Page 1 of 24

Supplementary Material

Investigation of Waste Incineration of Fluorotelomer-Based 

Polymers as a Potential Source of PFOA in the Environment

P. H. Taylora,*, T. Yamadaa, R. C. Striebicha, J. L. Grahama, and R. J. Giraudb

a University of Dayton Research Institute, Environmental Engineering Group, 300 

College Park, Dayton, OH 45469

b E. I. du Pont de Nemours and Company, Inc., 1007 Market Street, Wilmington, DE 

19898

* Corresponding author. Tel.: +1 937 672 3065; fax: +1 937 229 2503

E-mail address: ptaylor1@udayton.edu

Table of Contents

1.0 Stoichiometric Calculations ..................................................................................... 3

1.1 Establishing Experimental Conditions ............................................................. 3

1.1.1 Constraints ........................................................................................... 3

1.1.2 Calculating Experimental Run Duration................................................ 3

1.1.3 Summary .............................................................................................. 4

1.2 Setting Combustion Test Air and Methanol Feed Rates ................................. 4

1.3 References...................................................................................................... 6

Tables

Table A-1. Uncontrolled HF Emissions from Mass Burn MWCs

Table A-2. Stoichiometric Calculation of Complete Oxidation of PTFE in the 

Presence of Excess Methanol

Table A-3. Oxidation of Methanol: Stoichiometric Calculations with Refined 

Inputs

Table A-4. Combustion Stoichiometry Calculations for Combustion of FTBP 

Composite 1

Table A-5. Combustion Stoichiometry Calculations for Combustion of FTBP 

Composite 2
Page 2 of 24

Table S-1. Summary of FTBP Composites Elemental Analysis

Table S-2. PFOA Analysis Method Description

Table S-3. FTBP Combustion Test Analytical Results for Impinger Samples

Table S-4. Fluoride Ion Recovery & Exhaust Gas Hydrogen Fluoride (HF) Concentration

Table S-5. PFOA Exhaust Gas Concentration Calculations

Table S-6. 13C-PFOA Surrogate Spike Recovery for Combustion Test Aqueous Samples

Table S-7. Typical Waste Incineration Exhaust Gas Oxygen Levels

Figure S-1. Typical Structure of a Fluorotelomer-Based Polymer in this Study

Figure S-2. Thermogravimetric Analysis of FTBP Composites at 25oC/min

Figure S-3. Reactor Temperature Profile for FTBP Combustion Testing
Page 3 of 24

1.0 Stoichiometric Calculations

1.1 Establishing Experimental Conditions

Prior to conducting Phase I transport testing, planned Phase II combustion testing 

experimental conditions for certain operating parameters (i.e., duration of experimental 

run, target exhaust gas oxygen concentration, and target exhaust gas water 

concentration) were established to assure consistent operating conditions during both 

phases of the experimental program. 

1.1.1 Constraints

The Phase II Quality Assurance Project Plan (submitted to EPA prior to conduct of the 

Phase I transport test) clearly set the following constraints:

 High temperature reactor operation at a temperature of 1000oC (±10oC) for a gas 

residence time of 2 seconds (± 0.2 sec),

 Exhaust gas oxygen concentration “greater than 10% throughout the combustion 

test run following introduction of the methanol fuel”,

 Exhaust gas water concentration (calculated) of approximately 15% (within range of 

8% and 20%) resulting primarily from oxidation of methanol fuel, 

 Test substance composite weight of 100 ± 10 g, and

 Combustion test run duration between 15 and 75 minutes after pyroprobe insertion.

Furthermore, an ABB EL 3020 continuous gas analyzer (CGA) was in place prior to the 

Phase I transport test and planned for use to provide continuous monitoring of oxygen, 

carbon dioxide, and carbon monoxide during Phase II combustion testing. The CGA’s 

oxygen analyzer has a design flow rate of 30 to 60 liters per hour (ABB, 2005). 

Thereby, an additional constraint was to maintain a vapor flow rate greater than 30 liters 

per hour (i.e., greater than 500 sccm).

1.1.2 Calculating Experimental Run Duration

The elemental composition for the expected Phase II test substances were not known 

because such analyses (required for Phase II) had not been conducted prior to the 

Phase I transport test. Therefore, polytetrafluoroethylene (PTFE) was used as a model 

compound in combustion calculations because it is a fluorinated polymer of known 

molecular composition (76% F, 24% C).

Within the constraints above and for PTFE, it was possible to compute a target 

experimental run duration using a target exhaust gas hydrogen fluoride (HF) 

concentration and assuming complete oxidation of the PTFE and the methanol fuel. A 

target HF concentration of 10 mg HF per dry standard cubic meter (dscm) was used to 

correspond to the high end of typical uncontrolled (i.e., combustion section exit) HF 

emission levels from municipal waste combustors (MWCs), considering the range of 2.3 

to 7.9 mg/dscm based on available information summarized in Table A-1. (Oxidation of 
Page 4 of 24

a highly fluorinated polymer (i.e., PTFE) would be expected to yield a high end HF 

emission level.) Information from mass burn MWCs was used because these units 

represent over 76% of MWC waste capacity in the U.S. (IWSA, 2002).

Based on the design of the 3-zone furnace in the thermal reactor system, an effective 

isothermal reactor length of 20 inches (50.8 cm) was originally expected. (Subsequent 

temperature profile measurements for Phase I provided an effective reactor length of 23 

inches (58.4 cm) at 250oC for Phase I and of 26 inches (66 cm) at 1000oC for 

Fluorotelomers Phase II.) An effective reactor length of 50.8 cm was used with the 

reactor tube’s inside diameter (14 mm) to compute the reactor volume corresponding to 

a gas residence time of 2 seconds at 1000oC in the stoichiometric calculations shown in 

Table A-2. The calculated values in Table A-2 show run duration as well as 

corresponding exhaust oxygen concentration (dry basis) and exhaust gas water 

concentration at different excess air levels for a fixed methanol to PTFE ratio. This ratio 

was adjusted through iterative calculations until a run duration for complete oxidation of 

PTFE in the presence of excess methanol clearly greater than 15 minutes was obtained 

with an exhaust HF concentration close to the target value of 10 mg/dscm (i.e., 1.22 x 

10-3 %) while assuring the other constraints noted above had been met. Therefore, a 

run duration of 15.97 minutes (rounded to 16 minutes) was computed and the 

corresponding values for exhaust gas oxygen concentration (dry basis) and exhaust gas 

water concentration were 13.0% and 10.3%, respectively. 

