200000 1SOOOO 100000 SOOOO 0 Ion 118.00 <1ia.70 to 11S.70): TRe 0-2.0 5.00 10.00 15.00 20.00 26.00 30.00 36.00 >n lia.OO <1ia.70 to 113.T'0): TRSB.D 6.00 10.00 IS.00 20.00 2S.OO 30.00 3S.OO Ion 11S.OO C118-7010 11Q.70>:TR70,D 5.00 10.00 1 S-00 20.00 25.00 30.00 3S.OO Ion 119.00 <118.7'0 to 119.70): TR73,0 S.OO 10.00 IS.00 20.00 2S.OO 30.00 35.00 600C 650C 700C 725C Figure 3.9 Extracted Ion 119 (CFzCFa) for Treated Article at 600,650,700, and 725C. 30 At=>u ndes r 300000 250000 200000 150000 100000 50000 A fcaun Clarice 300000 250000 200000 150000 100000 50000 -rimca-- jAbiu ncJ a noe 300000 2SOOOO 200000 1SOOOO 100000 50000 300000 2SOOOO 200000 150000 Ion 131.00<130.70to1 31.7-0): T-ReO-2.D S.OO 1 0.00 1 9.00 20^00J-i-25.00 30.00 35.00 Ion 131.00 < 1 30 .70 to ^3^.70>:'T^:=Ees.O 5.00 1 0.00 1 5.00 20.00 25.00 30.00 35.00 lor* 131.00 <130.7"0t0 131.'7'0>: r FIT 0-0 S.OO 1 0.00 1 S.OO 20.00 25.00 30.00 35.00 Ion 131.00 <130.70to 131.7'0>:T1R73.0 600C 650C 700C 725C 5.66 1 0.00 1 5.00 20.00 25.00 30.00 3S.OO Figure 3.10 Extracted Ion 131 (*CF2CF=CF2) for Treated Article at 600,650,700, and 725C. Ion 122 Ion 149 Figure 3.11 Extracted Ion 122 (benzoic acid) and 149 (terephthalic acid derivative) for Treated Article Combustion at 1000C. 31 3.1.3 Fluorinated Acrylic Polymer Ions 69 ("CFs) and 77 ('CF2CH=CH2), which are the major ions from the gasification of the fluorinated acrylic polymer, were used to determine the thermal decomposition profile. Table 3.3 shows total ion counts and a summation of ions 69 and 77. Ions 69 and 77 still exist at 1000C, but the relative amount remaining is ^0.1%. The analysis was repeated at 1000C to ensure 99.9% sample destruction. The total ion counts were also normalized by gasified sample mass and relative degradation rate was calculated. Tg9.9 was obtained at 1000C. Figure 3.12 shows the degradation profile of the fluorinated acrylic polymer, and Figures 3.13 and 3.14 show the extracted Ion 69 at low (600 ~ 800C) and high (850 ~ 1000C) temperatures, respectively. Figures 3.15 and 3.16 show the extracted ion 77 ('CFzCHOIz) at low and high temperatures, respectively. Figures 3.17 and3.18show extracted ion 119(*CF2CF3)atlow and high temperatures, respectively. Figures 3.19 and 3.20 show the extracted ions 131 (CF2CP=CF2) and 169 ('CFaCFzCFs), respectively. All ions correspond to the fluorinated compound, with the exception that ion 69 ('CFa) is relatively small compared to ion 77(*CF2CH=CH2). and these ions are negligible at combustion temperatures over 800C. _______Table 3.3 Major Ion Counts of Fluorinated Acrylic Polymers._______ Temp(C) Ion 69 Ion 77 Total Mass(mg) Normalized Relative % by Mass 600 1.44E+09 2.08E+09 3.51E+09 1.60 2.20E+09 100.00 650 L21E+09 1.15E+09 2.36E+09 1.69 1.40E+09 63.58 700 1.02E+09 2.24E+08 1.25E+09 1.68 7.43E+08 33.81 750 8.13E+08 1.44E+07 8.27E+08 1.62 5.10E+08 23.24 800 6.80E+08 1.50E+07 6.95E+08 1.63 4.26E+08 19.41 850 3.29E+08 7.45E+06 3.36E+08 1.62 2.07E+08 9.45 900 1.14E+08 5.13E+06 1.19E+08 1.63 7.30E+07 3.32 95.0 4.79E+07 4.62E+06 5.25E+07 1.58 3.32E+07 1.51 1000 1.13E+06 1.54E+06 2.68E+06 1.61 1.66E+06 0.08 1000 4.43E+05 3.61E+06 4.06E+06 1.61 2.52E+06 0.11 1000 2.12E+06 1.08E+06 3.21E+06 1.58 2.03E+06 0.09 32 IUU s? 10 'S CO CH 1 1 0) 1 0.1 ~-..i . , i ''""--...., ,ii, >. , * : : - 1 - '^ '' \ : '. \ ................\4 ; n m . . , , , , 600 700 800 , , , , 900 1000 Temperature (C) Figure 3.12 Fluorinated Acrylic Polymer Thermal Destruction Profile. Afcu-i ri d .e n t -100 0000 500000 Afc* m r*cSs -1 000000 500000 Ion &.00 <SS.7-0 to Q.'7-0>: Pr^0-2.0 * .00 S.OO -10.00 -15.00 20.00 25.00 30.00 35.00 >n 69.00 <0-7'0 to &.70>; F'-IS-flSS-CS 10.00 ..i iix.iUliAi^ -15.00 20.00 25.00 30.00 30.00 100 0000 500000 | J /-''''. 5.00 .00 <eQ.70 to eQ."7"0>: f^t^/f TO .0 10.00 15.00 20.00 25.00 30.00 35.00 1000000 ^ 500 000i -^.fc> LJ n cd S.OO .00 <eQ.-7'0 to S&.7"0>: Fl^I7-5.l3 10.00 15.00 20.00 25,00 30.00 35.00 1000000 esooooo S.OO eo.oo <eet.7'o to st.'7'o>; I=*I\^QO.IO 10.00 15.00 20.00 25.00 30.00 35.00 Figure 3,13 Extracted Ion 69 (CF3) for Fluorinated Acrylic Polymer at 600,650,700,750, and 800C. 33 ^oi^nd&nce -4.00000 , 300000 200000 100000; 0 T"im--> f^^ouoclanc 4300000000004J 200000 -j 100000 J 0 T'ime--> AOLjndanoe 400000 300000 i 200000 -I 100000 I 0; .^.to^ndaince 400000 300000 I j 200000 J 100000 j 0 Ion 6S.OO (SS-70 to SS.70>: f=MeS.D 5.00 10.00 1S.OO 20.00 2S-00 30.00 3S.OO ion ea.oo CSS.TO to SQ.-T-O: PMSO.O <-> S.OO 10.00 1S.OO 20.00 2S-00 30.00 3S.OO Ion S9.00 <Sa.7-0 to SS.7"0>: I=MSS.O <-> S.OO 10.00 1S.OO 20.00 2S-00 30.00 3S-00 Ion 69.00 <S8.70 to 69.7'0>: F=>1\/1QS-3.0 <> S.OO 10.00 1S.OO 20.00 2S.OO 30.00 3S.OO Figure 3.14 Extracted Ion 69 (CFs) for Fluorinated Acrylic Polymer at 850,900,950, and 1000C. oi 3000000 | 2000000 1000000 - T-lrr,------ ^Kt=> u i-i d ia i~i c: Gi 300C3000 S 1000000 | o-^ 4000000 3000000 - =2000000 ioooooo i 04000000 -i 23000000000000|j -1000000 | 0 3000000 - SOOOOOO- -y'T'.oo <ye.'70 to 7^'.70>; t=*i\/ieo-2.o 5.00 1 0.00 15.00 20.00 25.00 30-00 Ion T'T'.OO C7G.~rO to ~T~r .~TQ)t F1\/1B.D <*> 35.00 i.OO 1 S.OO 20.00 25.00 30.00 Ion TT.OO <7.70 to 77.7'0>: F='JS^T'0. C3 <"-> 35.00 .00 "ToToO 15.00 20.00 25.00 3olo0 35.00 lean T'T.OO <7e.-?-0 to TT . -TO >.- F=>M7-5-D <-> 5.00 10.00 15.00 20.00 25.00 30.00 ion T-T-.OO <.~re.'ro to 7"r.'ro): F^^/I&O.O <-> 35.00 0- 5.00 1 0.00 15.00 20.00 25.00 30.00 35.00 Figure 3.15 Extracted Ion 77(*CF2CH=CHz) for Fluorinated Acrylic Polymer at 600,650,700,750, and 800C. 34 ^OLjnciance 1a0o0o0o0o0 J < 4600000000 ! 200000 - j^kOLtnclailc^ -I 0800000000'2. 4600000000 - aooooo--i 18000000000 I ' 4eo0o0o0o0 i. = 20000 ! 0-2. 100000 - aeoooooooo-- 4200000000 - 0- S.OO ion 77.00 <7-e.7o to 77-.70>; P'MSS.O A 10.00 -15.00 20.00 25.00 30.00 35.00 Ion 77.00 <7S.70 to 77.70}; FIS/ISO.O <-> lO.OO IS.00 ^L. 20.00 2S.OO 30.00 35.00 lor* 77-00 <7Q.70 to Ty^O^ PIS^S5.C3 <*> S.OO 5.00 10.00 1S.OO 20.00 2S.OO 30.00 35.00 lon 7-7-.00 (7S.70 to 77.70>: p'l'i^SS-3.0 <-> -10.00 15.00 --A^.^ 20.00 a;5-00 30.00 3S.OO 850C 900C 950C 1000C Figure 3.16 Extracted Ion 77 (CFzCB^CHz) for Fluorinated AcryUc Polymer at 850,900,950 and 1000C. ^Kfc? *j r d aa i- cs ^ 3000001 aoooo o| ^ an -110.00 <1tS.7'0 to -11Q.70>s ff^rwl 60-2.0 600C ^\.tz> t-t f~i cS a n c fa 300 000 200000 100000 ^\,t=> 1-1 r d aa r* <=o SOOOOOl S.OO 10.00 1S.OO 20.00 25.00 30.00 35.00 Ior 1-IS.OO <11<a.7'0 to 11."7'0>: F=*IS4S-0 650C .0 0 10.00 15.00 20.00 25.00 30.00 3S.OO ior iis.oo ^le.^o to I-*S.T'O>; F=*s^yo.o 700C 100000^ 300000i -^<fc> LJ ri d <a n ^^ . ------,. . S.OO . 1i0--.--00f=^__1_S__.O__OA..-..l.^.2L...0^a-...0..^0.^AiJ2^S....O^--O --.3..0.,..0..0.,----3S,--.O--O, Ion II.00 <11S.7'0 to IIQ.7'03: F^IVIT'S.CS 750C -^.fc>l-i*-ci^r-tt 200000} 1 0 0 0 00 ^ ,0 0 10.00 1S.OO 20-00 2S.OO 30.00 35.00 lor* 11Q.OO <11S.7'0 to 11S.70>: ff^QO.O 800C Figure 3.17 Extracted Ion 119(*CFzCF3) for Fluorinated Acrylic Polymer at 600,650,700,750, and 800C. 35 Ab <-i n ci e r <=; e 25000 20000 1 5000 I 0000 5000 0 -ATti>mu^--nd--a^ ri ce y \ ^5.00 25000 20000 1 5000 1 0000 5000 ^%^ Timo--a. 0 t.^irf^ ^kfc? L> n cj a f* oe 5.00 , 7^. ,..,, 25000 20000 -1 5000 1 0000 5000 0 A"rtiomi- t^n--d = * Q - n c^ 25000 20000 3^1^. S.OO -1 5000 1 0000 SOOO -rim--^ 0 ^ Ion 1-1 9.00 <118.'7'0 to -l-IS.'T'O): F=IS/l8S.O ^ , 10^00 15^00 20 100 .25.00 30.00 3S.OO lor* -1-1Q.OO (lie.70 to I-IQ.-T'O): F*I^IQO.D ,,. ,, .,,----^*^----> -10.00 15.00 '.- i----f--.----.. ..I 2 , i 0 y^. ,^ .00 ^^ 4 ^f,r 25 , , ^ ^ ^ - i.fr'itfihn.ijni^Bflf^V'r'^. .00 30.00 ^ ^ ^ 35.00 ^ V- T 'T' rfi ^i'"^.** -^iM-T-WrtT^J^LJU-Ah^ -10^00 15^00 SO-00 25^00 30^00 35^00 lor* 1-1&-00 <1ie.-7-0 to 1 -t Q .TO): F=B^/1&-3-C^ , , , , ^,,^..,...^..,.,,^.,. Figure 3.18 Extracted Ion l^-CFzCFa) for Fluorinated AcryUc Polymer at 850,900,950, and 1000C. G8O0O0O0O0O0 -4-00000 2000000 -T-*m<---=*. 680000000000 -2+0000000000 0 j<^kb >-i n d ^ r" c;^ 060000000000 -240000000000 0 Afc>u rd ffi r* c 860000000000 420000000000 0 /^^.b i r"d e n cs 800000000000 400 200 00 00 0 0 Ct ^.00 5.00 lor* -13-1.00 <-130.yo to -tS-l.T'O): ls^^0-2-^ 10.00 ..A ILlJjULi,. liS.OO 20.00 255.00 30.00 3S.OO Ion -131.00 C-130.7-0 to 131.7-0>: FI\/ies.l=> 10.00 ...i, il..[lJ,4lli^.. -t S.OO 3.0'.00 2S loO 30.00 35.00 0.00 lor-t -131.00 <130.7'0 to 131.'7'0):P>1\^-7'0.0 10.00 ... !, ll,.!.., .,{.. IS.00 20.00 ZS.OO 30.00 35.00 lor 13-1.00 <13Q.7'0 to 13-1.70): r=IS/l'7'5-C? S.bo 10^00 15^00 20^00 25^00 30^00 35^00 Ion 131.00 <130.-7-0to 131.7 0 >; WISO.C3 S.OO 10.00 1S-00 20.00 25.00 30.00 3S.OO Figure 3.19 Extracted Ion 131('CF2CF=CF2) for Fluorinated Acrylic Polymer at 600,650,700,750, and 800C. 36 600C 650C 700C 750C 800C Figure 3.20 Extracted Ion 169(*CF2CF2CF3) for Fluorinated AcryHc Polymer at 600,650,700,750, and 800C. 3.2 Treated & Untreated Articles: PFOA, Fluoride, and Chloride Determination at 1000C The reactor effluent from combustion tests of the treated and untreated articles at a temperature of 1000C was analyzed for PFOA, fluoride, and chloride. No PFOA, fluoride, and chloride were detected. The detection limit of PFOA, fluoride, and chloride were 10 ng/L, 10 |lg/L, and 40 (ig/L, respectively. The net amount of samples gasified is tabulated in Table 3.4. Raw data including the report provided by Exygen are provided in Appendix B. Fluoride and chloride analyses for treated article combustion at 1000C were also conducted at UDRI to provide verification of the prior results provided by Exygen. The analyses were conducted using flow injection analysis colorimetry (QuikChem Method 10-109-12-2-A and 10-117-07-1-C for fluoride and chloride, respectively. See Appendix G for detail). The detection limits were 100 (ig/L for both fluoride and chloride. No detectable amounts of fluoride and chloride were observed. The net amount of sample gasified is tabulated in Table 3.4 and the analytical results are shown in Appendix B. 37 Table 3.4 Gasified Sample Masses. Sample Name Gasified Mass (ing) Untreated article 1 analyzed at Exygen Untreated article 2 analyzed at Exygen Untreated article 3 analyzed at Exygen Treated article 1 analyzed at Exygen 2.13 2.05 2.13 2.54 Treated article 2 analyzed at Exygen Treated article 3 analyzed at Exygen Treated article 1 analyzed at UDRI 2.66 2.47 2.47 Treated article 2 analyzed at UDRI 2.49 3.3 SiF4 Analysis from Fluorinated Acrylic Polymer Combustion Silicon tetrafluoride (SiF4) is not formed by sample combustion but through interaction between hydrogen fluoride (HF) and the reactor surfaces (fused silica). SiF4 demonstrates HF formation from fluorinated acrylic polymer combustion. Figures 3.23 and 3.24 show the integrated peak area of extracted ion 85 for fluorinated acrylic polymer combustion tests at low temperatures (600 to 800C) and high temperatures (850 to 1000C), respectively. A significant amount of SiF4 was observed for the fluorinated acrylic polymer combustion tests, and the integrated peak area increased with temperature. Table 3.5 and Figure 3.25 show temperature vs. integrated peak area normalized by gasified sample mass. The peak area increases with a slight S-shape, except at 850C. Because the pyroprobe temperature programming for the gasification is identical throughout the fluorinated acrylic polymer combustion tests, it is clear that HF formed by combustion reacted with fused silica on the reactor surfaces to form SiF4. A.b-ii-*de ncs^ 0000 4000 2000 0 5.00 10.00 s.oo <s4..7'o to ea..'7"o>; -i~ro-3i.o 1 S-00 20.00 NA. SZS.OO 30.00 35.00 600C 650C eooo-4000 2000 ADLinclartc:^ SOOO -000 2000 0 A-riDmL--jo--c--df=f-iinCG lor* ^^^SH^^^!,^. S.OO 10.00 Ion ^^SiSS^f^^^^. S.OO 10.00 85.00 <S-d..70 to QiS.'T'O: UTeS.D IS.00 20.00 25.00 30.00 S5.00 <e-*-'7-0 to SS.70>: t-ITTO.O 15.00 20.00 25.00 30.00 35.00 35.00 700C 7251:)C eooo4 an 8S.OO <0-t.'7"0 to S5.70>: 1-*T"7'3.0 40 00-j 2000 j U^JOlU ^''^f'*^*^ 0 5.00 10.00 15.00 20.00 25.00 30.00 35.00 'fH. 750C eoooj Ion aooo^ 2000-j0 T--.f-t*>it|-l--f^--- J-.j- Jy 5-00 10.00 S5.00 <S-'I.