EPA/600/A-96/065
For Proceedings of 1996 International Incineration Conference
Development of PIC Target Analyte List for Hazardous Waste Incineration Processes
Jeffrey V, Ryan and Paul M. Lemieux
U.S. Environmental Protection Agency
National Risk Management Research Laboratory
Air Pollution Prevention and Control Division
Research Triangle Park, NC 27711
Christopher Lutes and Dennis Tabor
Acurex Environmental Corporation
PO Box 13109
Research Triangle Park, NC 27709
Abstract
Current analytical schemes for measuring organic emissions from hazardous waste incineration (HWI)
processes do not characterize the full spectrum of products of incomplete combustion (PICs) that may be emitted. In
fact, required incineration emissions measurements are oriented towards quantifying principal organic hazardous
consiituents (POHCs) and other noncombustion related organic compounds. As a result, the emissions measurement
approach is based more on what is fed into the incinerator than what may be emitted by the incineration process.
Experiments were performed to generate, collect, and characterize the organic emissions from a pilot-scale rotary
kiln hazardous waste incinerator using a complex, surrogate hazardous waste mixture in order to develop an analyte
list representative of volatile, scmivolatile, and nonvolatile organic HWI emissions that includes PICs. Organic
emissions were collected and analyzed using a combination of conventional and nonconventional techniques.
Emphasis was placed on expanding the capabilities of existing methodologies, such as gas chromatography/mass
spectrometry (GC/MS), to identify and quantify nontarget analytes. Analytes identified include: alkylated,
chlorinated, brominated, and mixed bromochloro aromatics, alkanes, alkenes, and alkynes; chlorinated, brominated,
mixed bromochloro, alkylated, oxygenated polyaromatic hydrocarbons; and chlorinated, brominated, mixed
bromochloro dibenzodioxins and furans. Of the volatile and semivolatile organic species found, less than half have
been identified. Less than 25% of those found were actual target analytes.
Introduction
The current regulatory approach for hazardous waste incineration (HWI) is based on assessing the
destruction of principal organic hazardous constituents (POHCs). As a result, associated EPA test methods
specifically focus on identifiying and quantifying these compounds. Concerns are increasing over the products of
incomplete combustion (PICs) that may be emitted as a result of incineration. Required analytical schemes for
measuring organic emissions from HWI processes do not fully characterize the spectrum of PICs that may be
emitted. Because POHCs are "target analytes" for identification and quantitation, only a small number of PICs are
typically identified. As a result, the number of PICs identified may be relatively small compared to the actual
number present.
The EPA's Office of Solid Waste (OSW) is interested in including PICs in their risk assessments for
hazardous waste combustors (HWCs). HWCs are defined as hazardous waste incinerators , hazardous-waste-burning
cement kilns, and hazardous-waste-burning lightweight aggregate kilns. A comprehensive list of hazardous PICs
from HWC sources is needed to augment risk assessments. While considerable data are available on PICs from HWI
processes, the data generated have been primarily collected using conventional methodologies - the EPA test
methods that focus on the quantititation of POHCs. As a result, they are not considered to encompass the breadth of
potential PICs. More innnovative sampling and analytical approaches are required.
To support OSW's Combustion Strategy, the EPA's National Risk Management Research Laboratory
(NRMRL), Air Pollution Prevention and Control Division (APPCD), Air Pollution Technology Branch (APTB)
conducted a study to help develop a target analyte list for PICs from hazardous waste incinerators.

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Experimental
The incineration tests were performed using the EPA/APPCD Rotary Kiln Incinerator Simulator (RKIS)
located in the EPA Environmental Research Center HWI research laboratory in Research Triangle Park, NC. The
facility has a Research Conservation and Recovery Act (RCRA) Research, Development, and Demonstration
(RD&D) permit to burn actual and surrogate hazardous waste. The RKIS, shown in Figure 1, consists of a 73 kW
(250,000 Btu/hr) rotary kiln section, a transition section, and a 73 kW (250,000 Btu/hr) secondary combustion
section. The RKIS was designed for the testing of liquid and solid surrogate hazardous waste materials.
/
Secondary Combustion Chamber
&
'///////////////////A
V/,