Selecting a target exhaust gas oxygen concentration of 13% dry basis (equivalent to 

11.6% wet basis) seemed appropriate to assure oxygen concentration in exhaust gas 

greater than 10% throughout the combustion test run following introduction of the 

methanol fuel as this level appeared high enough to compensate for a potential drop in 

thermal reactor system exhaust oxygen concentration when the polymer would be 

introduced to the reactor system via pyroprobe gasification.

1.1.3 Summary

The following target values for Phase II combustion testing were calculated prior to 

Phase I transport testing:

 Experimental run duration of 16 minutes, 

 Exhaust gas oxygen concentration (dry basis) of 13%, and

 Exhaust gas water concentration of 10.3%.

These values were established as targets in Phase I testing to assure consistent 

operating conditions during both phases of the experimental program.

1.2 Setting Combustion Test Air and Methanol Feed Rates

Once the effective reactor length was experimentally determined prior to Phase II 

combustion testing, the effective high temperature reactor volume and total exhaust gas 

flow corresponding to 2 seconds gas residence time were set for the 14 mm inside 

diameter reactor tube. Combustion stoichiometry calculations prior to Phase II testing 
Page 5 of 24

were used to iteratively evaluate combinations of synthetic air and methanol feed rates 

yielding this target total exhaust gas flow rate versus the target values for exhaust gas 

oxygen (O2) and water (H2O) concentrations established prior to Phase I (see section 

1.1.3 above), including consideration of the following factors to fine tune the combustion 

stoichiometry calculations: 

 methanol liquid density (as function of liquid temperature and pressure), 

 more refined values of Universal gas constant and methanol molecular weight, 

 same standard temperature used during calibration of the air mass flow controller, 

 oxygen level in the synthetic air on hand as noted on its certificate of analysis

 reactor pressure as sum of monitored values for room pressure + back pressure, and

 input setting/display resolution (number of available digits) for both the air mass flow 

controller and the methanol feed pump.

These calculations are based on complete oxidation of CH3OH according to the 

following reaction:

CH3OH + 1.5 O2  CO2 + 2 H2O

Therefore, for each mole of CH3OH combusted, 1.5 moles of O2 are consumed, 1 mole 

of CO2 is produced, and 2 moles of H2O are produced. As the O2 is supplied in 

synthetic air made up of nominally 21% O2 and 79% nitrogen (N2), each mole of CH3OH 

combusted is also accompanied by 79/21 moles of N2 as both an inert reactant and a 

product. The results of the refined methanol oxidation stoichiometry calculations shown 

in Table A-3 indicate the predicted concentrations for exhaust gas O2, CO2, and H2O.

Further calculations including the contribution of each test substance composite are 

described in Tables A-4 and A-5, which make use of the dry basis elemental analysis 

results provided by the analytical laboratories after normalizing to 100% to account for 

differences across the analytical techniques used. The “monitor” entries in the first 

column in Tables A-3, A-4, and A-5 point out the parameters that are monitored in the 

thermal reactor system; the “analyzed” entries in the first column of Tables A-4 and A-5 

point out the parameters were values from elemental analysis are used. Comparison of 

the reaction products in Tables A-4 and A-5 to the reaction products in Table A-3 

indicates that the oxidation of methanol is controlling.

Based on these calculations (i.e., described in Tables A-3,A- 4, and A-5), the estimated 

amount of oxygen needed for Phase II combustion testing to provide exhaust O2 and 

H2O concentrations comparable to those used in Phase I testing is 662 sccm synthetic 

air when 61.71 μL/min of methanol is fed. The resulting predicted exhaust H2O 

concentration of 10.2% for the Phase II combustion test (Tables A-3, A-4, A-5) is very 

consistent with the 10.3% calculated value used during the Phase I transport test. The 

resulting predicted exhaust O2 concentration of 13.1% (dry basis) is very consistent with 

the 13.0% O2 concentration for the Phase I transport test.
Page 6 of 24

1.3 References

ABB, 2005. EasyLine Continuous Gas Analyzers Model EL3020, Data Sheet 

10/24_4.10 EN.

Environmental Standards, Inc., December 27, 2005, revised June 23, 2006. Quality 

Assurance Plan for the ECA Incineration Testing Program—Phase II Fluorotelomer 

Incineration Testing.

IWSA (Integrated Waste Services Association), 2002. The 2002 IWSA Directory of 

Waste-to-Energy Plants.
Page 7 of 24

Table A-1. Uncontrolled HF Emissions from Mass Burn MWCs

Item Value Units Reference and/or Comment

Low 

end

reference mass burn MWC 

uncontrolled HF emission 

0.009 kg 

HF/metric 

ton MSW

EPA, Locating and Estimating Air 

Toxics Emissions from Municipal 

Waste Combustors, PB89-1952226, 

April 1989. [Table 4-3 for older mass 

burn MWCs]

MWC exhaust gas volume 

(typical)

5000 Nm3/metric 

ton MSW

Environment Agency of Japan in 

“Meeting on Measures to Control 

Dioxin Emission, the second report, 

25 June 1999” as reported by Ogura 

et al, Chemosphere 2001, 44, 1473-

1487.

mass burn MWC uncontrolled HF 

emission

1.8 mg HF/

Nm3

calculated (=0.009/5000*1E06mg/kg)

mass burn MWC

uncontrolled HF emission

1.9 Mg HF/

scm

calculated (=1.8*293/273)

EPA, Municipal Waste Combustion: 

Background Information Document 

for Promulgated Standards and 

Guidelines, EPA-453/R-95-0136, 

October 1995. [scm at 20 oC and 

Nm3at 0 oC]

MWC exhaust gas moisture

(typical) 

15 % Environmental Standards, Inc. 