-'7'0 to e5."?'0>: U'T-7'S-O 15.00 20.00 2S.OO 30.00 35.00. Figure 3.21 Extracted Ion 85 (SiFs) for Untreated Article at 600,650,700,725, and 7500C. 38 Figures 3.22 and 3.23 show the integrated peak areas ofSiF4 extracted ion 85, for untreated and treated article combustion tests at 600, 650,700,725, and 750C, respectively. No significant ion 85 peak was observed for these materials, consistent with the low levels ofF present in these materials. 40001 2000d S.OO 1 0.00 S.OO (SA.7'0 to SS.7"0>;; TT~RGO0--S. 15.00 20.00 A 4 . 2S.00 30.00 3&.00 600C 650C 4000^ sooo| 0 l^*^w^^MUf^4 S.OO --.oooj | 2000 5.00 ii UiiiiiiiiiliMW.tK *-ooo| 300o| ^s.to*jr*cdB *^!^ S-00 000-| aooo-j lor* as.00 <s^..-7'o to e5.7'o>; -rrsies.D 1 0.00 15.00 20.00 Ju^A 25.00 30.00 Ion G5.00 <S-il..-yo to &S.-7'0>; -T-R-yO.C? 35.00 i o.oo IG.OO 20.oo 25.00 3o.oo Ion GfS.OO <8-4. T'O to SS-TO; -T=e7'S 35.00 10.00 -15.00 20-00 SS5.00 30.00 5.00 <S-.70 to 05.7'0>: Tf^'T-tS.D 35.00 700C 725C 750C S.OO 10.00 IfiS.OO 20.00 25.00 30.00 3f5.00 Figure 3.22 Extracted Ion 85 (SiFa) for Treated Article at 600,650,700,725, and 750C. ^*fc_*r*deanc=;^ 3000000 2000000 1000000 0 -^l3>u r*dCTt"-c? 3000000 | 2000000| 1000000| 0^-r----' 3000000 2000000 1000000 S.OO 5.00 5.00 Ion 85.00 <Q-4-.7-0 to 85.70>: 1=1\^I0-2-I=> 1 0.00 15.00 JL 20.00 25.00 30.00 lor* -10.00 S5.00 <84.7-0 to 85.'7"05: l=r^efflt.C> /vLl 15.00 20.00 25.00 30-00 Ion 10.00 85.00 <ei^-.-7-0 to QS.7-0>; IF'tS/1 -T'O - D X/LJI 15.00 20.00 25.00 30.00 3S.OO 35.C 35.00 3000000 2000000 1000000 5.00 Ion G.S.OO (S-4.y0 tfc> S5.'7'0>: l^ft^l'T^-C 1 0.00 1 CS.OO ^A 20.0Cp 25.00 30.00 3000000-1 200000o| 1000000^ / ^ Ion 8S.OO (Q-O-.-T-O to eS-7'0>; 1=>\^QO-0 J Figure 3.23 Extracted Ion 85 (SiFa) for Fluorinated Acrylic Polymer at 600,650,700,750, and 800C. 600C 650C 700C 750C 800C 39 ^.l=*^n <d e i~t<=<to -a-oooooo 3000000 52000000 ,A.ta*^r-te4*s>i-i<=<! -.000000 3000000 ssoooooo 1000000- ^htoLjri<dB 3000000 zoooooo t000000 ion 66.oo <s.-*.yo to &S.TO>; FMa.D i..OO -t 0.00 1 0.00 20-00 2S.OO 30.00 lor* e.00 <&-4-. T'O to S.7'0>; tfr^O.E=> 3S.OO -lo.oo -i.oo ao.oo saes.oo 30.00 lo*-* as.oo <s"*.-ro to ss.yo>; F'IVI&S.O 1/1 -i o.oo i es.oo sso.oo 5.00 30.00 3.oo 3G.OO 850C 900C 950C 1000C -4.00 0000 3000000 aoooooo I 000000 ion ss.oo <e.<i..'yo t^ es.'yo'); Fi\/i0'0-^-o CS.OO 10.00 s.oo 20.00 ass.oo 30.00 3es.oo Figure 3.24 Extracted Ion 85 (SiFa) for Fluorinated AcryUc Polymer at 850,900,950 and 1000C. Table 3.5 Integrated Peak Area of Ion 85 (SiFs) Normalized by Mass for the Fluorinated Acrylic Polymer. Temperature (C) Peak Area Mass (mg) Peak Area Normalized by Mass 600 5.85E+08 1.60 3.66E+08 650 9.07E+08 1.69 5.36E+08 700 1.51E+09 1.68 8.98E+08 750 2.13E+09 1.62 1.32E+09 800 3.27E+09 1.63 2.00E+09 850 2.43E+09 1.62 1.50E+09 900 4.30E+09 1.63 2.64E+09 950 4.93E+09 1.58 3.12E+09 1000 5.28E+09 1.61 3.28E+09 40 3.5 10" a *J .IiUn9 .w 1 U I----------1]----------] 1 c 3 0 c 1 2109 ............... 1.5 109 --....o...... 0 HO9 1 w > -... - . Q < > n 500 600 700 800 900 1000 1100 Temperature (C) Figure 3.25 Temperature vs. Integrated Normalized Peak Area of Ion 85 (SiF3). 3.4 Treated Article Gasification; XPS Analysis of Pyroprobe Cartridge The surface of the sample cartridge used for treated article gasification was analyzed by XPS to determine if there was fluorine on the sample cartridge surface after pyrolysis. Table 3.6 shows the relative percentage of atom surface composition obtained from XPS analysis for one blank cartridge and one sample cartridge. The sample (1.15 mg) was gasified with synthetic air specifically for this study using the same pyroprobe and procedure applied for the combustion tests. Only C, 0, and Si were detected showing evidence ofC=0, C-0, C-C, and C-H bonding. The location of fluorine in the XPS results is shown in Figures 3.26, 3.27 and 3.28. No fluorine (F) peak is evident in either spectrum.. The relative carbon composition increased while 0 and Si compositions decreased for the cartridge used for sample gasification due to deposition of organic compounds on the cartridge surface during sample gasification. Sample Table 3.6 Approximate Atom % Surface Compositions.________ C 0 Si Blank "Treated 1st -Treated 2nd C=0 1.6 4.8 5.2 C-0 1.9 9.1 9.5 C-C, C-H 11.2 40.5 55.0 60.7 33.9 23.1 24.6 11.8 7.2 * Sample cartridge for the treated article was analyzed twice. Figures 3.26,3.27, and 2.28 show XPS results for the blank cartridge, title first analysis Of the sample cartridge, and the second analysis of the same cartridge, respectively. 41 ill - ' Ifi? -q < - . , Counts M<=3 - 1\3 <U 4^. 01 0 o ' 1 1 1 1 X ^ "i (B , UJ -L 0 8 ^ 03 ^01 tf)t i, o oo 8 S ca 5' 3' ^ I'r- Sm o) 3 0 ^S" 3(DO ? S- ^ ^ TO 4L " o i - ^ Iia ro S ^s-o ^ $ ^^yu y ^ ^^-S-o -c-^ 0 ,f- J1 ^ ^- g5 f-- a) ^, Q i i i i Counts - ro0 '. ) M 4!>. CD W 0 0 ----,--------,--------,--------)--------,---- g > ,, i ^^ i (6 U 5 ~k" ^ <3o y ^ s 16 a w S W 1 g- ?? m yi I . 5' <D 0 i J s 3 y--^- 0 ; ; i ; , ' t ^ ?- --' s ^ ^. 0 .1. 0 % >- 0 r?> 1 8 --S5 C. r2 i 0 '11 i i x10 4 C r 0 0 \Wv^^\ si si 'wltA<41^wl ^'WM^H 0 -1200 -1000 -800 r -600 -400 Binding Energy (eV) -200 Figure 3.28 XPS Spectrum for Sample Cartridge (Second Analysis). 3.5 Telomer B Alcohol Combustion GC/MS Analysis In-line GC/MS analysis was conducted for Telomer B Alcohol thermal decomposition at 200 and 600C in order to confirm that ion 77 formation observed in the fluorinated acrylic polymer combustion tests was from decomposition of the "Telomer" (X-CH2CH2-CnF2n+i) functionality. Figure 3.29 shows extracted ion 77 (CF2CH=CHz) for Telomer B Alcohol thermal decomposition at 200 and 600C. The mass of sample gasified and the integrated peak area for ion 77 ("CFzCr^CHz) normalized by mass is presented in Table 3.7. The data suggests that compounds containing the 'CFzCH^H; fragment form in greater amounts with increasing temperature. Raw Data are provided in Appendix C. A'\ 3000C 3000C ^ooooo-] s.Oo ?-y-oo <-yo.-yo o -7-7-.yo>t -T-I-FS/ISBO.C ./1l.A/</-^. yy-oo <-y^--7-o *<9 T--y.7'o>s ~r-i_r^*^o.o 200C 600C aooooo-i .'^!^ Figure 3.29 Extracted Ion 77 (CF2CH=CH2) for Telomer Alcohol Combustion at 200 and 600C. Table 3.7 Sample Gasified and Normalized Integrated Peak Area of Ion 77 ('CFzCH^CHz). Temperature (C) Gasified Mass (mg) Normalized Peak Area 200 1.24 104114725 600 1.68 347271963 3.6 Treated & Untreated Articles: Off-line GC/MS VOC Analysis at 1000C VOCs from untreated and treated article combustion at 1000C were collected in a Tedlar bag and analyzed using off-line GC/MS analysis. Figures 3.30 and 3.31 show the total ion chromatogram of untreated and treated article combustion at 1000C, respectively. Table 3.8 shows the net amount of sample gasified. All six chromatograms are nearly identical. Three major peaks in each chromatogram correspond to air, COz, and water. No other significant peaks were observed for both untreated and treated articles, indicating that volatile fluorocarbons were not detected. 44 Abundance 2.S--07 2--07 TIC: VOCUT-1 .0 1.S--07 r--07 5000000 0 Ttrrte-->- Abundance z.oo 4.00 e.oo a.oo 10.00 12.00 it.oo ie.oo IB.OO 20.00 zz.oo Z.StX-07 2e*07 1 .Bo--07 10--07 5000000 0 ATlbmu --= nd ei n e e -TIC: VOCUT2.0 2.00 4.00 e.OO 8.00 10.00 12.00 14.00 16.00 1 B.OO ZO.OO 22.00 2.SB-1-07 2--'07 1 .Be--07 Ht--07 5000000 oi'r TIC: VOCLIT3.D i i i T'r |'-'"l^'~^~~' lT~^l~T'"''^''n'"'"''"T'l''l^''- 2-oo 4.00 e.oo a.oo 10.00 i2.oo 14.00 le.oo ------r. is-oo 2..01.0,101z.z1.1o1o Figure 3.30 VOC Analysis for Untreated Article Combustion at 1000C. Abundance 2.Se<-07 2e<-07 1 .5e<-07 1e*07 SOOOOOO 0 Tlme--- Abundance 2.00 2.5e*07 2e<-07 1.5s)7 1a<-07 5000000 0 Tlma-->Abundeince 1' 2.00 TIC: VOCTR1.0 11 1L 4.00 e.OO 8.00 10.00 12.00 14.00 16.00 1S.OO 20.00 22.00 TIC: VOCTR2.D ' 11 4.00 1 V. e.OO 8.00 10.00 12.00 14.00 16.00 1S.OO 20.00 22.00 2.5<-07 2e<-07 I.Ss-07 1e<-07 SOOOOOO n 1' g Ii 2.00 i ii |! Ii 4.00 TIC: VOCTR3.D , 1 i - 6.00 8.00 ' 10.00 12.00 14.00 16.00 IB.OO 20.00 22.00 Figure 3.31 VOC Analysis for Treated Article Combustion at 1000C. 45 Table 3.8 Net Mass of Sample Gasified. Sample_____Gasified Mass (mg) Treated Article 1 2.18 Treated Article 2 2.24 Treated Article 3 2.09 3.7 Treated & Untreated Articles: CO and COz Analyses at 1000C CO and CO; analyses from the combustion of the treated and untreated articles at 1000C were conducted using off-line GC/TCD analysis. Table 3.9 shows the flow rate monitored, which is used to calculate gas exhaust volume (mL) and the number of moles of CO and COz collected. Table 3.10 shows the concentration of CO and COz, number of moles of CO and CO; collected, number of mole gasified, and carbon recovery. Columns 2 and 3 in Table 3.10 show CO and COz concentrations in the sampling bag, which are normalized by the mass of gasified samples. The average COz concentration is almost identical for untreated and treated article combustion. The average CO concentration differs somewhat between untreated and treated article combustion. Columns 4 through 6 in Table 3.9 show the molar number of collected CO, COz and their summation, respectively. Column 7 in Table 3.9 shows the molar number of gasified carbon calculated by sample weight and the relative carbon weight ratio provided by DuPont. Column 8 of Table 3.9 shows the carbon recovery, which is calculated based on the molar number of carbon collected and carbon gasified. Raw data for the VOC, CO and COz analyses are provided in Appendix D. Nearly 100% carbon recovery was obtained for both untreated and treated articles. The slight overestimation of the carbon recovery may result from the estimation of gas exhaust volume based on inlet flow rates before the sampling and collection time. Table 3.9 Flow Rate Monitored for CO and COz Analysis (Base Information ___Uni_t ______Used for CO and COz Flow Rate Recovery in Table 3.10). Gasification Tot_al___T_ota_l Inlet 1 (mL/min) Inlet 2 (mL/min) Makeup Gas (mL/min) Total (mL/min) Time (sec) Time (min) Volume (mL) Untreated 1 6.8 8.7 4.2 19.7 53.39 4.89 96.33 Untreated 2 6.8 8.6 4.4 19.8 54.86 4.91 97.30 Untreated 3 6.8 8.7 4.3 19.8 51.18 4.85 96.09 Treated 1 6.8 8.8 4.4 20.0 68.10 5.14 102.70 Treated 2 6.7 8.8 4.5 20.0 66.87 5.11 102.29 Treated 3 6.8 8.9 4.5 20.2 62.20 5.04 101.74 Table 3.10 Carbon Recovery for Untreated and Treated Article Combustion at 1000C. Sample Normalized CO Cone. (ppm) Normalized CO, Cone. (Ppm) Total Gas Volume (mL) CO Collected (Mol) CO, Collected (Mol) Number of C Collected (Mol) Number of C Gasified (Mol) Carbon Recovery (%) Untreated 1 826 9712 96.33 7.09E-06 8.34E-05 9.05E-05 8.92E-05 101.4 Untreated 2 635 10165 97.30 5.66E-06 9.06E-05 9.62E-05 9.16E-05 105.0 Untreated 3 468 9756 96.09 3.85E-06 8.01E-05 8.39E-05 8.55E-05 98.2 Average 643 Treated 1 351 9878 9737 102.70 5.53E-06 4.08E-06 8.47E-05 1.13E-04 9.02E-05 1.17E-04 8.S8E-05 1.15E-04 101.5 102.2 Treated 2 448 9485 102.29 5.09E-06 1.08E-04 1.13E-04 1.13E-04 100.2 Treated 3 321 10326 101.74 3.38E-06 1.09E-04 1.12E-04 1.05E-04 106.8 Average 373 9849 4.18E-06 1.10E-04 1.14E-04 1.11E-04 103.1 4fi 3.8. PFOA Absorption Study 3.8.1 PFOA in Aqueous Solution The PFOA absorption and transport efficiency tests are summarized in Table 3.11 and 3.12. The absorption tests showed that PFOA recovery fluctuated between 100 to 280%. The PFOA HPLC/MS/MS analysis measurement required multiple dilutions for the sample to be within the calibration range of the instrument. In the course of these analyses, the dilutions may not have been correctly recorded and thereby would account for the observed fluctuation in