Choke
i—Liquid Waste
Sample Ports
Rotary Leaf
Spring Seal

Afterburner
Liquid
Waste
Main
Burner
Ramrod
Kiln Section Transition Section
Figure 1. Rotary kiln incinerator simulator
The RKIS was designed to contain the salient features of full-scale kilns, but still be sufficiently versatile to
allow experimentation by varying one parameter at a time or controlling a set of parameters independently. The
rotating kiln section contains a recess which contains the solid waste during incineration. The recess was designed
with a length to diameter (L/D) ratio of 0.8, which is 20 to 25% of a full-scale system. The main burner, based on an
International Flame Research Foundation (IFRF) variable swirl design, is the primary heat source for the system.
Natural gas was used as the primary fuel during startup and idle, then was switched over to the surrogate waste feed
used throughout testing.
From the kiln section, the combustion gases enter the transition section. The gases then flow into the
experimental secondary combustion chamber (SCC). The SCC consists of three regions: the mixing chamber, the
plug flow section, and the stack transition section. A replaceable choke section separates the mixing chamber from
the plug flow section. A conical refractory insert has been installed into the first plug flow sub-section to provide a
gradual divergence from the choke diameter to the plug flow section diameter and minimize recirculation zones
downstream of the choke. The afterburner, also based on an IFRF variable swirl design, provides heat and flame to
the SCC, and was also fired with natural gas during startup and idle times, then switched to the liquid surrogate waste
during the tests.
Combustion gases exiting the afterburner pass through a water-jacketed convective cooling section of 20.3-
cm (8-in) diameter stainless steel (SS) ducting. Further cooling is achieved by adding ambient dilution air via a
dilution damper located upstream of the 9.9-m (35-ft) sampling duct. Emissions samples were collected at sampling
locations 66.7-cm (169.5-in) and 98.6-cm (250.5-in) downstream of the dilution damper. These sampling locations
2

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are oriented to meet isokinetic sampling requirements.
The surrogate hazardous waste that was fed during tests was designed to possess representative compounds
from many common classes of organic hazardous wastes. The composition of the surrogate hazardous waste feed
was developed based on recommendations from members of OSW. Table I lists the composition of the surrogate
waste feed. In addition to the organic surrogate waste, an aqueous mixture of metal salts, including zinc nitrate
hexahydrate, nickel nitrate hexahydrate, and copper nitrate hexahydrate, was also fed into the kiln. The purpose of
the metals injection was to provide a representative supply of metal catalyst to promote any heterogeneous reactions
forming polychlorinated dibenzodioxins and furans (PCDDs/PCDFs). The liquid surrogate waste was injected as
fuel into both the primary burner and afterburner. The liquid was injected using a pump, and was metered using
calibrated rotameters.
Class
Table 1. Waste Feed
Compound
Composition
Formula
Mass
carrier liquid
No. 2 fuel oil
n/a
50.0
chlorinated non-aromatic
methylene chloride
chloroform
carbon tetrachloride
CHjCI;
CHCI,
CCI4
15.93
8.94
4.79
chlorinated aromatic
monochlorobenzenc
dichlorobenzene
chlorophcnol
QH,CI
C6H4CI3
QH,CIO
6.65
7.69
3.00
non-chlorinated aromatic
toluene
xylene
c7hk
QH„,
10.40
10.43
alcohol
isopropanol
C,H(,0
4.71
ketone
methyl ethyl ketone
C4HsO
9.67
nitrated waste
pyridine
CjHjN
11,79
non-chlorinated polyaromatic
naphthalene
C10H,
3.00
brominated non-aromatic
bromoform
ethylene dibromide
CHBr,
C,H4Br,
1.50
1.50
Several different RKIS operating conditions were employed during the incineration tests. These operating
conditions were designed to simulate several operating modes for the incinerator system, including off-specification
combustion. Since this is a small idealized system, the RKIS was operated in a slightly off-specification mode to
produce measurable quantities of diverse PICs. The operating test conditions used are listed in Table 2.
Run
Date
5
5/3/95
6
5/4/95
9
5/12/95
10
5/16/95
13
8/14/95
14
8/16/95
Table 2. Test Conditions
Description
Baseline conditions, kiln T = 800 °C, SCC T = 1000 1
Baseline conditions, kiln T = 800 °C, SCC T = 1000 '
Low SCC temperature, SCC T = 650 °C
Low SCC temperature, SCC T = 650 °C
SCC fuel-rich, afterburner stoichiometric ratio = 0.9
SCC fuel-rich, afterburner stoichiometric ratio = 0 9
The RKIS was equipped with a continuous gas analysis and data acquisition system consisting of two sets of
continuous emissions monitors (CEMs) for oxygen (02), carbon monoxide (CO), carbon dioxide (C02), nitric oxide
(NO), and total hydrocarbons (THCs), with sample locations at both the kiln and SCC exits.
3