Quality Assurance Project Plan for 

the ECA Incineration Testing 

Program—Phase II Fluorotelomer 

Incineration Testing, December 27, 

2005, revised June 23, 2006.

mass burn MWC uncontrolled HF 

emission

2.3 mg HF/ 

dscm

Conc(Dry)= 

High 

end

typical mass burn MWC 

uncontrolled (spray dryer inlet) 

HF emission, corrected to 7% O2 

(test average) 

7.9 mg HF/

dscm

Clean Air Engineering, Report on 

Compliance Testing Performed for 

Covanta of Fairfax, Inc Units 1, 2, 3, 

and 4 SDA Inlets and FF Outlets 

(Stacks) I-95 Energy/Resource 

Recovery Facility, Volume I of III, 

August 7, 2001. [highest across 3 

units tested]

Conc(Wet)

100% - Volume% H2O

100%
Page 8 of 24

Table A-2. Stoichiometric Calculation of Complete Oxidation of PTFE in Presence of Excess Methanol

Sample: PTFE [C2F4] Mass (μg) 100 mol wt (g/mol) 100 Constants

MeOH : Sample Ratio (Variable) 19,000 R 0.0821 L-atm/(mol-K)

standard T 25oC

Reactor Inside Diameter Reactor Length T (C) RT (sec) pressure 1 atm

(mm) 14 (in) 20 1000 2

(cm) 50.8

x (xs Air)

Effluent O2 

(%)

Effluent 

H2O (%)

Effluent CO2 

(%)

Effluent HF 

(%)

Air 

Vol 

(L)

MeOH 

Vol (L)

Run 

duration 

(min)

MeOH 

Injection 

Rate

Air Flow 

Rate

MeOH 

Vapor Flow 

Rate 

Input 

Vapor 

Flow Rate

Variable Target: >10 Target: 15 (8-20) Target: 1.22E-3 (μL/min) scc/min scc/min wet scc/min

Dry Basis Dry Basis Dry Basis

0% 0.0 23.1 15.1 3.17E-03 3.32 0.46 6.90 111.5 481.50 67.41 548.91

10% 2.0 21.4 13.6 2.86E-03 3.65 0.46 7.50 102.5 486.94 61.97 548.91

20% 3.7 19.9 12.4 2.61E-03 3.98 0.46 8.11 94.8 491.56 57.35 548.91

30% 5.1 18.5 11.4 2.40E-03 4.32 0.46 8.71 88.2 495.54 53.36 548.91

40% 6.3 17.4 10.5 2.22E-03 4.65 0.46 9.32 82.5 499.01 49.90 548.91

50% 7.3 16.4 9.8 2.06E-03 4.98 0.46 9.92 77.5 502.05 46.86 548.91

60% 8.2 15.5 9.2 1.93E-03 5.31 0.46 10.53 73.0 504.74 44.16 548.91

70% 9.0 14.7 8.6 1.81E-03 5.64 0.46 11.13 69.1 507.14 41.76 548.91

80% 9.7 13.9 8.1 1.70E-03 5.98 0.46 11.74 65.5 509.30 39.61 548.91

90% 10.3 13.3 7.7 1.61E-03 6.31 0.46 12.34 62.3 511.24 37.67 548.91

100% 10.9 12.7 7.3 1.53E-03 6.64 0.46 12.95 59.4 513.00 35.91 548.91

110% 11.4 12.1 6.9 1.45E-03 6.97 0.46 13.55 56.7 514.60 34.31 548.91

120% 11.8 11.6 6.6 1.38E-03 7.31 0.46 14.16 54.3 516.07 32.84 548.91

130% 12.2 11.2 6.3 1.32E-03 7.64 0.46 14.76 52.1 517.41 31.49 548.91

140% 12.6 10.7 6.0 1.27E-03 7.97 0.46 15.37 50.0 518.65 30.25 548.91

150% 13.0 10.3 5.8 1.21E-03 8.30 0.46 15.97 48.1 519.80 29.11 548.91

160% 13.3 10.0 5.5 1.17E-03 8.63 0.46 16.57 46.4 520.86 28.05 548.91

170% 13.6 9.6 5.3 1.12E-03 8.97 0.46 17.18 44.7 521.85 27.06 548.91

180% 13.9 9.3 5.1 1.08E-03 9.30 0.46 17.78 43.2 522.77 26.14 548.91

190% 14.1 9.0 4.9 1.04E-03 9.63 0.46 18.39 41.8 523.63 25.28 548.91

200% 14.3 8.7 4.8 1.01E-03 9.96 0.46 18.99 40.5 524.43 24.47 548.91

210% 14.6 8.5 4.6 9.73E-04 10.29 0.46 19.60 39.2 525.19 23.72 548.91

220% 14.8 8.2 4.5 9.42E-04 10.63 0.46 20.20 38.0 525.90 23.01 548.91
Page 9 of 24

Table A-3. Oxidation of Methanol: Stoichiometric Calculations with Refined Inputs

Reactant: Methanol Units Value Reference/Comment

monitor liquid temperature oC 23.8 Feed pump isothermal T: measured with 1/16" calibrated thermocouple with chiller controlling to 24.0 C

monitor liquid pressure psig 2500 Feed pump controller readout: pump discharge pressure (typical value)

liquid pressure psia 2514.7

liquid density g/mL 0.80296 NIST "Isothermal Properties for Methanol", http://webbook.nist.gov/chemistry/fluid/ a

monitor injection rate μL/min 61.71 Feed pump controller readout 

injection rate mL/min 0.06171

mass feed rate g/min 0.0496 = density (g/mL) * injection rate (mL/min)

molecular weight g/mole 32.0419 NIST "Methyl Alcohol", http://webbook.nist.gov/cgi/cbook.cgi?Name=methanol&Units=SI

molar feed rate mol/min 0.0015 = mass feed rate / molecular weight

Reactant: Synthetic air

std temperature oC 21.1 Brooks gas mass flow controller calibration sheet

monitor room pressure torr 740 MKS pressure transducer readout (typical)

monitor back pressure in. W.C. 20 Magnehelic reading:back pressure on reactor = impinger liquid level + CGA back pressure

pressure Atm 1.0228 reactor pressure = room pressure + back pressure

% oxygen (O2) % 21.06 Airgas Certificate of Analysis, Reference Number 32-112669912-1