recoveries. Test Absorption 1 Absorption 2 Absorption 3 PFOA Gasified (ng) 1.93 1.95 1.96 Table 3.11 Summary of PFOA Absorption Tests. W ater Volu me Jarl (mL) Jar 2 (mL) Jai-3 (niL) PFOA Concentiration Jarl (ng/L) Jar 2 (ng/L) Jar 3 (ng/L) Total PFOA (ng/L) 60 60 60 79700 1000 17700000 25671000 00 60 60 60 34600 2480 10500000 10848480 0 60 60 60 3640 14100000 16900000 31003640 Recovered PFOA (mg) 4.62 1.95 5.58 PFOA Recovery (%) 239.4 100.1 284.7 Due to the poor PFOA recovery results, Wickbold Torch analysis was conducted to evaluate PFOA recovery based on total fluorine. The experimental setup and methods are described in Appendix E and G, respectively. The results are shown in Table 3.12. The sample collected during the first absorption test (corresponding to Absorption 1 in Table 3.11) was analyzed. The results show 69.3% fluorine recovery. However, nearly 50% of the PFOA loaded was recovered in Jar 3, the rinseate from extraction of the absorption test apparatus. This indicates that significant PFOA condensation upstream of the sampling system occurred under the conditions of these tests. The protocol used for this study is described in Section 2.11. Table 3.12 PFOA Recovery as Fluorine (Wickbold Torch Analysis). [Sample Used: Absorption 1] Sample Sample Weight (1) (g) Water Volume (2)(mL) Fluorine Weight (3) (UK) Total Fluorine (3) x [(2)-(1)] (me) Jarl 2.9928 60 19.4 0.39 Jar 2 3.0200 60 1.2 0.02 Jar 3 2.9904 60 46.1 0.92 Total (mg) 1.34 Gasified (mg) 1.93 Recovery <%) 69.3 3.9 PFOA Transport Studies 3.9.1 PFOA Transport Study - Aqueous Sampling The transport efficiency test at 170C showed very poor recoveries and large fluctuations from 0.5 to 4.4%. The transport efficiency test at 300C showed improved yet still poor recoveries and smaller fluctuation (14.8 to 20.6%). The protocol used is described in Section 2.11. 47 Test Transport @170C1 Transport @170C 2 Transport @170C3 Transport @170C Blank Transport @300C1 Transport @300C 2 Transport @300C 3 Transport @300C Blank Table 3.13 Summary ofPFOA Transport Studies. ] ?FOA G lasified (ing) 1.68 Watfsr VolUI!ae Jarl Jar 2 1(mL) (mL) 65 60 PFC)A Concen)tration Jarl (ng/L) Jar 2 (ng/L) 72400 0 Total PFOA (ng/L) Recovered I FOA (") 72400 0.01 PFOA Recovery (%) 0.5 1.71 65 60 604000 0 604000 0.08 4.4 1.9 65 60 662000 74.4 662074 0.08 4.4 0 65 60 965 304 1269 0.00 N.A. 1.75 65 60 207000 0 994 2070994 1.81 65 60 298000 0 954 2980954 1.75 65 60 255000 20000 2570000 0 0 65 60 212000 510 212510 0.26 0.37 0.32 0.03 14.8 20.6 18.4 N.A. To further analyze these samples, two aqueous solution samples were analyzed for total fluorine using the Wickbold Torch method. The first sample was from the first jar from the second transport efficiency test at 170C. The second sample was from the first jar from the third transport efficiency test at 300C. The results are shown in Table 3.14. The fluorine recovery was determined to be 9.8% at 170C and 45.9% at 300C. The PFOA recovery as total fluorine shows better results than the direct PFOA measurement. However, the low recoveries coupled with evidence of PFOA condensation from the total fluorine analysis of samples obtained from the absorption tests strongly suggest PFOA condensation in the unheated silicone tube transport line. Table 3.14 Wickbold Torch Determination of Total Fluorine. Sample PFOA Gasified (mg) Weight ratio of F in PFOA Calculated Fluorine Gasified Total Fluorine in Jar F (%) Recovery (Ug) (Hg) First jar of second 1.71 0.688 1176.5 115.2 9.8 transport efficiency test at 170C First jar of third 1.75 0.688 1204.0 552.9 45.9 transport efficiency test at 300C Following the initial transport tests described above, steam was used to extract the ATRS system according to the protocol described in Section 2.11.1. 5 mL of water was introduced as steam for each extraction followed by 5mL of water to rinse the tubing which connected the ATRS to the water bubblers. The steam extraction was performed after the all PFOA transport efficiency tests shown in Table 3.13 48 were conducted. Table 3.15 shows the steam extraction results. Over 80% of the steam was recovered from the system, except for the third extraction. The total PFOA recovered from the steam extraction was only 0.178 mg. The majority of PFOA was extracted during the first steam extraction, m addition, the pyroprobe was rinsed with water and analyzed. A negligible amount of PFOA was recovered as shown in Table 3.16. The sum of all the steam extractions and pyroprobe water rinse accounts for less than 2% of the total amount of PFOA introduced into the ATRS test system in these tests. Table 3.15 PFOA Recovered from Steam Extraction. Steam Collected Rinse Total PFOA PFOA Extraction 1st 2nd 3"> 4* 501 Steam (mL) 4.068 4.135 2.195 4.336 4.285 Water (mL) 5 5 5 5 5 Amount (mL) 9.068 9.135 7.195 9.336 9.285 Cone. (ng/L) 19200000 217000 92100 79200 55600 Recovered (mg) 0.174 0.002 0.001 0.001 0.000 Total 0.178 Table 3.16 PFOA Rfcovered fr<im Pyropr0 be Rinsing. Pyroprobe Rinse Water PFOA PFOA Used Cone. Recovered (mL) (ng/L) (ue) 1st 100 4295 0.4 ^nd 100 602 0.1 3rd 100 0 0.0 4i> 100 0 0.0 5th 100 0 0.0 Total 0.5 3.9.2 PFOA Transport Study - Gas Phase Sampling The protocol for this test is described in Section 2.11.2. Table 3.17 shows integrated total ion peak area corresponding to PFOA. The first three areas were obtained from PFOA transported through the ATRS and the last three were obtained from direct injection of PFOA into the GC injection port. Two system blank runs were performed for the PFOA transport through the ATRS to confirm no sample carryover from the previous experiment. The first blank runs showed small amount of carryover and second blank runs show no carryover for all 3 samples. One system blank was performed for the direct injection of PFOA into the GC injection port and no carryover was identified from the blank run. The peak areas obtained from the blank runs were added to the peak area obtained from the first GC run as shown in Table 3.17. Each peak area was normalized by the gasified sample mass and the three determinations were averaged. Based on the average peak area, 74.3% of transport efficiency was obtained by taking the ratio of the Average Peak Area 1 over Average Peak Area 2. 74.3% is within generally accepted recovery criteria (70-130%, US EPA, 1996). Figures 3.32 and 3.33 show the total ion chromatogram for the PFOA transport through ATRS and GC injection port, respectively. 4Q ATRS Run #1 ATRS Run #2 ATRSRun#3 Direct GC 1 Direct GC 2 Direct GC 3 Peak Area from First GC Run (1) 684994647 673277175 814730308 966189956 1030933423 1033245273 Table 3.17 PFOA Peak Area. Peak Area Total Peak from Blank Run Area = (1) + (2) (2) 10510992 695505639 4069277 677346452 289003 815019311 Sample Mass (ing) (3) 0.44 0.45 0.45 Average Peak Area 1 0 966189956 0.45 0 1.031E+09 0.48 0 1.033E+09 0.45 Average Peak Area 2 Transport Efficiency (%) (Peak Area 1) -i- (Peak Area 2) x 100 Total Peak Area Normalized by Mass ^(1+2)^3] 1580694634 1505214338 1811154024 1632354332 2147088791 2147777965 2296100607 2196989121 74.3 /\t3undancQ le+OTi 8000000 6000000 4000000 2000000 0 -Tlm<--sA.E>LirtClanc6 l.t.OT-i 8000000 soooooo 4000000 2000000 0 -rime-- Abundance io-t-OT, 8000000 6000000 4000000 2000000 0 Tims--- Tlc: P^ATI ATRS RUI 4.00 ^ 6.00 a.00 10.00 12.00 14.00 16.00 4.00 i i| Sl \ e.oo Tlc: PFAT3.D a.00 io.oo 12.00 IA.OO 16.00 TIC: F>f=AT4.0 ATRS RUI ATRSRur 4.00 ; 6.00 a.00 10.00 12.00 14.00 1--'----'----T 18.00 Figure 3.32. Total Ion Chromatograms Obtained from PFOA Transport Test Through ATRS. 50 Ato u n d .4-0000001 ^. & Linda i .am-*-o~r i 1 - OT'^ ; : F 1=<3 C 1 .0 Direct GC 1 10.00 12.00 14.00 18.00 - I 0 : P F= <3 C; ; Direct GC 2 j<\.b>unclancei 1 .2-- 07 1 1 *-OTJ BOOOOOO 400000 0 2.00 14.00 18.00 TIC;; P- ^ <3 CS S 0 . Direct GC 3 Figure 3.33. Total Ion Chromatograms Obtained from Direct Injection. 3.10 PFOA Calibration Curve and Detection Limit Studies The mass of sample introduced and the corresponding peak area are tabulated in Table 3.18 and the calibration curve is shown in Figure 3.34. The extracted ion 131, which is the most abundant ion of the major PFOA ions, is shown in Figure 3.35 for 1.10,5.50,10.16, 50.80, and 100.40 p.g injection. PFOA appeared at a 16 min retention time. A secondary peak emerged for 50.80 and 100.40 (Ag injection; however, the mass spectrum shows a nearly identical pattern for the main and secondary peaks as shown in Figure 3.38. Both peaks were integrated and summed to determine the peak area. The secondary peaks at varying retention times may be attributed to the sorption and desorption in the detector due to the relatively large quantity and the high polarity of the analyte. Raw data for this study is presented in Appendix F. S1 Table 3.18 PFOA Mass vs. Corresponding Peak Area. PFOA Ion 131 Peak Area Mass Qlg) 1st 2nd Average 1.10 293383 456475 374929 5.50 2554771 2893790 2724281 10.16 5692993 5769835 5731414 50.80 28143180 23799422 25971301 100.40 50366258 45606352 47986305 PFOA (microgram) Figure 3.34. PFOA Calibration Curve. ^ Abundance 600000 Ion 131.00 (130.70 to 131.70): DL1 .D UO^lg 400000 200000 Time--> O Abundance 600000 -n- 5.00 10.00 15.00 20.00 25.00 30.00 35.00 Ion 131.00 (130.70 to 131.70): DL2.D 5.50 Ug 400000 200000 Time--> O^ Abundance 600000 400000 5.00 --i--i--[--i--i--r- 10.00 15.00 20.00 25.00 30^00 35.00 Ion 131.00 (130.70 to 131.70): DL3.D 10.16^g 200000 Time--> O^T-r-T-r-pr-r-i-i- .,,,.,. ^--^--.^.-^...^-^-.^-^--,.--?-,--j----,-..,. Abundance 5.00 10.00 15.00 20.00 25.00 30.00 35.00 Ion 131.00 (130.70 to 131.70): DL4.D 600000 !-[-- I 50.80 (lg 400000 200000 Time--> O Abundance 600000 5.00 10.00 15.00 20.00 25.00 30.00 35.00 Ion 131.00 (130.70 to 131.70): DL5.D 100.40 ng 400000 200000 Time--> O'T-i-i-7-j-r-r-i- ^- Figure 3.35. PFOA Extracted Ion (131) Chromatograms for 1.10,5.50,10.16,50.80, and 100.40 p-g. St Figure 3.36 shows the reference spectrum ofPFOA obtained from the NIST129K library (G1701BA Version B03.00, Agilent Technologies). The five most abundant ions shown in the reference spectra are 131 (-CFzCF^CFz), 69 (CF3). 31 (CF), 44 (CQz), and 93 (CsFs), in this order. Figure 3.37 shows the fall scan PFOA peak spectra for the 100.40,50.80,10.16, 5.50, and 1.10 |Xg injections. The spectra contained ions 131,69,31, and 93. These common ions were used to establish the PFOA detection limit. All of the PFOA peak spectra, from 100.40 to 1.10 p,g, show major ions with similar abundance ratio to the reference spectra. However, the spectra for the 1.10 p.g injection shows ion 18 as the third largest ion, which is not compatible with the reference spectra. Ion 18 is water, HzO, associated with background trace water in the test system. The PFOA limit ofquantitation (LOO) was established using extracted ion 131and is 1 u.g based upon 1 ng as the lowest standard of calibration. The limit of detection (LOD) is lower than the LOQ. PFOA fall scan spectrum for 1.10 p,g injection shows that the signal (131) to noise (S/N) ratio is more than 20. Therefore, LOD could be less than one sixth (1/6.67) of LOQ if S/N of LOD is defined as ca. 3:1. Based on the 1.10 (ig limit ofquantitation (LOQ), on a mass basis obtained in this study, the detection limit of gas phase PFOA concentration can be estimated. Typical gasification times were 20 to 30 sec for the articles and 30 to 40 sec for the polymer combustion tests. The gasification time of 30 sec provides 0.94 mL/sec x 30 sec = 28.20 mL synthetic air at 25C. The molar amount of 1.10 (AgPFOA is LlOxlO'6 / 414 = 2.66xl0"9 mol, which gives gas phase volume of: [2.66xlO-9(mol)x0.0821(atm-Vmol-K)x298K]/latmxlOOOmL/l = 65.1x10-" mL at 25C. 1 (Xg PFOA can produce gas phase concentration of59.2xl0"6/28.2 = 2.31 ppmby volume. Therefore, the gas-phase LOQ and LOD are 2.31 and ca.. 0.35 ppm, respectively. jid, X- ^ 1 '-,'ao ".,<('-; so .I'BoiaSg 'WAo =-*o S&S zoo1-aSS a ^ti 320 s.