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

  TOC \o "1-3" \h \z \u   HYPERLINK \l "_Toc273556574" 1.0 
Stoichiometric Calculations	  PAGEREF _Toc273556574 \h  3  

 HYPERLINK \l "_Toc273556575" 1.1	Establishing Experimental Conditions	 
PAGEREF _Toc273556575 \h  3  

 HYPERLINK \l "_Toc273556576" 1.1.1	Constraints	  PAGEREF _Toc273556576
\h  3  

 HYPERLINK \l "_Toc273556577" 1.1.2	Calculating Experimental Run
Duration	  PAGEREF _Toc273556577 \h  3  

 HYPERLINK \l "_Toc273556578" 1.1.3	Summary	  PAGEREF _Toc273556578 \h 
4  

 HYPERLINK \l "_Toc273556579" 1.2	Setting Combustion Test Air and
Methanol Feed Rates	  PAGEREF _Toc273556579 \h  4  

 HYPERLINK \l "_Toc273556580" 1.3	References	  PAGEREF _Toc273556580 \h 
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

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

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”,

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 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 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.

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.

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 Nm3 at 0 oC]

	MWC exhaust gas moisture

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



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]

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

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

	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).



 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.



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 

rrelation 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-n-octanoic
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



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.





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) %])



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





	

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”.

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

 

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

(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.

 PAGE   

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Conc(Wet)

100% - Volume% H2O

100%

Hydrocarbon

Side Chain

Crosslinker Monomer  

X

FC

R

FC

FC

Fluorotelomer

Side Chain 

Hydrocarbon

Polymer

Backbone