% nitrogen (N2) % 78.94 = 100 - % oxygen [COA says N2 = balance]

monitor flow rate scc/min 662 Brooks mass flow controller readout for Synthetic Air

flow rate std L/min 0.662

moles O2 mol/min 0.0059 Calculated using Ideal Gas Law [n = PV/RT] with Universal Gas Constant (R) of 0.08206 L-atm/(mol-K)

moles N2 mol/min 0.0221 Calculated using Ideal Gas Law [n = PV/RT] with Universal Gas Constant (R) of 0.08206 L-atm/(mol-K)

Product moles

moles CH3OH mol/min 0.0000 Assuming complete oxidation: all CH3OH converts to CO2 and H20

mole CO2 mol/min 0.0015 Assuming complete oxidation: moles CO2 out = moles CH3OH in

moles H2O mol/min 0.0031 Assuming complete oxidation: moles H2O out = 2 * moles CH3OH in

moles O2 mol/min 0.0036 Assuming complete oxidation: moles O2 out = moles O2 in - moles O2 consumed

moles N2 mol/min 0.0221 Assuming N2 is unreacted: Moles N2 in = Moles N2 out

total mol/min 0.0304

Product volumes

CO2 std L/min 0.0365 Calculated using Ideal Gas Law [V = nRT/P] & Universal Gas Constant (R) of 0.08206 L-atm/(mol-K)

H2O std L/min 0.0730 Calculated using Ideal Gas Law [V = nRT/P] & Universal Gas Constant (R) of 0.08206 L-atm/(mol-K)

O2 std L/min 0.0847 Calculated using Ideal Gas Law [V = nRT/P] & Universal Gas Constant (R) of 0.08206 L-atm/(mol-K)

N2 std L/min 0.5226 Calculated using Ideal Gas Law [V = nRT/P] & Universal Gas Constant (R) of 0.08206 L-atm/(mol-K)

total std L/min 0.7168 Calculated using Ideal Gas Law [V = nRT/P] & Universal Gas Constant (R) of 0.08206 L-atm/(mol-K)

total scc/min 716.7602
Page 10 of 24

Table A-3. Oxidation of Methanol: Stoichiometric Calculations with Refined Inputs (continued)

Product composition wet basis dry basis (Note: Volume % = Mole %)

CO2 vol % 5.09% 5.67%

H2O vol % 10.19%

O2 vol % 11.81% 13.15%

N2 vol % 72.91% 81.18%

total vol % 100.00% 100.00%

Excess Air

Entering moles 

O2 mol/min 0.0059 Portion of monitored synthetic air flow input that is oxygen, on a molar basis

Required moles 

O2 mol/min 0.0023 Moles of O2 required for complete oxidation: 1.5 * moles CH3OH in

Excess air % 154.6%

a

E.W. Lemmon, M.O. McLinden and D.G. Friend, "Thermophysical Properties of Fluid Systems" in NIST Chemistry WebBook, NIST 

Standard Reference Database Number 69, Eds. P.J. Linstrom and W.G. Mallard, June 2005, National Institute of Standards and Technology, 

Gaithersburg, MD 20899 (http://webbook.nist.gov).
Page 11 of 24

Table A-4. Combustion Stoichiometry Calculations for Combustion of FTBP Composite 1

Units Value Reference and/or Comment

Reactant: FTBP Composite 1

monitor sample mass μg 100 target value for measured polymer sample mass, as is basis

analyzed solids content wt % 72.02% Akron Rubber Development Lab (ARDL) C & H Report, Table 5, average

sample mass μg, dry 72.02 target value for measured polymer sample mass, dry basis

normalized C content wt %, dry 57.7% Table S-2

normalized H content wt %, dry 3.73% Table S-2

normalized F content wt %, dry 38.62% Table S-2

total wt %, dry 100.00%

mass C in polymer μg, dry 41.52 = normalized dry wt % * sample mass (dry basis)

mass H in polymer μg, dry 2.68 = normalized dry wt % * sample mass (dry basis)

mass F in polymer μg, dry 27.81 = normalized dry wt % * sample mass (dry basis)

moles C in polymer mol 3.46E-06 atomic weight = 12.011 g/mol, ref: Morrison & Boyd, Organic Chemistry , 3rd ed, 1973.

moles H in polymer mol 2.66E-06 atomic weight = 1.0080 g/mol, ref: Morrison & Boyd, Organic Chemistry , 3rd ed, 1973

moles F in polymer mol 1.46E-06 atomic weight = 18.9984 g/mol, ref: Morrison & Boyd, Organic Chemistry , 3rd ed, 1973

Reactant: Methanol 

monitor liquid temperature oC 23.8 Feed pump isothermal T, measured with 1/16" calibrated thermocouple with chiller controlling to 24.0 C

monitor liquid pressure psig 2500 Feed pump controller readout: pump discharge pressure (typical value)

liquid pressure psia 2514.7

liquid density g/mL 0.80296 NIST "Isothermal Properties for Methanol", http://webbook.nist.gov/chemistry/fluid/ a

monitor injection rate μL/min 61.71 Feed pump controller readout

injection rate mL/min 0.06171

mass feed rate g/min 0.049551 = density (g/mL) * injection rate (mL/min)

molecular weight g/mole 32.0419 NIST "Methyl Alcohol", http://webbook.nist.gov/cgi/cbook.cgi?Name=methanol&Units=SI

molar feed rate mol/min 0.001546 moles = molecular weight / mass

Reactant: Synthetic air

std temperature oC 21.1 Brooks gas mass flow controller calibration sheet

monitor room pressure torr 740 MKS pressure transducer readout (typical value)

monitor back pressure in. W.C. 20 Magnehelic reading: back pressure on reactor = impinger liquid level + CGA back pressure

reactor pressure atm 1.02283 33.91 ft W.C. = 1 atm; 760 torr = 1 atm; reactor pressure = room pressure + back pressure