-.o Figure 3.36. PFOA Reference Spectra Obtained from NIST129K Library. 54 11:a- *,-,, :r :l: ^s-ss^ -^j ,LT,Ll-, ^ ^12..^^ 4--.!- ". i. i i -?. ii , -... --- 100.40 ng 50.80 |J,g 10.16 ng 5.50 ng ""ssTM"*' - ' <-> l-lOng Figure 3.37. PFOA FuU Scan Spectra for 100.40,50.80,10.16,5.50, and 1.10 |J.g Injection. "iS 16.2mm r .T, i, U^i .1 r TSC* in "n -. C. T 1 BO ;--:.i=- ,a.c.,-o?J-M. Ja!" > SXAO : 16.6min V^L fflic: Figure 3.38. PFOA Full Scan Peak Spectra at 16.2 and 16.6 min for 100 p,g Injection. 3.11 PFOA Analysis from Combustion Tests of the Treated & Untreated Articles and the Fluorinated Acrylic Polymer Using In-line GC7MS Analysis The ion chromatograms obtained from the actual treated and untreated article combustion tests shown in Section 3.1 were examined to identify the potential existence and quantity of PFOA. Ion 131 was selected for this analysis because it was the largest based on the calibration work in Section 3.9 and the standard reference library spectrum. Figures 3.39 and 3.40 show extracted ion 131 chromatograms for the treated and untreated article combustion tests at 600, 650,700, 725, and 1000C. The elution time between 14 and 18 min was monitored because this is where PFOA is expected to elute under these GC conditions. No PFOA peak was detected at a limit of detection of 0.35 ppm. Figures 3.41 and 3.42 show extracted ion 131 chromatograms for the fluorinated acrylic polymer at 600 to 800C and 850 to 1000C. Peaks appear at 16.35,17.10,17.70 and 17.95 min at temperatures of 600, 650,700, and 750C. None of these peaks are for PFOA based upon evaluation of their mass spectra which are shown in Figure 3.43. The peak at 16.35 min is tentatively identified as CeHFis, based on the NIST library. None of the other peaks correlated with a reference spectrum in the NIST library. The re-examination of the ion chromatogram for the actual combustion tests shows that there is no indication of PFOA formation at the sub-ppm level for the three samples studied at the temperature between 600 to 1000C with 85% excess air. ^ BOOOj BOOO-J ,600 ^ -i i..oo aooo 0000 -4-000 zooo ja<fcjr^clj 1 4.00 aooo aooo 4000sooo 14. so I 4. BO i s.oo i a. so i a. oo i o-aso ^vA,,-,..^^ - y.oo ion iai.00 <i &o.7"o ca -i ;a i . yo >. T I'^Ges.D 650C IB. 00 i G.OO > a.ao IT. oo i y.co 700C imiri lai-oo (1^0,'yo to ia>"i -yo>i "rrsiya. ^ -A. 725C i j*.oo aooo' BOOO a-OOO aooo' 14. eso i cs.oo i a. so i a.oo i ion -i3i.oo ci^O.yo to -iat.7 -ly.oo <-1 .0 fy.oo B-tSO 1 y.OO - 'T'.SO noooc Figure 3.39. Extracted Ion 131 for Treated Article from 14 to 18 min Retention Time at 600,650, 700,725, and 1000C. A. t=* fcji n d is 4000 I 2000-1 lort -131.00 <130.70 to 131.7'0>: U-TSO-a.C 600 "C jc^bLjnclfii 6000 -4000 2000 14.00 6000 4-000 2000 14. so 131 .00 <1 30.7'0 to 131 .70>: LJTTe i s.oo t e 131 .00 <1 S 17.00 IT.SO 650C 700C 6000 4000 2000 .A to t-i n el e 1 4.00 14; SO 131.00 <130.7'0 t= 131.70>; l-*T"7"3.t3 1 S.OO 1 S'.GO ' 1 6:00 I 6; SO 1 7".00 1 T'.SO 725C 'r 1000C eooo 4000 2000 131.00 C130.70 to 131.7'0>: t_-TCBS-1 . C* 14. SO 1 S.OO 1 S-SSO 16.00 16.SO 1 T. 00 17-. SO Figure 3.40. Extracted Ion 131 for Untreated Article from 14 to 18 min Retention Time at 600,650, 700,725, and 1000C. ^7 4-00000 300000 200000 100000 *00000i 2000001 1000001 ion 1 31.00 <i SO.'T'O DO 131 .'ro>f FTwqeo-sz.c s.so ic.oo ia.5o ^ i T-.OO S-1 .00 <1 S0.70 to 1 St -70>; IF>vlSS.O A i 7 .so i600"C 6500C 3.00 1S.KO 17.00 17.SO 700C *t"l 13.1 .00 <t S30.70 Co 1 3^ -70>i F'tvIT'0-0 soooool 1000004 1-.00 43.00000000001I 200000 I 1-.(SO 1S.OO Ion I 31 .00 <1S0.7 3.60 t'r.c 1 -70>; Frrt7tS-0 750C jc^fcn-<i-cta 1 4 .00 1 4. .SO I 5 .00 50 16.00 1 .'7'0>; Ff^e.0.0 800C 2000001 1000004 S.OO 1 CS.GO 17'.00 Figure 3.41. Extracted Ion 131 for Fluorinated Acrylic Polymer from 14 to 18 min Retention Time at 600,650,700,750, and 800C. .A, ton ri dam-to 850C sooo 2000 .,).. AA ,...----... ^u J^f ^ ,, . ^..1^-lh.^ J-. 900C ^ s-t .00 <-i ao.70 < -i -f. yo>; TMr^sc*. = . .,,-^^.A ^.^..^..^^..^..^,.^^^.^ .-..j...^.^. .^a^s^-,'-. 950C 30 <ta0.70 i i . yc>; F"r^*ro. tai .00 <i so.'yo ' 00 yo>; irw4^Q-ai. i -l7.0 1000C Ij ^A.{. ^^^ ,, ^ ..Ji^..^A.^., .. ..{.^^t.,.,-^ ,.f, ,,..^.^. Figure 3.42. Extracted Ion 131 for Fluorinated Acrylic Polymer from 14 to 18 min Retention Time at 850,900,950, and 1000C W *0000 16.35 min ,t 4so.11 sfa0o0c*^- 1 'T^*?-''''SZBO 300 -. =oa.?3?"a9^i=ag3o,s*aa aso 4-00 .q^ta^n^. eso 17.10mm l- j _ -^ "--" 'L'.. -->--^'uj i' 1 , .jr-- t-eia" 17.70 min - *S1 ff-^"*^,A^^^-a-_ ? -* o--.SKS.^syBt ^,.^,c?>.aa ' -".a^S" 17.95 min 1 1 ""> ,'J.t^ 'cl * -i^ST-, iTM ^ IcfRKaSa.'afSSSQa.K'sstiLs.s-.sua.'EtSteaassQSSs'-jis.-s Figure 3.43. Spectra for the Peaks at 16.35,17.10,17.70, and 17.95 min at 600C in Figure 3.41. W 4. Discussion The purpose of this study was to investigate the thermal degradation of a polyester/cellulose fabric substrate ("article") treated with fluorotelomer-based acrylic polymer under laboratory conditions conservatively representing typical municipal waste combustor conditions of time, temperature, and excess air level. The treated article is reasonably expected to be present in municipal waste as discarded textile or paper. Therefore, the principal focus of this work was to determine the environmental fate of the treated article when it is incinerated. Supplementary studies examined an untreated article, the fluorotelomer-based acrylic polymer, and Telomer B Alcohol raw material to assist in the interpretation of the experimental observations for the treated article. The test protocols used were similar to those developed for recent testing offluorinated materials (Yamada and Taylor, 2003, Graham, 2002). Thermogravimetric analysis was used to define the gasification conditions. Thermal experiments were then conducted at non-flame reactor temperatures from 600 to 1000C for a mean, gas-phase residence time of 2.0 sec. 85% excess air was used for all experiments. The studies emulated typical municipal waste incinerator combustion conditions with an average temperature of 1000C or greater over approximately 2 sec residence time (Giraud, 2004). Combustion tests for the treated article, the untreated article, and the fluorotelomer-based acrylic polymer were completed. The following objectives were addressed: 1) determination of the temperature for 99.9% conversion, 2) determination of major products of incomplete combustion at 1000C for the treated and untreated article, 3) determination of carbon mass balances at 1000C for the treated and untreated article, 4) determination of the concentration ofPFOA in the effluent from all tests, and 5) determination of the concentration of fluoride ion in the 1000C tests for the treated and untreated articles. The temperature for 99.9% destruction of the treated and untreated articles was 725C. This temperature regime (700-750C) for 99.9% conversion is consistent with the results of prior tests of hydrocarbonbased materials using UDRI thermal instrumentation systems (Dellinger, et al. 1984; Dellinger, 1989; Taylor, et al. 1990). The temperature for 99.9% destruction ^99.9) of the fluorotelomer-based acrylic polymer was 1000C. The T99.9 value for the fluorotelomer-based acrylic polymer was slightly higher than that measured for other fluorinated materials using the same experimental apparatus (Graham, 2002). The difference may be related to the levels of excess air present in the respective combustion tests. Combustion tests with the fluorotelomer-based acrylic polymer used 85% excess air, while previous tests with other fluorinated materials employed considerably higher excess air levels. Excellent carbon mass balances were obtained from the combustion tests of the untreated and treated articles (101.9 and 103.6%, respectively) at 1000C. The only product of incomplete combustion that was observed under these conditions was carbon monoxide. Fluorinated organic byproducts were not observed via GC/MS in the combustion tests of the treated and untreated articles. In-line GC/MS was employed to determine the presence of heavier, less volatile fluorinated byproducts. None were identified. Additionally, off-line GC/MS was employed to determine the presence of volatile fluorinated byproducts in the gas exhaust from the 1000C tests of the treated and untreated articles. None were identified. Combustion tests of the fluorotelomer-based acrylic polymer were conducted to facilitate interpretation of the treated article combustion results. At 1000C, 99.9% destruction of the polymer was observed. Based upon this result, the fluorotelomer-based acrylic polymer would be destroyed under typical municipal incinerator conditions. Analysis of the reactor effluent from additional combustion tests of the fluorotelomer-based acrylic polymer indicated the formation of a variety of compounds at temperatures ^n below 1000C. Many of these compounds could not be identified using either the NIST mass spectral library or manual mass spectral interpretation. As a result, a limited number of combustion experiments were conducted on the Telomer B Alcohol raw material to try to determine the origin of these unidentifiable peaks. The experiments confirmed that selected ions were the same for the polymer and alcohol indicating their origin was indeed from the telomer functionality. Potential volatile combustion byproducts from the combustion of the fluorotelomer-based acrylic polymer were not analyzed. Of additional interest was to determine whether PFOA was formed as a result of combustion of the treated article to determine if incineration of treated articles may be a source of PFOA in the environment. Analysis for PFOA in combustion tests of the treated and untreated article at 1000C using both HPLC/MS/MS and in-line GC/MS were conducted. No detectable level of PFOA was determined. It can therefore be concluded that under typical municipal waste incineration conditions no significant quantity of PFOA would be formed from the incineration of a textile or paper substrate treated with a fluorotelomer-based acrylic polymer. In addition, transport efficiency tests for PFOA using aqueous sampling (followed by HPLC/MS/MS results) and gas-phase sampling (followed by in-line GC/MS analysis) were conducted. Aqueous sampling with HPLC/MS/MS analysis produced transport efficiencies of less than 20% using ATRS reactor and transfer line temperatures of 170C. Alternatively, in-line GC/MS tests using ATRS reactor and transfer line temperatures of235C produced transport efficiencies of greater than 70% (determined by dividing the ATRS PFOA response by the response obtained by direct injection of PFOA into the gas chromatograph). A plausible PFOA loss mechanism during the aqueous sampling transport tests may have involved absorption onto the unheated silicone transfer line tubing between the ATRS vent and the bubblers (see Fig. 2.15). The basis for this hypothesis was the strong interaction observed between PFOA and the DB-5 capillary columnsupport (phenyl-methyl siloxane) during the in-line GC/MS analysis and the evidence for PFOA condensation in the absorption and transport tests. Cryogenic temperatures were not required to trap PFOA. PFOA was effectively trapped using this column at a temperature of40C, thus indicating a strong interaction between the capillary column support and the analyte of interest. Based upon the combustion product analyses, it was clear that carbon-fluorine bonds were severed at 1000C. This would result in the formation of fluorine atoms [F], Fluorine atoms are highly reactive and would be expected to form hydrogen fluoride [HF] by reaction