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Standard EPA sampling methodologies were used to collect volatile, semivolatile, and nonvolatile organic
emissions. Volatile organics (VOCs) were collected using two different methods: Method 0040 (TedtarBag)' and
the Volatile Organic Sampling Train (VOST)1, Semivolatile organics (SVOCs) were also collected using two
different methods: Modified Method 5 (MM5)J and the Source Assessment Sampling System (SASS)4, Dioxins
were collected using Method 23'. These are the same standard methods that would be used during actual compliance
testing.
The volatile, semivolatile, and nonvolatile organic samples were analyzed following the analytical
methodologies associated with each respective sampling method, Additional analytical procedures were
incorporated to expand the range of qualitative analyses.
The Tedlar bag samples were analyzed using two separate analytical procedures based on target analytes. Gas
chromatography with flame ionization detection (GC/FID) was used to screen for CI through C4 straight chain
alkanes, alkenes, and alkynes. The actual target analyte list is presented in Table 3. The Tedlar bag samples were
also analyzed by gas chromatography/mass spectrometry (GC/MS) following the procedures described in SW-846
Methods 5040 and 82 406,7. Method 8240 quantifies VOCs with boiling points ranging from —30 to - 200 °C The
Method 8240 VOC target analyte list for these tests is presented in Table 4.
The VOST samples were also analyzed by SW-846 Methods 5040 and 8240. The target analyte list presented
in Table 4 was also used for the VOST analyses.
Table 3. CI - C4 Target Analytes
Methane
Ethene
Propyne
Propane
Acetylene (Ethyne)
Ethane
Propene
n-Butane
Table 4. Target Volatile Organic Compounds
Dichlorodifluoromethane
Chloromethane
Vinyl Chloride
Bromomethane
Chloroethane
Trichlorotrifluoromethane
I. I -Dichloroethene
lodomethane
Carbon Disulfide
Acetone
Methylene Chloride
1,2-Dichloroethene (total)
1.1-Dichloroethane
Chloroform
1.2-Dichloroethane
2-Butanone
1,1,1 -Trichloroethane
Carbon Tetrachloride
Benzene
Trichloroethene
1,2-Diehloropropane
Dibromomcthane
Bromodichloromethane
cis-1,3-Dichloropropcne
2-Hexanone
trans- 1,3-Dichloropropene
1.1.2-Trichloroe	thane
Dibromochloromethanc
1,2-Dibromoethane
Bromoform
4-Methyl-2-pentanone
Toluene
Tetrachloroethenc
Chlorobenzcne
Ethylbenzene
1,1,1,2-Tetrachloroethane
m/p-Xylenc
o-Xylene
Styrene
1,1,2.2 Tetrachloroethane
1.2.3-Trichloropropane
trans-1,4-Dichloro-2-butene
Pentachloroethane
l,2-Dibromo-3-chioropropanc
4