% oxygen (O2) % 21.06 Airgas Certificate of Analysis, Reference Number 32-112669912-1

% nitrogen (N2) % 78.94 Airgas Certificate of Analysis, Reference Number 32-112669912-1

monitor flow rate scc/min 662 Synthetic air flow rate monitored by Brooks gas mass flow controller

flow rate std L/min 0.662

moles O2 mol/min 0.005906 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mol-K)

moles N2 mol/min 0.022137 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mol-K)
Page 12 of 24

Table A-4. Combustion Stoichiometry Calculations for Combustion of FTBP Composite 1 (continued)

monitor Run Duration min 16 Preset value for combustion test experimental run

H consumption

convert F in polymer to HF mol/min 1.83E-07 1 mole H (i.e., 1/2 mole H2) per mole F to form HF, over run duration

excess H from polymer mol/min 1.55E-07 (moles H in polymer - moles of H need to convert F to HF) over run duration; note excess H --> H2O

moles H20 from xs polymer H mol/min 7.75E-08 2 moles H (i.e., 1 mole H2) per mole H20, over run duration

O2 consumption

convert C in polymer to CO2 mol/min 3.46E-06 1 mole O2 per mole C for C + O2 --> CO2, over run duration

convert H in polymer to H2O mol/min 3.88E-08 for excess H from polymer to H2O; 0.5 mol O2 per mole of H2O formed, over run duration

convert C & H in MeOH mol/min 0.0023 1.5 mole of O2 per mole of MeOH: CH3OH + 1.5 O2 --> CO2 + 2 H2O

Product moles

moles CH3OH mol/min 0.0000 Assuming complete oxidation: all CH3OH converts to CO2 and H20

mole CO2 mol/min 0.0015 Assuming complete oxidation: moles CO2 out = moles CH3OH in + moles C in (from polymer)

moles H2O mol/min 0.0031 Assuming complete oxidation: moles H2O out = 2 * moles CH3OH in + moles H20 in (from polymer)b

moles O2 mol/min 0.0036 Assuming complete oxidation: moles O2 out = moles O2 in - moles O2 consumed

moles N2 mol/min 0.0221 Assuming N2 is unreacted: Moles N2 in = Moles N2 out

total mol/min 0.0304

Product volumes

CO2 std L/min 0.0366 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mol-K)

H2O std L/min 0.0730 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mol-K)

O2 std L/min 0.0846 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mol-K)

N2 std L/min 0.5226 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mol-K)

total std L/min 0.7168 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mol-K)

total scc/min 716.7612

Product composition wet basis dry basis (Note: Volume % = Mole %)

CO2 vol % 5.10% 5.68%

H2O vol % 10.19%

O2 vol % 11.80% 13.14%

N2 vol % 72.91% 81.18%

total vol % 100.00% 100.00%

a

E.W. Lemmon, M.O. McLinden and D.G. Friend, "Thermophysical Properties of Fluid Systems" in NIST Chemistry WebBook, NIST Standard

 Reference Database Number 69, Eds. P.J. Linstrom and W.G. Mallard, June 2005, National Institute of Standards and Technology, Gaithersburg MD

 20899 (http://webbook.nist.gov).

b

Consistent with the requirement in Section C.2.2 of ECA Appendix C.2 to first convert weight % values from the labs to molar quantities on a dry basis,

the very small amount of water evaporated from the starting polymer sample is not accounted for here. 
Page 13 of 24

Table A-5. Combustion Stoichiometry Calculations for Combustion of FTBP Composite 2

Units Value Reference and/or Comment

Reactant: FTBP Composite 2

monitor sample mass μg 100 target value for measured polymer sample mass, as is basis

analyzed solids content wt % 75.70% Akron Rubber Development Lab (ARDL) C & H Report, Table 5, average

sample mass μg, dry 75.70 target value for measured polymer sample mass, dry basis

normalized C content wt %, dry 62.80% Table S-2

normalized H content wt %, dry 5.09% Table S-2

normalized F content wt %, dry 32.10% Table S-2

total wt %, dry 100.00%

mass C in polymer μg, dry 47.54 = normalized dry wt % * sample mass (dry basis)

mass H in polymer μg, dry 3.86 = normalized dry wt % * sample mass (dry basis)

mass F in polymer μg, dry 24.30 = normalized dry wt % * sample mass (dry basis)

moles C in polymer mol 3.96E-06 atomic weight = 12.011 g/mol, ref: Morrison & Boyd, Organic Chemistry , 3rd ed, 1973.

moles H in polymer mol 3.83E-06 atomic weight = 1.0080 g/mol, ref: Morrison & Boyd, Organic Chemistry , 3rd ed, 1973

moles F in polymer mol 1.28E-06 atomic weight = 18.9984 g/mol, ref: Morrison & Boyd, Organic Chemistry , 3rd ed, 1973

Reactant: Methanol 

monitor liquid temperature oC 23.8 Feed pump isothermal T, measured with 1/16" calibrated thermocouple with chiller controlling to 24.0 C

monitor liquid pressure psig 2500 Feed pump controller readout: pump discharge pressure (typical value)

liquid pressure psia 2514.7

liquid density g/mL 0.80296 NIST "Isothermal Properties for Methanol", http://webbook.nist.gov/chemistry/fluid/ a

monitor injection rate μL/min 61.71 Feed pump controller readout

injection rate mL/min 0.06171

mass feed rate g/min 0.049551 = density (g/mL) * injection rate (mL/min)

molecular weight g/mole 32.0419 NIST "Methyl Alcohol", http://webbook.nist.gov/cgi/cbook.cgi?Name=methanol&Units=SI

molar feed rate mol/min 0.001546 moles = molecular weight / mass

Reactant: Synthetic air

std temperature oC 21.1 Brooks gas mass flow controller calibration sheet

monitor room pressure torr 740 MKS pressure transducer readout (typical value)

monitor back pressure in. W.C. 20 Magnehelic reading: back pressure on reactor = impinger liquid level + CGA back pressure

reactor pressure atm 1.02283 33.91 ft W.C. = 1 atm; 760 torr = 1 atm; reactor pressure = room pressure + back pressure