with hydrogen available in the combustion matrix. Analysis for fluoride ion (indicative ofHF formation) in combustion tests of the treated and untreated article at 1000C by trapping the gaseous effluent in aqueous bubblers followed by sampling and ion chromatography indicated fluoride [F"] below analytical detection limits. Subsequent examination of different sections of the experimental apparatus provided clues as to what happened to the fluoride generated from combustion. XPS analysis of the pyroprobe cartridges used to contain the test sample did not indicate me presence of fluorine on the surface. Removal and visible examination of the high-temperature reactor did, however, indicate significant etching of the reactor surface, most notably downstream of the midpoint of the reactor. This is very likely due to the reaction of hydrogen fluoride (HF) with the silica groups (Si0i, SiOH) of the reactor surface. Strong evidence confirming this interpretation was obtained from in-line GC/MS total ion chromatograms from the combustion of the fluorotelomer-based acrylic polymer at temperatures between 600 and 1000C. Silicon tetrafluoride (SiF4) was observed as a byproduct in these tests. The signal response for SiF4 showed a near-linear increase with increasing temperature, consistent with increasing yields ofHF at higher temperature arising from carbon-fluorine bond breaking. SiF4 has been observed in previous combustion tests of highly fluorinated materials using high-temperature fused silica reactors (Yamada and Taylor, 2003, Graham, 2002). In the test system, carbon-fluorine bond breaking does occur. In summary, the fluoride formed from carbon-fluorine bond breaking reacts with the silica surface of the test apparatus to form silicon tetrafluoride. ^1 5. Conclusions This study reports the first known studies to investigate the thermal degradation of a polyester/cellulose fabric substrate ("article") treated with a fluorotelomer-based acrylic polymer under laboratory conditions conservatively representing typical municipal incineration conditions of time, temperature, and excess air level. The treated article is reasonably expected to be present in municipal waste as discarded textile or paper. Therefore, the principal focus of this work was to determine the environmental fate of the treated article when it is incinerated. Laboratory-scale incineration studies of the treated article, untreated article and the fluorotelomer-based acrylic polymer were conducted. Combustion tests from 600-1000C for gas-phase residence times of 2.0 sec and excess air levels of 85% indicated that 99.9% destruction was achieved at temperatures of725C (treated and untreated article) and 1000C (fluorotelomer-based acrylic polymer). Analysis of the reactor ef&uent indicated that laboratory-scale incineration of these materials does not emit detectable levels of PFOA. Aqueous sampling (followed by off-line HPLC/MS/MS analysis) and in-line GC/MS analysis was used to analyze for PFOA. Transport efficiency testing indicated the in-line sampling to be the most accurate sampling method. The detection limit for PFOA analysis using in-line sampling followed by GC/MS analysis was 0.35 ppmv in the gas phase. Excellent carbon mass balances were obtained from the incineration tests of the treated and untreated articles at 1000C. Fluorinated combustion byproducts were not observed for combustion of these samples under these conditions. Attempts to recover fluorine from the combustion tests as HF were unsuccessful. Fluoride formed appears to have reacted rapidly with the silica surfaces of the test system. The detection of SiF4 in the reactor effluent is a strong indication of the likelihood of this interaction. These results demonstrate that the polyester/cellulose fabric treated with a fluorotelomer-based acrylic polymer is destroyed and no detectable amount of PFOA is formed under typical municipal incineration conditions. Therefore, textiles and paper treated with such a fluorotelomer-based acrylic polymer disposed of in municipal waste and incinerated are expected to be destroyed and not be a significant source of PFOA in the environment. fi? 6. References ASQ (American Society for Quality). 1994. Specifications and Guidelines for Quality Systesm for Environmental Data Collection and Environmental Technology Programs. ANSI/ASQC E4-1994. Milwaulkee, WI. Banks, R.E., Smart, B.E., and Tatlow, J. C. (Eds.), Organofluorine Chemistry: Principles and Commercial Applications, Plenum Press, New York, 1994. Dellinger, B., Torres, J., Rubey, W., Hall, D., Graham, J., and Cames, R., Hazard. Waste Hazard. Mater., 1984,1,137. Dellinger, B., in Hazard Assessment of Chemicals Current Developments. Vol. 6, J. Saxena, ed., Hemisphere Publ. Corp., Washington, DC, 1989. Dimitrov, S.; Kamenska, V.; Walker, J. D.; Windle, W.; Purdy, R.; Lewis, M.; Mekenyan, 0., SAR and QSAR in Environmental Research (2004), 15(1), 69. Giraud, R., "Combustion Operating Conditions for Municipal and Medical Waste Incinerators in the U.S.," 2004, in preparation. Graham, J., Overall Thermal Oxidation Testing ofLodyne 2010 and a Paper Sample Treated With Lodyne 2010, Final Report Ciba Specialty Chemicals Corporation, November 2002. Hekster, Floris M.; Laane, Remi W. P. M.; de Voogt, Pirn, Reviews of Environmental Contamination and Toxicology (2003), 179, 99. Kissa, E., FluorinatedSurfactants and Repellents," Marcel Dekker, New York, 2001. Ohtani, H; Tsuge, S., "Degradation Mechanisms of Condensation Polymers." Polymers in applied Pyrolysis Handbook" Marcel Dekker", New York. Radlein, D.; Piskorz, J.; Scott, D., Fast Pyrolysis of Natural Polysaccharides as a Potential Industrial Process, JAAP (1991), 19,41. Schultz, Melissa M.; Barofsky, Douglas F.; Field, Jennifer A., Environmental Engineering Science (2003), 20(5), 487. Stock, Naomi L.; Lau, Fiona K.; Ellis, David A.; Martin, Jonathan W.; Muir, Derek C. G.; Mabury, Scott A., Environmental Science and Technology (2004), 38(4), 991. Taylor, P.H., Dellinger, B., and Lee, C. C., Environ. Sci. Technol., 1990, 24,316. Taylor, P. H.; Tirey, D. A.; Dellinger, B., "The High-Temperature Pyrolysis ofHexachloropropene: Kinetic Analysis of Pathways to Formation ofPerchloro-arylbenzenes," Combustion and Flame (1996), 105.486. Taylor, P. H.; Tirey, D. A.; Dellinger, B. "The High Temperature Pyrolysis of 1,3-Hexachlorobutadiene," Combustion and Flame (1996), 106. 1. fil Taylor, P. H.; Tirey, D. A.; Dellinger, B., "A Comprehensive Kinetic Model of the High Temperature Pyrolysis ofTettachloroethene," Combustion and Flame_(1996) 104.260. Taylor, P. H.; Tirey, D. A.; Rubey, W. A.; Dellinger, B-, "Detailed Modeling of the Pyrolysis of Trichloroethene: Formation of Chlorinated Aromatic Species," Combustion Science and Technology, (1995) 101.73. Tirey, D. A.; Taylor, P. H.; Kasner, J. H.; Dellinger, B., "Gas Phase Formation of Chlorinated Aromatic Compounds from the Pyrolysis ofTetrachloroethylene," Combustion Science and Technology (1990), 74. 137. U.S. EPA. EPA Requirements for Quality Assurance Project Plans (EPA QA/R-5). EPA.240/B-01/003. Office of Environmental Information. Washington. D.C. U.S. EPA Method 8000B, Section 8.4.9, p 39, "Determinative Chromatographic Separations", revision 2, 1996. Wehrmeier, A.; Lenoir, D.; Sidhu, S. S-; Taylor, P. H.; Rubey, W. A.; Kern-up, A.; Dellinger, B., "Role of Copper Species in Chlorination and Condensation Reactions of Acetylene," Environmental Science & Technology (1998), 32,2741. Yamada, T. and Taylor, P. H., "Laboratory Scale Thermal Degradation ofPerfluoro-octanyl Sulfonate and Related Precursors," Final Report, 3M Company, UDR-TR-03-00044, July 2003. M. Appendix A Experimental Condition (Temperature, Flow Rate, and Pressure) and Total Ion Chromatograms for In-line GC/MS Analysis A-l Appendix A FIGURE LIST OF FIGURES Al Total Ion Chromatogram for Untreated Article Combustion at 600, 650,700,725,750,750 (duplicate), and 1000C A2 Total Ion Chromatogram for Treated Article Combustion at 600, 650,700, 725,750,750 (duplicate), and 1000C A3 Total Ion Chromatogram for Fluorinated Acrylic Polymer Combustion at 600, 650, 700,750, 800, 850,900,950,1000, 1000 (duplicate), and 1000C (triplicate) PAGE A-7 A-8 A-9 LIST OF TABLES TABLE___________________________________________PAGE Al Flow Rate at Different Temperature A-3 A2 Experimental Condition of Untreated Article Combustion Test A-4 (Before and After) A3 Experimental Condition of Treated Article Combustion Test A-5 (Before and After) A4 Experimental Condition of Fluorinated Acrylic Polymer Combustion A-6 Test (Before and After) A-2 Table Al. Nominal Flow Rate at Different Temperatures Temp (C) Inlet 1 (mL/min) Inlet 2 (mL/min) 600 12.8 6.4 650 12.1 6.1 700 11.5 5.8 725 11.2 5.6 750 11.0 5.5 800 10.4 5.2 850 10.0 5.0 900 9.6 4.8 950 9.2 4.6 1000 8.8 4.4 A-3 Table A2. Experimental Condition of Untreated Article Combustion Test (Before and After) Sample' (befaft) SetT F. R. 1" F.R.2" T1* T2 T3 T4 T5 T6" T7" 1?TQS1 C mL/min mL/min C C C C C C C atm Blank (bef) 600 12.8 6.4 Blank (aft) 600 12.9 6.5 UT 600 12.9 6.4 UT 600 12.9 6.4 Blank 650 12.2 6.0 Blank 650 12.1 6.1 UT 650 12.1 6.1 UT 650 11.9 6.0 Blank 700 11.4 5.7 Blank 700 11.3 5.8 UT 700 11.5 5.7 UT 700 11.4 5.7 Blank 725 11.3 5.7 Blank 725 11.1 5.7 UT 725 11.3 5.6 UT 725 11.1 5.5 Blank 750 10.9 5.6 Blank 750 10.9 5.5 UT 750 10.9 5.5 UT 750 10.9 5.5 Blank 750 10.9 5.6 Blank 750 10.9 5.5 UT 750 . 11.1 5.6 UT 750 11.0 5.6 Blank 1000 8.9 4.4 Blank 1000 8.6 4.2 UT 1000 8.8 4.4 UT 1000 8.9 4.4 301 300 325 601 345 305 -125 A.P. 299 301 322 600 340 301 -130 A.P. 300 301 309 601 328 300 -125 A.P. 300 300 309 600 330 297 -130 A.P. 300 300 315 651 343 303 -125 A.P. 299 300 318 651 349 300 -127 A.P. 299 300 324 650 353 312 -125 A.P. 300 300 325 625 357 306 -130 A.P. 300 300 343 701 382 315 -125 A.P. 300 301 343 702 380 313 -130 A.P. 300 300 345 702 384 314 -125 A.P. 300 300 346 702 386 311 -128 A.P. 299 301 377 726 416 295 -125 A.P. 299 300 377 726 417 295 -128 A.P. 299 301 375 725 413 297 -125 A.P. 301 302 374 724 415 299 -127 A.P. 299 300 331 750 376 295 -125 A.P. 299 299 340 750 380 297 -125 A.P. 300 300 366 750 414 313 -125 A.P. 301 301 368 750 414 310 -129 A.P. 299 300 331 750 376 295 -125 A.P. 299 299 340 750 380 297 -125 A.P. 300 299 347 750 388 297 -125 A.P. 300 301 349 749 391 298 -128 A.P. 300 301 496 1000 584 306 -125 A.P. 299 301 507 1001 592 362 -127 A.P. 302 301 529 1000 611 406 -123 A.P. 301 301 532 1000 611 406 -123 A.P. " Conditions were monitored and logged before and after the experiment. Blank: blank experiment before combustion, UT: untreated article b Reactor set temperature c Inlet 1 flow rate d Inlet 2 flow rate e Measured temperature at each position f Reactor pressure, AP: atmospheric pressure A-4 Table A3. Experimental Condition of Treated Article Combustion Test (Before and After) Sample' (bef/aft) IW SetT" F. R. 1 F. R. 2" T16 T2" T3" T46 T5" T6" T7" C mL/min mL/min C C C C C C C atm I I Is>-, Blank (bef) 600 12.8 6.3 Blank (aft) 600 12.9 6.3 TR 600 12.8 6.3 TR 600 12.8 6.4 Blank 650 12.0 6.2 Blank 650 12.1 6.2 TR 650 12.0 6.2 TR 650 12.0 6.2 Blank 700 11.4 5.7 Blank 700 11.5 5.7 TR 700 11.4 5.9 TR 700 11.5 5.8 Blank 725 11.3 5.5 Blank 725 11.2 5.4 TR 725 11.2 5.5 TR 725 11.2 5.4 Blank 750 10.9 5.6 Blank 750 10.9 5.6 TR 750 11.0 5.6 TR 750 10.9 5.6 TR 750 11.0 5.5 TR 750 10.9 5.5 Blank 1000 8.9 404 Blank 1000 8.9 4.5 TR 1000 8.8 4.4 TR 1000 8.9 4.5 300 301 341 600 360 305 -125 A.P. 299 300 320 600 334 297 -130 A.P. 299 299 313 599 327 298 -125 A.P. 299 300 315 601 324 300 -125 A.P. 300 299 309 649 332 305 -125 A.P. 300 300 311 650 335 305 -128 A.P. 300 301 312 650 335 311 -125 A.P. 299 301 312 651 338 303 -123 A.P. 299 300 326 700 360 308 -125 A.P. 299 300 