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The MM5 samples were analyzed in general accordance with SW-846 Methods 3542 and 8270IW, The front
half (filter), back hall (XAD-2), and condensate sample fractions were extracted separately. In addition, the front
half and back half sample fractions were extracted with acetone, and then toluene, following the dichloromethane
extraction, to enhance the recovery of organic compounds with differing polarities. Each dichloromethane extract
was analyzed separately. The Method 8270 semivoiatile organic target analyte list used for these tests is presented in
Table 5.
Table 5. Target'Semivolatile Organic Compounds
N-Methyl-N-nitroso-ethanamine
Dimethylphathalate
bis(2-chloroethy 1 )Ether
2,6-Dinitrotoluene
Aniline
Acenaphthene
Phenol
4-Nitroaniline
2-Chlorophenol
2,4-Dinitrophenol
1,3-Dichlorobenzene
Dibenzofuran
1,4-Dichlorobenzene
Pentachlorobenzene
1,2-Dichlorobenzene
2,4-Dinitrotoiuene
Benzyl alcohol
2,3,4,6-Tetrachlorophenol
bis(2-chloroisopropyl)Ether
4-Nitrophenol
2-Methylphenol
Fluorene
Acetophenone
Diethyl phathalate
Hexachloroethane
4-Chlorophenyl phenyl ether
Methylphenol
2-MethyI-4,6-dinitrophenol
N-Nitrosodipropylatnine
Diphenylamine
Nitrobenzene
4-Bromophenyl phenyl ether
1-Nitrosopiperidine
Phenacetin
Isophorone
Hexachlorobenzene
2,4-Dimethylphenol
Pentachlorophenol
bis(2-chloroethoxy)Methane
Pentachloronitrobenzene
2,4-Dichiorophenol
Phenanthrene
1,2,4-Trichlorobenzene
Anthracene
Naphthalene
Dibutyl phthalate
2-Nitrophenol
Fluoranthene
2,6-Dichlorophenol
Pyrene
Hexacliloropropene
P-Dimethylaminoazobenzene
4-ChloroaniIine
Benzyl butyl phthalate
Hexachlorobutadiene
Chryscne
N-Butyl-N-nitroso-butanamine
Benzo(a)anthracene
4 -C h 1 oro- 3 - meth y 1 - p heno 1
di-N-Octyl phthalate
2-Methylnaphthalene
Benzo(b)fluoranthene
1,2,4,5-Tetrachlorobenzene
7,12-Dimcthylbenz(a)anthracene
Hexachlorocyelopentadiene
Benzo(k)fluoranthene
2,4,6-Trichlorophenol
Benzo(a)pyrene
2,4,5-Trichlorophenol
3-Methylcholanthrenc
2-ChloronaphthaIene
lndeno( 1,2,3-cd)pyrene
2-NitroaniIine
Dibenz(a,h)anthracene
(continued)
5

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Tabic 5 (continued)
3-Nitroaniline
Benzo(ghi)peryIene
Accnaphthylenc
Nontarget organic compounds present in both volatile and semi volatile organic samples were tentatively
identified primarily through mass spectral matching. The mass spectra from unknowns were compared to known
mass spectra contained in a database. Through probability-based matching, tentative identifications were assigned.
The quality of the match, along with the analyst's judgement, were the primary basis for tentatively assigning
identification to unknowns. Confirmation with known standards has not been performed at this time. The number of
compounds identified for spectral matching is based on the analytical system response of individual compounds
relative to the other compounds present in the sample. Typically, the 10-20 nontarget compounds with the greatest
system response are identified for spectral matching. For these analyses, the number was 30.
PCDDs/PCDFs were analyzed by an approach that is similar to Method 23, except that: the analyses were
performed by low resolution mass spectrometry (LRMS) as opposed to high resolution mass spectrometry (HRMS);
and the target analytes were expanded to include mono-, di-, and tri- CDD/CDF congeners. The 2,3,7,8 isomers
were not confirmed as required by Method 23. All PCDDs/PCDFs are reported as total mass per congener.
The PCDD/PCDF sample extracts were also analyzed to screen for the presence of polybrominated dibenzo
dioxins and furans (PBDDs/PBDFs) and mixed bromochloro dibenzodioxins and furans (MBCDDs/MBCDFs).
Standardized analytical techniques for these target compounds do not exist. The analysis for MBCDDs/MBCDFs is
particularly hindered by the lack of both isotopically labelled and unlabel led standards. Because of the lack of the
standards, the screening approach targeted only those PBDD/PBDF and MBCDD/MBCDF isomers for which
standards could be obtained. These included BrCl,DD, Br2Cl,DD, Br„DD, Br5DD, BrCI,DF, Br. DF. and BrsDF.
Samples were analyzed by LRMS using isotope dilution techniques similar to those used to analyze for
PCDDs/PCDFs. Prior to extraction, the samples were spiked with known amounts of isotopically labelled Br4DD
and Br4DF. These were used as internal standards to quantify the target native PBDDs/PBDFs and
MBCDDs/MBCDFs as well as assess method performance.
Results and Discussion
It must be emphasized that the results reported here are both preliminary and incomplete. Test conditions in
addition to those presented in Table 2 were also evaluated. Most importantly, the tentative nontarget analyte
identifications are just that, tentative. Their identities have not been confirmed. Readers are cautioned to keep these
considerations in mind when drawing information from this paper.
Tedlar bag results are limited at this time. No CI - C4 alkenes, alkenes, or alkynes were detected. Estimated
minimum detection limits are on the order of 1 - 2 ppm. The VOC GC/MS data have not yet been interpreted.
The VOST analytical results indicate that a significant number of VOC PICs have been identified both as
target analytes and as tentatively identified compounds (TICs). For the analytical data evaluated, PICs identified
both as target analytes and TICs are presented in Tables 6 and 7, respectively. Of the 44 target analytes. 38 were
detected. It should be noted that several of these compounds are POHCs. Over 50 nontarget analytes were
tenatively identified as PICs. However, a large number of PICs present in the VOST samples were not identified.
To aid in perspective, at least 82 compounds were detected in a single sample. Of those, 28 were identified as target
analytes, 21 were tentatively identified, and 33 remained unidentified.
An interesting comparison was made of the CI and C2 halogenated alkanes, alkenes, and alkynes. A table
was made of the possible chloro, bromo, and mixed bromochloro organics with one and two carbons (Table 8). With
only several exceptions, each compound was detected in at least one sample. These CI and C2 compounds are of
particular interest as these species are considered to be precursors in aromatic ring propagation reactions leading to
higher molecular weight PICs'0.
Table 6. Target Volatile Organic Compounds Detected
Dichlorodifluoromethane
1,2-Dichloropropane
Dibromomethane
Chloromethane
Vinyl chloride
Bromomclhane
Bromodichloromethane
cis-1,3-Dichloropropenc
(continued)
6