% oxygen (O2) % 21.06 Airgas Certificate of Analysis, Reference Number 32-112669912-1

% nitrogen (N2) % 78.94 Airgas Certificate of Analysis, Reference Number 32-112669912-1

monitor flow rate scc/min 662 Synthetic air flow rate monitored by Brooks gas mass flow controller

flow rate std L/min 0.662

moles O2 mol/min 0.005906 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mole-K)

moles N2 mol/min 0.022137 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mole-K)
Page 14 of 24

Table A-5. Combustion Stoichiometry Calculations for Combustion of FTBP Composite 2 (continued)

monitor Run Duration min 16 Preset value for combustion test run

H consumption

convert F in polymer to HF mol/min 1.60E-07 1 mole H (i.e., 1/2 mole H2) per mole F to form HF, over run duration

excess H from polymer mol/min 2.29E-07 (moles H in polymer - moles of H need to convert F to HF) over run duration; note excess H --> H2O

moles H20 from xs polymer H mol/min 1.15E-07 2 moles H (i.e., 1 mole H2) per mole H20, over run duration

O2 consumption

convert C in polymer to CO2 mol/min 3.96E-06 1 mole O2 per mole C for C + O2 --> CO2, over run duration

convert H in polymer to H2O mol/min 5.73E-08 for excess H from polymer to H2O; 0.5 mol O2 per mole of H2O formed, over run duration

convert C & H in MeOH mol/min 0.0023 1.5 mole of O2 per mole of MeOH: CH3OH + 1.5 O2 --> CO2 + 2 H2O

Product moles

moles CH3OH mol/min 0.0000 Assuming complete oxidation: all CH3OH converts to CO2 and H20

mole CO2 mol/min 0.0016 Assuming complete oxidation: moles CO2 out = moles CH3OH in + moles C in (from polymer)

moles H2O mol/min 0.0031 Assuming complete oxidation: moles H2O out = 2 * moles CH3OH in + moles H20 in (from polymer)b

moles O2 mol/min 0.0036 Assuming complete oxidation: moles O2 out = moles O2 in - moles O2 consumed

moles N2 mol/min 0.0221 Assuming N2 is unreacted: Moles N2 in = Moles N2 out

total mol/min 0.0304

Product volumes

CO2 std L/min 0.0366 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mole-K)

H2O std L/min 0.0730 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mole-K)

O2 std L/min 0.0846 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mole-K)

N2 std L/min 0.5226 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mole-K)

total std L/min 0.7168 Calculated using Ideal Gas Law & Universal Gas Constant of 0.08206 L-atm/(mole-K)

total scc/min 716.7616

Product composition wet basis dry basis (Note: Volume % = Mole %)

CO2 vol % 5.11% 5.69%

H2O vol % 10.19%

O2 vol % 11.80% 13.14%

N2 vol % 72.91% 81.18%

total vol % 100.00% 100.00%

a

E.W. Lemmon, M.O. McLinden and D.G. Friend, "Thermophysical Properties of Fluid Systems" in NIST Chemistry WebBook, NIST Standard

 Reference Database Number 69, Eds. P.J. Linstrom and W.G. Mallard, June 2005, National Institute of Standards and Technology, Gaithersburg MD

 20899 (http://webbook.nist.gov).

b

Consistent with the requirement in Section C.2.2 of ECA Appendix C.2 to first convert weight % values from the labs to molar quantities on a dry basis,

the very small amount of water evaporated from the starting polymer sample is not accounted for here. 
Page 15 of 24

Table S-1. Summary of FTBP Composites Elemental Analysis

Sample % Solids % Water

Carbon 

(As Is)

Hydrogen 

(As Is) a

Carbon 

(Dry Basis)

Hydrogen 

(Dry Basis)b

Fluorine 

(Dry Basis)

Reported 

Result Calculated

Reported 

Result

Reported 

Result

Normalized 

Value

Normalized 

Value

Normalized 

Value

% % % % %

FTBP 

Composite 1 72.02 27.98 45.80 6.092 57.7 3.7 38.6

FTBP 

Composite 2 75.70 24.30 47.54 6.575 62.8 5.1 32.1

a Reported value for Hydrogen (H) includes H present due to H2O in sample.

b Corrected to exclude H in H2O in sample.
Page 16 of 24

Table S-2. PFOA Analysis Method Description

Sample Matrix Impinger water (HPLC water with absorbed reactor exhaust gas)

Method 

Summary

40 mL of aqueous sample (spiked with surrogate) concentrated via 

C18 SPE cartridge eluted with 5 mL of methanol then determined via 

electrospray liquid chromatography/tandem mass spectrometry 

(LC/MS/MS) using selected reaction monitoring (SRM)

Sensitivity Limit of Quantitation: 25 ng/L 

Limit of Detection: 5 ng/L 

Calibration Calibration standards prepared in water with final concentrations of 

0, 25, 50, 100, 250, 500, and 1000 ng/L. Linear regression 

calibration curve (using 1/x weighting) with correlation coefficient (R) 

≥ 0.992 (R2≥ 0.985) for initial calibration.

QC Criteria Laboratory Control Standard (LCS) recovery: 70 – 130%

Extracted check standard recovery: 85 – 115%

Surrogate spike recovery: 70 – 130%

Surrogate Phase I transport test: 13C-PFOA: mass-labeled perfluoro-n-octanoic 

acid (m+2) provided by DuPont (custom synthesized by PerkinElmer), 

i.e., perfluoro-n-[1,2-

13C2]-octanoic acid or 1,2-13C2-PFOA

Phase II combustion test:

13C-PFOA: mass-labeled perfluoro-noctanoic acid (m+4) purchased from Wellington Laboratories, i.e., 

perfluoro-n-[1,2,3,4-

13C4]-octanoic acid or 1,2,3,4-13C4-PFOA

Chromatography

Instrument Micromass Quattro Ultima

HPLC Column Genesis C-8, 5 cm x 2.1 mm i.d. x 4 μm

Mobile Phase A 2 mM ammonium acetate in water

Mobile Phase B methanol

Ions Monitored: Analyte Transition Retention Time

PFOA 413  369 ~5 min

1,2-

13C2-PFOA 415  370 ~5 min

1,2,3,4-

13C4-PFOA 417  372 ~5 min

Linear PFOA and branched PFOA are not chromatographically 

resolved by this method and thereby cannot be distinguished.