328 702 364 311 -128 A.P. 299 301 333 701 365 319 -125 A.P. 300 299 339 700 374 306 -128 A.P. 301 301 372 727 411 295 -125 A.P. 301 302 374 727 413 294 -126 A.P. 300 302 373 725 410 298 -125 A.P. 299 301 374 724 411 299 -123 A.P. 299 299 349 751 391 298 -125 A.P. 300 300 351 751 395 299 -130 A.P. 300 299 354 750 396 299 -125 A.P. 300 300 354 751 398 297 -128 A.P. 300 300 356 750 398 299 -125 A.P. 299 300 356 751 399 297 -125 A.P. 302 300 532 1001 611 425 -125 A.P. 299 299 533 1000 612 419 -125 A.P. 299 301 534 1002 612 430 -125 A.P, 299 300 535 1001 614 424 -127 A.P. a Conditions were monitored and logged before and after the experiment. Blank: blank experiment before combustion, TR: treated article b Reactor set temperature 0 Inlet 1 flow rate d Inlet 2 flow rate e Measured temperature at each position f Reactor pressure, AP: atmospheric pressure A-5 Table A 4. EX(erimentail Condition of 3Fluoriniated A(srylic P olyrneiCombiustion'rest (Befo:re and.After) Sample' (bef/aft) Set I* F.R-l" F.R.2" Tl' T2' T3" T46 T5 T6 T7 Pres^ C mL/min mL/min "C C C C C C C atm Blank (bef) 600 12.8 6.5 Blank (aft) 600 12.7 6.4 PM 600 12.7 6.3 PM 600 12.9 6.3 Blank 650 12.1 6.1 Blank 650 12.0 6.1 PM 650 12.2 6.2 PM 650 12.1 601 Blank 700 11.5 5.7 Blank 700 11.6 5.8 PM 700 11.4 5.9 PM 700 11.5 5.8 Blank 750 11.0 5.4 Blank 750 10.9 5.4 PM 750 11.0 5.4 PM 750 10.9 5.4 Blank 800 10.4 5.2 Blank 800 10.6 5.1 PM 800 10.4 5.2 PM 800 10.4 5.1 Blank 850 10.0 5.0 Blank 850 10.0 5.0 PM 850 10.1 5.0 PM 850 10.1 5.0 Blank 900 9.7 4.7 Blank 900 9.6 4.7 PM 900 9.7 4.7 PM 900 9.6 4.7 Blank 950 9.2 4.7 Blank 950 9.3 4.7 PM 950 9.3 4.7 PM 950 9.2 4.7 Blank 1000 8.9 4.4 Blank 1000 8.9 4.4 PM 1000 8.9 4.5 PM 1000 8.9 4.5 PM 1000 8.9 4.5 PM 1000 8.9 4.5 PM 1000 8.8 4.5 PM 1000 8.9 4.5 250 250 304 602 334 305 -125 A.P. 251 250 299 600 327 312 -125 A.P. 250 250 295 599 314 309 -125 A.P. 250 250 293 599 313 306 -127 A.P. 251 251 295 651 328 295 -125 A.P. 249 249 294 650 329 297 -128 A.P. 250 250 295 650 330 308 -125 A.P. 250 250 295 650 330 301 -128 A.P. 249 251 307 700 357 307 -125 A.P. 250 250 310 702 357 303 -124 A.P. 251 251 314 700 358 310 -125 A.P. 249 251 314 701 360 309 -128 A.P. 249 250 318 750 374 312 -125 A.P. 249 251 323 750 379 311 -125 A.P. 250 251 331 750 385 317 -125 A.P. 249 251 332 748 387 303 -127 A.P. 251 250 356 801 416 310 -125 A.P. 251 252 357 800 420 307 -126 A.P. 251 250 361 800 423 305 -125 A.P. 250 251 362 800 424 310 -126 A.P. 251 250 361 849 436 296 -125 A.P. 251 251 369 850 444 296 -128 A.P. 251 250 388 851 458 318 -125 A.P. 249 250 390 850 462 315 -127 A.P. 250 250 411 900 491 321 -125 A.P. 250 252 414 899 492 326 -128 A.P. 251 250 420 899 500 296 -125 A.P. 251 249 425 900 505 297 -126 A.P. 251 250 443 951 530 302 -125 A.P. 250 250 449 948 533 320 -124 A.P. 250 250 456 948 540 331 -125 A.P. 252 250 461 948 545 332 -128 A.P. 251 250 486 1001 579 334 -125 A.P. 252 250 492 1001 586 328 -123 A.P. 251 250 499 1001 589 349 -125 A.P. 250 251 505 1002 595 352 -123 A.P. 256 250 524 1002 601 359 -125 A.P. 256 250 520 1001 606 369 -123 A.P. 250 251 520 1001 607 360 -125 A.P. 252 251 525 1001 610 363 -123 A.P. " Conditions were monitored and logged before and after the experiment. Blank: blank experiment before combustion, PM: fluorinated acrylic polymer b Reactor set temperature 0 Inlet 1 flow rate d Inlet 2 flow rate Measured temperature at each position ''Reactor pressure, AP: atmospheric pressure A-6 Abundance 1.5e+07 1e+07| 5000000 0 Time--> Abundance 5.00 TIC: UT60-2.D 10.00 15.00 ^ 20.00 25.00 30.00 35.00 1.5e+07| 1e+07| 5000000 0 Time--> Abundance ^ J \ 5.00 TIC: UT65.D 10.00 15.00 .--- U 20.00 25.00 30.00 35.00 1.5e+071 1e+071 J 5000000r 0 Time--> Abundance \ 5.00 TIC: UT70-3.D 10.00 15.00 20.00 25.00 30.00 35.00 1.5e+07 1e+07 5000000 0 Time--> Abundance P\ 5.00 TIC: UT73.D 10.00 15.00 r- 20.00 25.00 30.00 35.00 1 .5e+07| 1e+07| 5000000 0 Time--> Abundance TIC: UT75.D 5.00 10.00 15.00 20.00 25.00 30.00 35.00 1.5e+07| 1e+07 50000001, 0 Time--> Abundance /"-- 5.00 TIC: UT75-2.D ^1 10.00 15.00 20.00 25.00 30.00 35.00 1.5e+07 50010e+00070__'i r\\ 0s Tjme--> 5.00 Figure Al. Total Ion TIC: UT99-1.D 10.00 15.00 20.00 25.00 30.00 35.00 Chromatogram for Untreated Article Combustion at 725,750,750 (duplicate), and 1000C 600,650,700, A-7 Abundance TIC: TR60-2.D 1e+07 5000000 Time--> 0 . . . . i . . . . , Abundance 5.00 10.00 luA, 15.00.,-^" ^gg-g.OO 30.00 35.00 1e+07 I \ 5000000^ \ Time--> 0 Abundance . . . . 5 . , 0 . 0 . A 1e+07 . . , 10.00 5000000 Time--> Abundan 0 ce . . . . 5 . , 0 0 . . . . 1 0 , . 0 0 r\ 1e+07 5000000 '\;' Time--> 0 . . . . , . . Abundance 5.00 i 10.00 ^ 1e+07 | \ 50000001 ^ \ Time-Abund > a n 0 c e . . .5. . ,00 . ,10. 0 0 1e+07 50000001 ^J Time--> 0 Abundance 5.00 10.00 U.^Ai^f^.A.,,,.,,,.. , 15.00-,-,y.p^Qg.OO 30.00 35.00 ,-'' 15.00.,-^y-p^3r>g.00 30.00 35.00 15.00-^^^^ ^^.00 30.00 35.00 ...''' 15.00I.,1-(<-.:>"I 'K""f,O-^-"^r.-UpO 30.00 35.00 ^ )5ocr\crrR'9Q-^CD)o 30-00 35.00 1e+07 5000000 f \ / O'liiiiiiiiiiiiiii Time--> Figure A2. Total Ion Chromatogram T-r^i i i' i i for Treated i|i i Article i i ii i i i i Combustion at 600,650,700,725, 750,750 (duplicate), and 1000C A-8 Abundance 2e+071 Ab^d^mce 2e+07l Ab'u^d'ance 2e+07^ 5-00 5-00 10.00 10.00 TIC: PM60-2.D AA. 15.00 20.00 25.00 TIC: PM65.D ,l^,iXAJL 15.00 20.00 25.00 TIC: PM70.D 30.00 30.00 35.00 35.00 Ab^d^nce 2e+07l 500 10.00 15.00 20.00 25.00 30.00 35.00 TIC: PM75.D , , ^ ^ - -,-. ^ O"^--'--'--'--| i i i i | i i f^--]--i--f--r"--|^--_i _^ _' _i--_h--_j_' _i __ i--^___ --i--') _r'_")^_""_r--_f--_r^_]--_i--_r Abundfance S-OO 10.00 15.00 20.00 25.00 30.00 35.00 2e+07l TIC: PM80.D Xb^d^mce 2e+071 5-00 10.00 15.00 20.00 25.00 30.00 35.00 TIC: PM85.D |l Abidance 5-00 2e+07l ^S^d^nce 5-00 2e+07^ -----/ Time--> 04-, Abundance 2e+07 5.00 Ab'u^d^mce 2e+07j 5-00 10.00 10.00 10.00 k 15.00 20.00 25.00 TIC: PM90.D 15.00 20.00 25.00 TIC: PM95.D | J-" 15.00 20.00 25.00 TIC: PM99-3.D 30.00 30.00 30.00 35.00 35.00 35.00 10.00 15.00 20.00 25.00 30.00 35.00 TIC: PM99-4.D Figure A3. Total Ion Chromatogram for Fluorinated Acrylic Polymer Combustion at 600, 650,700,750,800, 850,900,950,1000,1000 (duplicate), and 1000C (triplicate) A-q Appendix B Experimental Condition (Temperature and Flow Rate) and Results for PFOA, F, and Cl Aqueous Solution Analysis R-1 Appendix B FIGURE LIST OF FIGURES B 1 Fluoride Analysis Result at UDRI B2 Chloride Analysis Result at UDRI LIST OF TABLES TABLE B 1 Experimental Condition of PFOA, F', and Cl" Aqueous Solution Analysis at 1000C (All Under Atmospheric Pressure) B2 Aqueous Solution Analytical Results from EXYGEN2' R-2 Table Bl. Experimental Condition ofPFOA, F", and Cl" Aqueous Solution Analysis at 1000C (All Under Atmospheric Pressure) Sample8SetT" F.R.1'1F.R.2'1FPTVT"?77T^Tl?T"^ExiT (beffaft) C mL/min mL/min C C C C C C C C Sample for EXYGi;N Blank (bef) 1000 8.8 4.5 299 300 433 998 525 302 303 24 Blank (aft) 1000 8.7 4.5 301 300 471 999 558 304 303 24 UT 1000 8.8 4.5 302 301 516 1000 597 310 299 24 UT 1000 8;8 4.4 302 301 520 1001 601 315 299 24 Blank 1000 8.8 4.5 300 302 528 1002 608 321 299 24 Blank 1000 8.9 4.4 302 302 531 1002 611 323 299 24 UT 1000 8.9 4.4 302 302 532 1001 611 324 300 24 UT 1000 8.9 4.5 302 302 534 1003 613 326 301 24 Blank 1000 8.8 4.5 301 303 536 1001 615 330 300 24 Blank 1000 8.8 4.5 301 300 538 1002 616 334 301 24 UT 1000 8.8 4.5 300 301 538 1000 617 338 301 24 UT 1000 8.8 4.5 303 303 539 1002 617 340 301 24 Blank 1000 8.9 4.5 302 301 540 1002 617 343 301 24 Blank 1000 8.9 4.5 301 302 541 1002 618 345 300 24 Blank 1000 8.8 4.5 302 302 543 1003 619 357 302 24 Blank 1000 8.9 4.5 301 302 543 1001 619 358 301 24 TR 1000 8.8 4.4 302 300 543 1001 619 358 301 24 TR 1000 8.9 4.5 301 301 543 1003 619 359 301 24 Blank 1000 8.8 4.4 300 301 543 1002 619 359 302 24 Blank 1000 8.8 4.4 302 300 543 1001 619 360 303 24 TR 1000 8.8 4.4 300 301 543 1001 620 360 302 24 TR 1000 8.9 4.4 301 302 543 1002 619 360 301 24 Blank 1000 8.8 4.4 300 300 543 1001 619 360 301 24 Blank 1000 8.9 4.4 300 300 543 1002 619 360 300 24 TR 1000 8.9 4.4 299 301 543 1003 620 360 300 24 TR 1000 8.8 4.4 300 302 543 1002 619 360 299 24 Blank 1000 8.9 4.4 302 302 543 1002 619 361 299 24 Blank 1000 8.8 4.4 302 302 543 1002 619 361 299 24 Sample for UDRI Blank 1000 8.8 4.5 300 299 455 1000 545 347 305 24 Blank 1000 8.7 4.5 300 299 489 1000 575 370 303 24 TR 1000 8.7 4.5 300 301 489 1001 575 371 303 24 TR 1000 8.7 4.4 301 299 500 1001 584 380 302 24 Blank Blank 1000 8.7 4.4 301 301 525 1001 599 398 302 24 1000 8.7 4.5 302 301 524 1000 601 401 302 24 a Conditions were monitored and logged before and after the experiment. Blank: blank experiment before combustion, UT: untreated article, TR: treated article b Reactor set temperature 0 Inlet 1 flow rate d Inlet 2 flow rate e Measured temperature at each position f Temperature at the downstream of aqueous solution vial exhaust line B-3 Sample ID UTBKM UTBK1-2 UT1-1 UT1-2 UTBK2-1 UTBK2-2 UT2-1 UT2-1 UTBK3-1 UTBK3-2 UT3-1 UT3-2 UTBK.4-1 UTBK4-2 BK1 TRBK1-1 TRBK1-2 TR1-1 TR1-2 TRBK2-1 TRBK2-2 TR2-1 TR2-2 TRBK3-1 TRBK3-2 TR3-1 TR3-2 TRBK4-1 TRBK4-2 BK2 Table B2. Aqueous Solution Analytical Results from EXYGEN" PFOA r cr Notation ND ND ND 1stjar for blank run before 1st untreated article combustion ND ND ND 2ndjar for blank run before 1st untreated article combustion ND ND ND 1stjar for 1stuntreated article combustion ND ND ND 2ndjar for 1stuntreated article combustion ND ND ND 1stjar for blank run before 2nd untreated article combustion ND ND ND 2ndjar for blank run before 2nd untreated article combustion ND ND ND 1stjar for 2nduntreated article combustion ND ND ND 2ndjar for 2nduntreated article combustion ND ND ND 1stjar for blank run before 3"1untreated article combustion ND ND ND 2ndjar for blank run before 3rd untreated article combustion ND ND ND 1stjar for 3rduntreated article combustion ND ND ND 2ndjar for 3rduntreated article combustion ND ND ND 1stjar for blank run after 3rd untreated article combustion ND ND ND 2ndjar for blank run after 3rd untreated article combustion ND ND ND HPLC water blank ND ND ND 1stjar for blank run before 1st treated article combustion ND ND ND 2'"1jar for blank run before 1sttreated article combustion ND ND ND 1stjar for 1sttreated article combustion ND ND ND 2ndjar for 1st treated article combustion ND ND ND 1stjar for blank run before 2nd treated article combustion ND ND ND 2ndjar for blank run before 2ndtreated article combustion ND ND ND 1stjar for 2ndtreated article combustion ND ND ND 2ndjar for 2ndtreated article combustion ND ND ND 1stjar for blank run before 3rd treated article combustion ND ND ND 2ndjar for blank run before 3"* treated article combustion ND ND ND 1stjar for 3rd treated article combustion ND ND ND 2ndjar for 3"1treated article combustion ND ND ND 1stjar for blank run after 3rd treated article combustion ND ND ND 2ndjar for blank run after 3rd treated article combustion ND ND ND HPLC water blank a ND: compound not detected, < lOng/L. R-4 Figure Bl. Fluoride Analysis Result at UDRI Notations: HPLC Blank, ExpBlankI, ExpBlank2, Trl-1, Trl-2, Tr2-l, and Tr2-2 correspond to HPLC grade water, 1st and 2ndbottles of aqueous solution for blank run at 1000C, 1st and 2'10 bottles of aqueous solution for 1sttreated article combustion at 1000C, and 1st and 2ndbottles of aqueous solution for 2 treated article combustion at 1000C, respectively. R-5 Figure B2. Chloride Analysis Result at UDRI Notations: HPLC Blank, ExpBlankI, ExpBlank2, Trl-1, Trl-2, Tr2-l, and Tr2-2 correspond^) HPLC grade water, 1st and 2ndbottles of aqueous solution for blank run at 1000C, 1st and 2 bottles of aqueous solution for 1sttreated article combustion at 1000C, and 1stand 2 bottles of aqueous solution for 2nd treated article combustion at 1000C, respectively. B-6 Appendix C Experimental Condition (Temperature, Flow Rate, and Pressure) and Total Ion Chromatogram for Telomer In-line GC/MS Analysis C-l Appendix C LIST OF FIGURES FIGURE__________________________________________PAGE Cl Total Ion Chromatogram for Telomer Combustion at 200 and 600C C-3 LIST OF TABLES TABLE_____________________________________________PAGE Cl Experimental Condition of Telomer Combustion C-3 c-2 Sample' (befaft) Table Cl. Experimental Condition of Telomer Combustion SetT" F. R. I" P. R. 2" T1" T2" T3" T4'5 T56 T6" T7" "C mL/min mL/min "C C C C C C C Presf C Blank (bef) 200 Blank (aft) 200 Telom 200 Telom 200 Telom 600 Telom 600 24.1 23.8 23.3 23.7 12.8 12.7 11.7 11.3 11.6 117 6.5 6.5 149 151 151 151 151 151 150 151 150 149 151 157 133 199 157 134 201 161 133 201 148 133 201 149 150 601 205 170 601 232 134 -125 A.P. 139 -123 A.P. 150 -125 A.P. 149 -127 A.P. 154 -125 A.P. 151 -128 A.P. Conditions were monitored and logged before and after the experiment. Blank: blank experiment before combustion, Telom: telomer sample b Reactor set temperature c Inlet 1 flow rate d Inlet 2 flow rate e Measured temperature at each position f Reactor pressure, AP: atmospheric pressure Abundance 8000000 7000000 8000000 5000000 4000000 3000000 2000000 1000000 0 Time--sAbundance 8000000 7000000 8000000 SOOOOOO 4000000 3000000 2000000 1000000 n 5.00 10.00 ; \ v . - s.oo 10.00 TIC; T1-M20.0 16.00 20.00 25.00 30.00 T1Q -n-MSO.D i J 'l^l\Ih 11j 1 L-,JJ 15.00 20.00 '^.