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Table 6 (continued)

Chloroethane
trans- 1,3-Dichloropropene
Trichlorotrifluoromethane
Dibromochloromeihane
1,1-Dichloroethene
1,2-Dibrornoethane
Carbon disulfide
Bromoform
Acetone
4-Methyl-2-pentanonc
Methylene chloride
Toluene
1,2-Dichloroethene
Tetrachloroethane
1,1 -Dichloroethane
Chlorobenzene
Chloroform
Ethylbenzene
1,2-Dichloroethane
1,1,1,2-Tetrachloroethane
2-Butanone
Xylene (M,P)
1,1,1 -Trichloroethane
Xylene (O)
Carbon tetrachloride
Styrene
Benzene
trans-1,4-Dichloro-2-butene
Trichloroethene
1,2-Dibromo-3-chloropropane
Table 7.
Bromotrichloromethane
Chloroethyne
Bromoelhyric
Bromochloroethyne
Dichlorocthync
Bromoethene
Bromochloroethene
Dibromoethcnc
B romod ich lorocthcne
Dibromochlorocthene
Tribromoelhene
Bromotrichloroethcnc
Tribromochlorocthcnc
Dibromodichloroethenc
Tclrabromoethcne
Bromoehloroethane
Bromopropyne
Bromochloropropync
B romod ich loropropy ne
Bromopropene
Pcntachloropropcne
Dibromopropane
Hexachlorobutadiene
Pentachlorobutadicnc
Chlorobutane
Tentatively Identified Volatile Organic Compounds
Propene
Methyl propene
Methyl butane
Butadiyne
Butadiene
Pentene
Pentane
Hexene
Hexanc
Methylcyclohexane
Heptane
Methylheptane
Dimethylheptane
Octane
Nonane
Decane
Methyldecane
Undecane
Methylfuran
Benzaldehyde
Methylpentenal
Benzonitrile
Chlorothiophene
Tetrachlorothiophcne
Dibromothiophene
(continued)
7

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Tabic 7 (continued)
Bromoheptane
Chlorooctane
Benzylchloride
Bromobenzene
Bromomcthylbenzenc
Bromodimethylbenzene
Bromochlorobenzene
Dibromobenzene
Bromodichlorobcnzenc
Table 8. CI and C2 Chloro, Bromo, and Mixed Bromochloro Organics
CI Hydrocarbons
Target
Compound
Analyte
Detected
chloromethane
Yes
•
bromomethane
Yes
•
dicliloromclhane
Yes
•
dibromomethane
Yes
•
bromochloromethane
Yes
•
irichloromethane
Yes
•
tribromomethanc
Yes
•
bromodichloromethane
Yes ; •
dibrotnochloromethane
Yes •
tetrachloromethane
Yes
•
tetrabromomethanc
No
•
broinolrichloromethanc
No
•
dibromodichloromelhane
No