Laboratory MPI Research Inc., State College, PA
Page 17 of 24

Table S-3. FTBP Combustion Test Results for Impinger Samples

Test Substance Sample Identification

Fluoride

(mg/L)

PFOA 

(ng/L)

None Pre-Test Thermal Blank <0.05 Not analyzed

Pre-Test Steam Clean 0.82 Not analyzed

Composite 1 Pre-Run Thermal Blank #1 0.20 ND

Experimental Run #1 0.58 ND

Steam Clean #1 0.59 ND

Post-Run Thermal Blank #1 0.19 ND

Pre-Run Thermal Blank #2 <0.05 ND

Experimental Run # 0.48 ND

Steam Clean #2 0.72 ND

Post-Run Thermal Blank #2 <0.05 ND

Pre-Run Thermal Blank #3 <0.05 ND

Experimental Run #3 0.28 ND

Steam Clean #3 0.78 ND

Post-Run Thermal Blank #3 <0.05 ND

HPLC Water Blank <0.05 ND

Composite 2 Pre-Run Thermal Blank #4 0.16 ND

Experimental Run #4 0.45 ND

Steam Clean #4 1.56 ND

Post-Run Thermal Blank #4 0.11 ND

Pre-Run Thermal Blank #5 0.10 ND

Experimental Run #5 0.47 ND

Steam Clean #5 1.30 ND

Post-Run Thermal Blank #5 0.12 ND

Pre-Run Thermal Blank #6 0.12 ND

Experimental Run #6 0.29 ND

Steam Clean #6 0.98 ND

Post-Run Thermal Blank #6 0.11 ND

HPLC Water Blank 0.05 ND

ND – Compound not detected. Limit of Detection (LOD) for this matrix is 5 ng/L.

As the pre-test thermal blank and pre-test steam cleaning show, the source of 

fluoride for the post-run steam cleaning runs was determined to be thermal 

degradation of the perfluoroelastomer O-ring on the exit end of the reactor.
Page 18 of 24

Table S-4. Fluoride Ion Recovery, Exhaust Gas Hydrogen Fluoride (HF) Concentration, and Fluoride Yield

E

xperim

ental

RunM

e

asured

Fluoride ionconcentrationM

ass of

poly

m

er

Fluorine inpoly

m

er

W

ater v

olum

e

PredictedFluoride ionconcentrationFluoride ionR

eco

v

ery

Observ

ed H

F

concentration

Run 

Avg 

O2 

conc Observ

ed H

F

concentrationat 7%

O2

Predicted H

F

concentrationat 7%

O2

Observ

ed

Fluoride ionYieldObserv

ed H

F

Yield

(mg/L) (μg) (%) (mL) (mg/L) (%) (mg/dscm) (%) (mg/dscm) (mg/dscm)

(g F/ kg 

Polymer)

(g HF/ kg

Polymer)

1 0.58 102 38.6 60.28 0.65 89 3.6 13.32 6.6 7.4 343 361

2 0.48 104 38.6 60.51 0.66 72 3.0 13.29 5.5 7.5 279 294

3 0.28 103 38.6 60.43 0.66 43 1.8 13.25 3.2 7.4 164 173

4 0.45 108 32.1 60.81 0.57 79 2.9 13.20 5.1 6.4 253 267

5 0.47 108 32.1 60.69 0.57 82 3.0 13.22 5.3 6.4 264 278

6 0.29 91 32.1 60.20 0.49 60 1.8 13.23 3.3 5.4 192 202

Measured Fluoride ion concentration from MPI Report. Lab notes "QC measurements did not meet the criteria specified in the method or 

QAPP. The data should be considered estimated values."

Mass of polymer is Sample Net Weight.

Concentration of Fluorine in polymer is normalized fluorine concentration on dry basis.

Water volume is total water volume in impingers for run, assuming water density = 1 g/mL.

Predicted Fluoride ion concentration = [(mass of polymer) * (% Fluorine in polymer)/100] / (water volume)

Fluoride ion Recovery (%) = (measured Fluoride ion concentration) / (predicted Fluoride ion concentration) * 100

Observed HF concentration = (measured F ion conc) * (water volume) / 1000 * [(Molecular Wt of HF)/(Atomic Wt of F)] / (dry gas volume)

Molecular weight of HF = (atomic weight of H) + (atomic weight of F)

Atomic weight of H = 1.008 g/mole

Atomic weight of F = 18.998 g/mole

Dry gas volume is volumetric flow rate on dry basis * duration of pyroprobe heating (16 min)

Volumetric flow rate = 6.32E-04 dscm/min (from stoichiometric calculations)

Run Avg O2 conc is run average oxygen concentration from CGA for run.