--- 25.00 30.00 35.00 35.00 Figure Cl. Total Ion Chromatogram for Telomer Combustion at 200 and 600C C-3 Appendix D Experimental Condition (Temperature and Flow Rate) for VOC, CO and C02 Off-line GC/MS Analysis D-l Appendix D LIST OF TABLES TABLE Dl Experimental Condition of Off-line GC/MS VOC Analysis (All under Atmospheric Pressure) D-2 Table Dl. Experimental Condition of Off-line GC/MS VOC Analysis (All under Sample" (bef^aft) SetT" C F. R. 1" mL/min F.R.2'1 AMtmakoesupph' erTicl^PrTe2sf suTr3ef )_T_^___T_5f___T6_^___j.^__ mL/min mL/min C C C C c C C Blank (bef) 1000 8.8 4.3 6.7 300 302 399 1002 486 292 302 Blank (aft) 1000 8.7 4.2 6.8 UT 1000 8.7 4.2 6.8 UT 1000 8.6 4.2 6.8 301 302 425 1002 507 301 302 425 1002 507 300 300 439 1001 513 297 303 297 303 304 303 UT 1000 8.6 4.4 6.8 300 300 439 1001 513 304 303 UT 1000 8.7 4.3 6.8 301 302 435 1002 517 311 302 UT 1000 8.7 4.3 6.8 301 302 435 1002 517 311 302 UT 1000 8.7 4.4 6.8 302 301 440 1002 522 319 302 Blank 1000 8.9 4.5 6.8 301 301 398 1002 484 282 308 Blank 1000 8.8 4.4 6.8 302 301 416 1000 500 297 304 TR 1000 8.8 4.4 6.8 302 301 416 1000 500 297 304 TR 1000 8.8 4.5 6.7 300 302 425 1001 508 307 303 TR 1000 8.8 4.5 6.7 300 302 425 1001 508 307 303 TR 1000 8.9 4.5 6.8 301 302 432 1002 514 312 302 TR 1000 8.9 4.5 6.8 301 302 432 1002 514 312 302 TR 1000 8.8 4.4 6.8 301 301 437 1001 518 318 300 " Conditions were monitored and logged before and after the experiment. Blank: blank experiment before combustion, UT: untreated article, TR: treated article b Reactor set temperature c Inlet 1 flow rate d Inlet 2 flow rate e Makeup gas flow rate f Measured temperature at each position D-3 Appendix E Experimental Condition (Temperature and Flow Rate) for PFOA Transport Efficiency Test and System Steam Extraction E-l Appendix E LIST OF TABLES TABLE El Experimental Condition ofPFOA Transport Test (All under Atmospheric Pressure) E2 Experimental Condition of Steam Extraction (All under Atmospheric Pressure) E-2 Table El. Experimental Condition ofPFOA Transport Test (AH under Atmospheric Sample' (bsf/aft) SetT" F.R.1'' F. R. 2" MakeuPp"reTsVsurTe2')__T_31__T_4_1__T_5_1__^_6_f ^.^f C mL/min mL/min mL/min "C C C C C C C Blank (bef) 170 12.6 6.5 6.9 Blank (aft) 170 12.7 6.5 6.9 PFOA 170 12.7 6.5 6.9 PFOA 170 12.8 6.5 6.9 PFOA 170 12.8 6.5 6.9 PFOA 170 12.9 6.5 6.9 PFOA 170 12.9 6.5 6.9 PFOA 170 12.8 6.4 6.9 Blank 300 12.7 6.3 6.9 Blank 300 12.9 6.5 6.9 PFOA 300 12.9 6.5 6.9 PFOA 300 12.9 6.4 6.9 PFOA 300 12.9 6.4 6.9 PFOA 300 12.7 6.4 6.9 PFOA 300 12.7 6.4 6.9 PFOA 300 12.8 6.4 6.9 171 169 170 170 214 159 165 170 171 170 170 214 158 165 170 171 170 170 214 158 165 169 169 170 171 214 158 165 169 169 170 171 214 158 165 171 170 170 170 214 158 166 171 170 170 170 214 158 166 170 170 170 171 214 158 166 171 172 221 201 205 300 295 169 169 221 299 305 302 295 169 169 221 299 305 302 295 169 170 222 302 306 305 296 169 170 222 302 306 305 296 169 170 225 302 306 300 296 169 170 225 302 306 300 296 169 171 225 301 306 298 296 a Conditions were monitored and logged before and after the experiment. Blank: blank experiment before combustion b Reactor set temperature 0 Inlet 1 flow rate d Inlet 2 flow rate e Makeup gas flow rate f Measured temperature at each position Table E2. Sample3 (befaft) 1st Extract 1st Extract 2nd Extract 2nd Extract 3rd Extract 3rd Extract 4th Extract 4th Extract 5th Extract 5th Extract Experimental SetT" C F. R. I0 mL/min 300 4.1 300 3.8 300 3.8 300 3.9 300 3.9 300 4.6 300 4.6 300 4.1 300 4.1 300 4.1 Condition of Steam Extraction (All F. R. 2" Makeup0 T1* T2f T3f mL/min mL/min C C C 8.2 7.9 8.2 7.4 300 300 299 301 300 300 8.2 7.4 8.0 8.1 8.0 8.1 8.4 8.0 8.4 8.0 301 300 300 299 300 300 299 300 300 300 300 295 300 300 295 7.7 8.3 7.7 8.0 299 300 290 299 300 290 8.0 8.1 300 299 291 under T4f C 300 299 299 299 299 301 301 301 301 301 . Atmospheric Pressure) T5f T6f -p^f C C C 311 296 298 311 294 302 311 294 302 305 300 298 305 300 298 305, 305 296 305 305 296 305 305 303 305 305 303 307 305 305 a Conditions were monitored and logged before and after the experiment b Reactor set temperature 0 Inlet 1 flow rate d Inlet 2 flow rate e Makeup gas flow rate f Measured temperature at each position E-3 Appendix F Experimental Condition (Temperature and Flow Rate) for PFOA Calibration and Detection Limit Study F-l Appendix F LIST OF TABLES TABLE________________________________-_________PAGE Fl Experimental Conditions for PFOA Calibration and Detection Limit Study F-3 F-2 Table Fl. Experimental Conditions for PFOA Calibration and Detection Limit Study Sample" (be&aft) SetT" F.R.10 F.R.2" Tl" C mL/min mL/min C Blank (bef) 300 19.6 9.8 301 Blank (aft) 300 19.7 9.6 300 PFOA lug 300 19.6 9.8 300 PFOA l|ig 300 19.6 9.6 300 PFOA l(ig 300 19.7 9.7 300 PFOA lu.g 300 19.6 9.7 301 Blank 300 19.8 9.8 299 Blank 300 19.7 9.8 301 PFOA 5|ig 300 19.8 9.8 300 PFOA 5ng 300 19.7 9.9 300 PFOA 5ug 300 19.6 9.8 300 PFOA 5[ig 300 19.7 9.7 301 Blank 300 19.8 9.6 301 Blank 300 19.7 9.8 300 PFOA 10p.g 300 19.7 9.6 301 PFOA lOug 300 19.8 9.7 302 PFOA lOug 300 19.8 9.6 301 PFOAlOHg 300 19.8 9.7 300 Blank Blank 300 19.7 9.9 302 300 19.7 9.8 301 PFOA 50(lg 300 19.8 9.8 300 PFOA SOiig 300 19.7 9.9 301 PFOA 50(lg 300 19.9 9.8 299 PFOA50^g 300 19.8 9.8 300 Blank 300 19.8 9.6 300 Blank 300 19.7 9.7 300 PFOA lOOug 300 19.8 9.7 300 PFOA 100[j.g 300 19.6 9.8 302 PFOA 100[j.g 300 19.8 9.6 299 PFOA 100% 300 19.8 9.6 298 Blank 300 19.7 9.8 300 Blank 300 19.6 9.7 299 T2" C 300 301 301 302 302 301 301 302 302 302 300 300 301 302 302 301 299 301 300 300 301 299 300 302 301 301 302 301 301 300 302 301 T3 C 270 270 270 270 270 270 271 270 269 269 270 270 270 270 270 269 270 270 271 270 270 269 269 270 270 269 268 268 270 270 270 370 T4 C 302 301 301 299 300 299 301 302 300 300 301 299 300 302 300 299 302 301 301 300 301 300 298 300 302 300 298 302 300 299 298 299 " Conditions were monitored and logged before and after the experiment. combustion. b Reactor set temperature c Inlet 1 flow rate65 T5 C 299 299 299 298 301 300 301 301 301 301 301 300 299 299 299 300 299 300 300 301 300 300 301 301 298 298 298 298 301 300 299 300 Blank: T6 C 301 301 301 300 301 300 301 301 301 301 300 300 300 299 302 301 300 299 301 301 301 301 299 299 301 301 301 301 301 301 301 302 blank T7' C -125 -125 -125 -125 -125 -120 -125 -123 -125 -124 -125 -123 -125 -125 -125 -125 -125 -125 -125 -128 -125 -122 -127 -125 -124 -120 -125 -128 -125 -122 -125 -124 experiment fres1 atm A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. A.P. before d Inlet 2 flow rate e Measured temperature at each position f Reactor pressure, AP: atmospheric pressure F-3 Appendix G General Description ofATRS Standard Procedure, Wickbold Torch Methods for Total Fluorine, and QuikChem Method for Fluoride and Chloride in Water G-l Appendix G TABLE OF CONTENTS SECTION Gl Thermal Decomposition of Organic Materials Using the Advanced Thermal Reactor System G2 Wickbold Torch Method for Total Fluorine G3 QuikChem Method 10-109-12-2-A, Fluoride in Water (0.10to5.0mgF/L) G4 QuikChem Method 10-117-07-1-C, Chloride in Water (O.ltolO.OmgClTL) LIST OF FIGURES PAGE G-3 G-7 G-9 G-9 FIGURE__________________________________________PAGE Gl General Schematic of the Advanced Thermal Reactor System (ATRS) G-4 G2 Wickbold Oxyhydrogen Torch Apparatus G-7 G-2 Gl. Thermal Decomposition of Organic Materials using the Advanced Thermal Reactor System The University of Dayton Research Institute's (UDRI) Environmental Engineering Group (EEG) has been conducting thermal stability measurements of organic materials since 1971 beginning with a study on the products evolved from the thermal decomposition of polymers used in beverage containers [1, 2]. This early work was conducted using a system consisting of the thermogravimetric analyzer connected in series with a high-speed gas chromatograph. Since then the EEG has developed a series of specialized instrumentation systems to study the thermal decomposition of organic materials [3-8]. Background Regardless of the material being studied a similar overall approach to measuring the thermal decomposition is used. The sample, which can be a gas liquid or solid, is thermally vaporized, mixed with flowing gas (normally dry air), and swept through a high temperature reactor. The exhaust leaving the reactor is collected and analyzed by GC/MS. The fraction of parent species remaining (destruction efficiency) and products are determined by comparing GC/MS analyses taken at relatively low reactor temperatures (where the rate of oxidation is negligible) with data obtained at higher temperatures (where the rate of oxidation is significant). Data is typically taken at ever increasing temperatures until all of the parent species and products are oxidized. For exposures where air is in great excess this typically requires temperatures on the order of 800C with a mean residence time of 2 s. The exposure conditions are generally defined by the mean temperature, residence time, and level of excess air (in excess, near-stoichiometric, pyrolysis). With adequate method development the residence time distribution and a more precise measure of excess air (equivalence ratio) may be defined. The exposure temperature is measured at the reactor mid-point using a thermocouple. The mean residence . time (MRT) is determined from the flow rate (measured at room temperature and corrected to the reactor temperature assuming ideal gas behavior) and the volume of the reactor. The residence time distribution is taken as being sufficiently narrow that plug flow may be assumed. This is an appropriate assumption for MRTs less than on the order of 10 sec. For longer MRTs the plug flow assumption should be checked. The level of excess air for fluids (liquids and gases) is estimated from the chemical oxygen demand of the sample (assuming complete conversion to COz, HzO, etc.) and relative concentrations of oxygen and sample as calculated from their measured flow rates. The estimation of excess air for solid samples is similar, though solids may not be easily introduced to the reactor system at a fixed rate. The nominal method is to evaporate small quantities of the sample using a pyroprobe, a device designed to vaporize samples by heating them at a fixed rate. The rate of evaporation