tribromochloromethane
No
C2 Alkynes

clilorocthyne
No ¦ •
bromoethyne
No
•
dichloroethyne
No
•
dibromoethyne
No

bromochloroethyne
No i •
C2 Alkenes


chloroeihene
Yes
•
bromoelhene
No
•
dichlorocthene (total)
Yes
•
dibromocthene
No ! •
bromochloroethene
No
•
trichloroethenc
Yes
•
(ribromoethene
No
•
bromodichloroethene
No

dibromochloroethene
No
•
tetrachloroethene
Yes
•
tetrabromoethene
No
•
bromotrichlorocthene
No
•
dibromodichloroethene
No
•
tribromochloroethene
No
•
C2 Alkanes


chloroethanc
Yes
•
broinocthane
No

dichloroetliane
Yes
•
dibromocthane
Yes 1 •
hiomochlorocthane
No ! •
(continued)

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Table 8 (continued)
trichloroethane
Yes
•
tribromoethane
No

bromodichloroethane
No

dibromochlorocthane
No

tctrachloroethane
Yes
•
tetrabromoethane
No

bromotnchloroethane
No

dibromodichloroelhane
No

tribromochloroethane
No

The semivolatile organic analytical results also indicate that a significant number of PICs have been identified
both as target analytes and as TICs. For the analytical data evaluated, PICs identified both as target analytes and
TICs are presented in Tables 9 and 10, respectively. Many of the target analytes were detected. Of the 77 target
analytes, 42 were detected. It should be noted once again that several of these compounds are POHCs. Over 50
nontarget analytes were tenatively identified as PICs. Many of the PICs present in the MM5 samples were not
identified. Also, the mix of PICs found on the filter sample fraction differed from that of the XAD-2 sample
fraction. For a selected filter sample, at least 174 compounds were detected: 25 were identified as target analytes, 11
were tentatively identified, and 138 remained unidentified. For a selected XAD-2 sample, at least 194 compounds
were detected: 18 were identified as target analytes, 17 were tentatively identified, and 159 remained unidentified.
The large number of unidentified compounds is not due to an inability to identify them, but rather to the fact that
only a fixed number were targeted for spectral matching. This also holds true for the volatile organic analyses.
Table 9. Target Semivolatile Organic Compounds Detected
Hexachlorobutadiene
Dibenzofuran
Hexachlorocyclopentadiene
Acetophenone
1,3-Dichlorobcnzene
Naphthalene
1,4-Dichlorobenzene
2-Methylnaphthalene
1,2-Dichlorobenzene
2-Chloronaphthalene
1,2,4-Trichlorobenzene
Acenaphthylene
1,2,4,5-Tetrachlorobenzenc
Acenaphthene
Pentachlorobenzene
Fluorene
Hexachlorobcnzene
Phenanthrene
Phenol
Anthracene
Methylphenol
Fluoranthene
2-Nitrophenol
Pyrene
2,4,6-Trich.lorophenol
Chrysene
2,4,5-Trichlorophenol
Benzo(a)anthracene
2,3,4,6-Tetrachlorophenol
Benzo(b)fluoranthene
Pentachlorophenol
7,12-Dimethylbenz(a)anthracene
Dimethylphthalate
Benzo(k)fluoranthene
Diethyl phthalate
Benzo(a)pyrene
Dibutyl phthalate
Indeno( 1,2,3-cd)pyrene
Benzyl butyl phthalate
Dibenz(a,h)anthracene
di-N-Octyl phthalate
Benzo(ghi)perylene
9