Observed HF concentration at 7% O2 = (observed HF concentration) * (21.1% - 7%) / (21.1% - [(Run Avg O2 conc) %])

Predicted HF concentration at 7% O2 = (predicted HF concentration) * (21.1% - 7%) / (21.1% - [(Run Avg O2 conc) %])

Predicted HF concentration = (predicted F ion conc) * (water volume) / 1000 * [(Molecular Wt of HF) / (Atomic Wt of F)] / (dry gas volume)

F ion Emission Factor = (measured F ion conc)*(water volume)*1000/(mass of polymer)

HF Emission Factor = (measured F ion conc)*(water volume)*1000/(mass of polymer)*(Molec Wt of HF)/(Atomic Wt of F)

Notes:
Page 19 of 24

Table S-5. PFOA Exhaust Gas Concentration Calculations

Experimental 

Run

Measured 

PFOA 

concentration 

Equivalent 

PFOA 

concentration, 

assuming 

ND = LOD

Water 

volume

Equivalent 

PFOA 

exhaust gas 

concentration

Run 

Avg 

O2

conc

Equivalent 

PFOA 

exhaust gas 

concentration 

at 7% O2

(ng/L) (ng/L) (mL) (ng/dscm) (%) (ng/dscm)

1 ND 5 60.28 30 13.32 54

2 ND 5 60.51 30 13.29 54

3 ND 5 60.43 30 13.25 54

4 ND 5 60.81 30 13.20 54

5 ND 5 60.69 30 13.22 54

6 ND 5 60.20 30 13.23 53

Notes:

Water volume is total water volume in impingers for run, assuming water density = 1 g/mL.

Dry gas volume is volumetric flow rate on dry basis * duration of pyroprobe heating (16 min)

Volumetric flow rate (dry) = 6.3184E-04 dscm/min (from stoichiometric calculations)

Run Avg O2 conc is run average oxygen concentration from CGA for run.

Exhaust gas concentration at 7% O2 = (exhaust gas concentration) * (21.1% - 7%) / (21.1% - [(Run Avg O2 conc) %])
Page 20 of 24

Table S-6. 

13C-PFOA Surrogate Spike Recovery for Combustion Test Impinger Samples

Sample Identification

13C-PFOA Found 

(ng/L)

Amount 13C-PFOA 

Added (ng/L)

13C-PFOA Recovery 

(%)

Pre-Run Thermal Blank #1 525 500 105

Experimental Run #1 529 500 106

Steam Clean #1 536 500 107

Post-Run Thermal Blank #1 531 500 106

Pre-Run Thermal Blank #2 537 500 107

Experimental Run # 527 500 105

Steam Clean #2 468 500 94

Post-Run Thermal Blank #2 546 500 109

Pre-Run Thermal Blank #3 536 500 107

Experimental Run #3 527 500 105

Steam Clean #3 524 500 105

Post-Run Thermal Blank #3 556 500 111

HPLC Water Blank 510 500 102

Pre-Run Thermal Blank #4 495 500 99

Experimental Run #4 519 500 104

Steam Clean #4 492 500 98

Post-Run Thermal Blank #4 549 500 110

Pre-Run Thermal Blank #5 587 500 117

Experimental Run #5 531 500 106

Steam Clean #5 536 500 107

Post-Run Thermal Blank #5 596 500 119

Pre-Run Thermal Blank #6 526 500 105

Experimental Run #6 544 500 109

Steam Clean #6 474 500 95

Post-Run Thermal Blank #6 507 500 101

HPLC Water Blank 515 500 103
Page 20 of 24

Table S-7. Typical Waste Incineration Exhaust Gas Oxygen Levels 

Exhaust O2 Level 

(dry basis)

Type of Incinerator Reference

10% (nominal) Mass burn MWCa Blount Energy Resource Corp. Correlation Procedure 

for Continuously Monitoring Furnace Temperatures 

(Warren County Resource Recovery Facility), March 

22, 1989.

10.8% (average) Mass burn MWC Clean Air Engineering. Test Report for Covanta of 

Fairfax, Inc. I-95 Energy/Resource Recovery Facility, 

1997.

8.4%b(average) Refuse Derived Fuel 

(RDF) MWC

Finklestein, A. and R. D. Klicius. National Incinerator 

Testing and Evaluation Program: The Environmental 

Characterization of Refuse-derived Fuel (RDF) 

Combustion Technology, Mid-Connecticut Facility, 

Hartford, Connecticut, EPA-600/R-94-140 (NTIS 

PB96-153432), December 1994.

10 – 13% Modular MWC Pace Analytical. Comprehensive Emissions Test 

Report: MSW Incinerator Unit No. 1 ESP Outlet & 

MSW Incinerator Unit No. 2 ESP Outlet (Polk County 

Solid Waste Plant), March 11-14, 2003.

13.5% Medical waste 

incinerator

EPA. Medical Waste Incineration Emission Test 

Report: Weeks Memorial Hospital, Lancaster, New 

Hampshire, EMC Report 96-MWI-11, March 1996.

a MWC = municipal waste combustor

b Calculated from spray dryer inlet O2 concentrations (basis not specified) across 8 runs over range of 

steam loads during performance test runs indicative of “good combustor operation”.
Page 21 of 24

Figure S-1. Typical Structure of a Fluorotelomer-Based Polymer in this Study

Hydrocarbon

Side Chain

Crosslinker 

Monomer 

X

FC

R

FC FC

Fluorotelomer

Side Chain 

Hydrocarbon

Polymer

Backbone
Page 22 of 24

Figure S-2. Thermogravimetric Analysis of FTBP Composites at 25oC/min
Page 23 of 24

Figure S-3. Reactor Temperature Profile for Combustion Testing

100

200

300

400

500

600

700

800

900

1000

1100

0 10 20 30 40 50 60 70 80 90 100

Distance from Furnace Inlet (cm)

T

e

m

p

erature (

oC)

(Target Temperature = 1000°C)

With 600 standard cc/min of synthetic air (21.1% oxygen, balance 

nitrogen; Airgas) flowing through the reactor, the reactor temperature 

profile was performed by sequentially measuring the reactor internal gas 

temperature every 2.54 cm along the length of the quartz tube. This 

profiling was conducted in air (without methanol fuel present) prior to 

combustion testing due to safety reasons. The effective reactor length 

(indicative of gas residence time) at 1000oC was 66 cm of the 76 cm long 

section of the quartz tube radiantly heated by the split tube furnace. 

Supplemental calculations after the completion of the testing program 

indicate that oxidation of the methanol fuel feed to the reactor could have 

resulted in temperature overshoot as high as 1283oC (adiabatic reaction 

temperature) at the inlet end of the reactor followed by approximately 0.15 

second cool down. Such overshoot would result in the mean gas 

temperature of the reactor increasing from 1000oC to 1003oC during 

combustion testing.