from the probe can be estimated using TGA data obtained under the same conditions of sample size, atmosphere, and heating rate. A typical flow reactor system used for thermal decomposition research is the Advanced Thermal Reactor System (ATRS) shown in Figure Gl. This system is unique in that the design allows optical access to the reactor so that photochemical reactors may be conducted at high temperatures in addition to conventional thermal decomposition. As shown in Figure Gl the ATRS consists of a reactor assembly and inline analytical systems connected via a cryogenic interface. The reactor assembly consists of a thermally insulated enclosure housing the sample introduction, reactor, and transfer line systems. The reactor feed system includes two independent sample inlets; a low-volume inlet for the controlled introduction ofgasand liquid-phase samples, and a multi-purpose inlet which may be fitted with special probes for the introduction of gas-, liquid-, or solid-phase samples and heterogeneous materials. The flow through these inlets is independently controlled and connected to the reactor through heated transfer lines. The reactor is housed within its own small tube furnace and may be independently heated to 1,200C. The furnace can accommodate reactors as large as 2cm in diameter and 25cm long. The exhaust line from the reactor is heat traced to prevent cool regions where reactor products may be lost through condensation. The G-3 cryogenic interface is a shell and tube design in which the shell can be cooled to near liquid nitrogen temperatures (-193C). This permits the collection of all but the lightest reactor products. The incondensable products, typically carbon monoxide and methane, can be collected at the exhaust vent in Tedlar sample collection bags for separate analysis. The analytical system used on the ATRS is a Hewlett Packard 5890/5970 GC/MS/FID. The GC oven can be fitted with dual columns for simultaneous MS and FID analysis of the reactor products. Further details of the ATRS are presented in Graham, et al. [9]. Reactor Assembly Inlets Gas Chromatograph ----' Figure Gl. General Schematic of the Advanced Thermal Reactor System (ATRS). Generalized Standard Operating Procedure System Preparation Prior to introducing the sample, activate set-points for the various temperatures and flow rates to ensure that the desired experimental conditions are established. Analytical System 1. Prepare the in-line GC/FID/MS analytical subsystem in a stand-by mode with the appropriate analysis programs (temperature program, scanning ranges, detector sensitivity, etc.) set as per manufacturer's SOP. Inlet. Exhaust Line. and Cold Trap Temperatures 2. Check the set points on the inlet temperature controllers. Observe the indicated temperatures of each controller to ensure that they are properly cycling about their respective set points. 3. Check the dial settings on the variable transformer controlling the exhaust line heaters and the exhaust line temperature to ensure that it is stable. G-4 4. Check the dial settings on the variable transformer controlling the cold trap enclosure heater and the cold trap temperature. Observe the indicated temperature to ensure that it is stable. Reactor Gas Feed Rate 5. Check the settings on the flow controllers to the inlet channels. Measure the total flow rate using a bubble flow meter at the cold trap vent. Adjust the total flow as needed to the desired value. Reactor Temperature 6. Check the set point on the reactor temperature controller. Observe the indicated temperature to ensure that the controller is properly cycling about the set point Cold Trap Preparation and Effluent Collector 7. Check cold trap nitrogen purge is on stand-by (metering valve two turns open). Fill the coolant dewar with liquid nitrogen (or other coolant as required). Check the cold trap temperature. Adjust nitrogen flow so that the cold trap temperature is correctly set 8. Attach a Tedlar sample collection bag to the system exhaust port. Check the sampling valve is in the VENT position. Reactor Operation Once the system is ready, the sample may be admitted and a test conducted. Test Monitoring 9. While the sample is being admitted to the ATRS, monitor the cold trap temperature and coolant level. Also monitor the reactor temperature. After the sample has been introduced to the system, continue the test monitoring for 2 minutes to ensure complete transport of sample through the system. Post-Test Operations 10. Continue to monitor the coolant level and cold trap temperature. 11. Set the Tedlar sample bag valve to VENT, stopping the collection of exhaust. 12. Switch the reactor carrier gas OFF and the helium purge system ON. Wait for 2 minutes before proceeding. 13. Switch the analytical system from stand-by to active and hold at initial conditions. 14. Seal the cold trap vent. Observe the rise in total system pressure and adjust the flow of helium so the initial pressure is correctly set. 15. Initiate analytical system data acquisition program (i.e., switch from hold to active). G-5 16. Switch cold trap coolant OFF. 17. Monitor analytical program as per manufacturer's SOP. The ATRS has been used to conduct several programs for the U.S. EPA under operating guidelines developed to meet the requirements of Category III and IV Quality Assurance Program Plans (QAPPs) [10,11]. References 1. W. A. Rubey, "Design of a System for Simultaneous Thermogravimetric-Gas Chromatographic Analysis of Stabilized Polyacrylonitrile Fiber," Report UDRI-TR-71-28, September 1971. 2. W. A. Rubey and D. S. Duvall, "Description of Apparatus for Conducting Isothermal Aging Evolved Gas Analysis Tests with High-Temperature Polymers," Report UDRI-TR-72-01, December 1972. 3. D. S. Duvall and W. A. Rubey, "Laboratory Evaluation of High-Temperature Destruction ofKepone and Related Pesticides," US-EPA report, EPA-600/2-76-299, December 1976. 4. W. A. Rubey, "Design Considerations for a Thermal Decomposition Analytical System (TDAS)," US-EPA report, EPA-600/2-80-098, August 1980. 5. J. L. Graham, W. A. Rubey, B. Dellinger, and R. A. Cames, "Determination of the Thermal Decomposition Properties of Toxic Organic Substances," Proceedings of 1982 Summer National Meeting of American Institute of Chemical Engineers, Cleveland, OH, August 1982. 6. W. A. Rubey, I. B. Fiscus, and J. L. Torres, "Description and Operation of a Thermal Decomposition Unit-Gas Chromatographic System," Report for US-EPA, Cooperative Agreement CR-807815-01-0, December 1982. 7. J. L. Graham, W. A. Rubey, and I. B. Fiscus, "Design and Evaluation of the Prototype Packaged Thermal Reactor System," Report for US-EPA, Cooperative Agreement CR-807811-01-0, March 1984. 8. W. A. Rubey and R. A. Grant, "Design Aspects of a Modular Instrumentation System for Thermal Diagnostic Studies," Review of Scientific Instruments. 59.265,1988. 9. Graham, J. L., Berman, J. M., and Dellinger, B., "High-Temperature thermal-photolytic oxidation of monochlorobenzene." J. Photochem. Photobiol. A: Chem.. 71, 65,1993. 10. J. L. Graham, B. Dellinger, J. Swartzbaugh, "Category in Quality Assurance Project Plan for Development of A Photothermal Detoxification Unit," Cooperative Agreement No. CR8195 94-01-0, July 1995. 11. J. L. Graham, B. Dellinger, J. Swartzbaugh, "Category IV Quality Assurance Project Plan for Photothermal Treatment of Hydrocarbon Vapors Using Mercury Lamps," Contract No. 68-C2-0108, March 1996. G-6 G2. WICKBOLD TORCH METHOD FOR TOTAL FLUORINE 1. Introduction "The carbon-fluorine bond is exceptionally strong, and extremely vigorous conditions are needed for quantitative" analysis of fluorine in organic compounds. (Kissa, 1998) The "most vigorous" technique for measurement of fluorine in organic compounds is "combustion in an oxyhydrogen flame" referred to as the Wickbold torch. (Kissa, 1998) 2. Apparatus A typical configuration for the Wickbold oxyhydrogen torch apparatus as described by Sweetser (1956) is shown in Figure G2. DRAIN Figure G2. Wickbold Oxyhydrogen Torch Apparatus. G-7 3. Method Description The sample size for the standard sample boat is up to 20 mg for a solid or up to 5 mL for a liquid. With the oxyhydrogen torch in operation, the sample is pyrolyzed or vaporized with a Bunsen burner moving on a rail below the volatilization chamber. The vapors and pyrolysis products are swept through the oxygen-hydrogen flame chamber operating at up to approximately 2000 C to mineralize the fluorine in the sample to fluoride ion. The resulting fluoride ion is absorbed in the collection tower containing water or an alkaline solution. The absorbed fluoride ion is measured via fluoride ion-selective electrode or ion chromatography. The reported limit ofquantitation for total fluorine via the Wickbold Torch method is 0.5 ppm (0.5 mg/kg). The accuracy of this method for determination of total fluorine in fluorinated polymers is exemplified by total fluorine values of 75.35% to 75.84% for PTFE with known total fluorine content of 76.0%. (Sweetser, 1956) 4. Safety Considerations Use of hydrogen presents a potential fire and explosion hazard. Use of oxygen presents a potential fire hazard. Safe operation of the oxyhydrogen torch is assured by the use of specialized equipment with shielding and elaborate safety devices by well-trained personnel at a qualified laboratory. 5. References Kissa, E. "Analysis ofAnionic Fluorinated Surfactants," Chapter 8 in Anionic Surfactants: Analytical Chemistry - 2nd Edition, Revised and Expanded, edited by John Cross. Marcel Dekker Surfactant Science Series, volume 73,1998. Sweetser, P. B. "Decomposition of Organic Fluorine Compounds by Wickbold Oxyhydrogen Flame Combustion Method,"Analytical Chemistry, vol. 28, pp. 1766-1768,1956. ,, G-8 G3. QuikChem Method 10-109-12-2-A, Fluoride in Water (0.10 to 5.0 mg F7L) - Principle Fluoride is determined potentiometrically using a combination fluoride electrode and the Lachat QuikChem Flow Injection Analyzer. The fluoride electrode consists of a lanthanum fluoride crystal across which a potential is developed by fluoride ions. The reference cell is a Ag/AgCl/Cl- cell. The reference junction is of the annular liquid-junction type and encloses the fluoride-sensitive crystal. - Interferences - 1. The polyvalent cations, Si4"1"A,13"1"a,nd Fe3"*",interfere by forming complexes with fluoride. CDTA (1,2-cyclohexylene dmitrilotetracetic acid) is added to preferentially complex these cations and eliminate this interference when these concentrations do not exceed 3.0 mg Al^+fL and 20 mg Fe^+TL. 2. For US users determing Total or Total Dissolved Fluoride, the Bellack distillation is required for NPDES monitoring but is not required for SDWA monitoring. G4. QuikChem Method 10-117-07-1-C, Chloride in Water (0.1 to 10.0 mg C17L) - Principle Thiocyanate ion is liberated from mercuric thiocyanate by the formation of soluble mercuric chloride. In the presence of ferric ion, free thiocyanate ion forms the highly colored ferric thiocyanate, of which the absorbance is proportional to the chloride concentration. Ferric thiocyanate absorbs strongly at 480 nm. The calibration curve is non-linear.. - Interferences -- 1. Substances which reduce iron (EH)to iron (n) and mercury (III) to mercury (n) (e.g. sulfite, thiosulfate). 2. Halides which also form strong complexes with mercuric ion (e.g. Br", I") give a positive interference. 3. If any question of interferences arise, calibration curves should be prepared in water and in the suspected interfering matrix. If the two curves differ significantly, then there is interference, and the standards must be prepared in the interfering matrix instead of in water. Calcium and magnesium ions may precipitate if present in sufficient concentration. G-9