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Tabic 10. Tentatively Identified Semivolatile Organic Compounds
Bromomethylpropane
Methyphenanthrene
T ribromomethane
Methylanthracene
Bromotrichloroethene
Dimethylphenanthrene
Dibromod ichloroethene
B romonaphthalene
T ribromochloroethene
B romoanthracene
T etrabromoethene
Xanthenone
Tribromobutane
Phenalenone
Bromocyclohexane
Benzopyranone
Dibromocyclohexane
Naphthalenedione
Bromobenzene
Isobenzofurandione
Bromomethylbenzene
Anthracenedione
Bromochlorobenzene
Ethylhexanol
Dibromobenzene
Butoxyethanol
Dibromochlorobenzene
Bromocyclohexanol
Bromodichlorobenzene
Bromochlorocyclohexanol
Bromotrichlorobenzene
Bromomethoxycyclohexane
Bromodiehlorophenol
Phenoxybiphenyl
Dibromochlorophenol
Hexanoic acid
Tribromophenol
Ethylhexanoic acid
Benzaldehydc
Benzoic acid, methyl ester
Benzonitrile
Butanedioic acid, dimethyl ester
Bromobenzoniirile
Dibromoacetic acid, methyl ester
Dibromothiophenc
Hexanedioic acid, dimethyl ester
Chloropyridine
Decamethylcyclopentasiloxane
Dichloronaphthyridine
Dodecamethylcyclohexasiloxane
Biphenyl
Tetradecamethylcycloheptasiloxane
Nonane
Benzofuran
Decane
Trimethylhexane
PCDD/PCDF anlytical results indicate that all mono- through octa PCDD/PCDF congeners were detected.
Several samples indicated that PBDDs/PBDFs and MBCDDs/MBCDFs were indeed present. For the low
temperature test condition, Run 10, BrCl,DD, Br2Cl2DD, Br4DF, and Br5DF were detected.
Summary and Conclusions
Pilot-scale incineration tests have been performed under varied combustion conditions feeding a mixed
surrogate waste, resulting in the generation of numerous PICs. While many of these PICs were identified as target
analytes using required, standardized sampling analytical methods, the majority of PICs present in the incineration
emissions were not target analytes. Although a substantial number have been tentatively identified, a considerably
larger number have not been identified at this time. It can be concluded from these experiments that the current
sampling and analytical schemes for characterizing HWI emissions provide an incomplete picture of the emission
profile.
As a result of these experiments, an expanded list of PIC target analytes has been developed. This list is by no
means complete or comprehensive. This list should be viewed in context with this particular set of experiments; i.e.,
waste mix. The PICs resulting from other mixed waste streams have not been evaluated.
The PICs identified fall into several chemical classes. A wide variety of chloro, bromo, and mixed
bromochloro alkanes, alkenes, alkynes, aromatics, and polyaromatics were detected. In addition, nonhalogenated
hydrocarbon homologues along with oxygenated, nitrogenated, and sulfonated organics were detected. Analytical
10

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methods specifically suited to these chemical classes are needed to enhance PIC characterizations.
Future Plans
The data and chemical analyses performed to date are by no means complete. More comprehensive data and
chemical analyses are intended. These include:
•	Perform more rigorous spectral analysis of existing samples
•	Confirm tentative identifications with known standards where possible
•	For semivolatile organics, fractionate samples into functional classes and perform more thorough analyses
•	Analyze the toluene and acetone sample extracts
•	Use more innovative analytical techniques such as gas chromatography with atomic emission detection
(GC/AED) and liquid chromatography/mass spectroscopy (LC/MS) to further characterize samples
•	Conduct additional tests to verify initial results and investigate other surrogate waste mixes
References
1)	EPA Test Method 0040 "Sampling of Principal Organic Hazardous Constituents from Combustion Sources
Using Tedlar Bags " in Test Methods for Evaluating Solid Wastes, Volume II, SW-846 (NTIS PB88-239223).
Environmental Protection Agency, Office of Solid Waste, Washington, DC. (August 1994)
2)	EPA Test Method 0030 "Volatile Organic Sampling Train " in Test Methods for Evaluating Solid Wastes,
Volume II, SW-846 (NTIS PB88-239223). Environmental Protection Agency, Office of Solid Waste, Washington,
DC. (September 1986)
3)	EPA Test Method 0010 "Modified Method 5 Sampling Train " in Test Methods for Evaluating Solid Wastes,
Volume II, SW-846 (NTIS PB88-239223). Environmental Protection Agency, Office of Solid Waste, Washington,
DC. (September 1986)
4)	EPA Test Method 0020 "Source Assessment Sampling System " in Test Methods for Evaluating Solid
Wastes, Volume II, SW-846 (NTIS PB88-239223). Environmental Protection Agency, Office of Solid Waste,
Washington, DC, (September 1986)
5)	EPA Test Method 23 "Determination of Polychlorinated Dibenzo-p-dioxins and Polychlorinated
Dibenzofurans from Stationary Sources" in Code of Federal Regulations, Title 40, Part 60, Appendix A, U.S.
Government Printing Office, Washington DC. (July 1991)
6)	EPA Test Method 5040 "Protocol for Analyis of Sorbent Cartridges from Volatile Organic Sampling Train" in
Test Methods for Evaluating Solid Wastes, Volume I, SW-846 (NTIS PB88-239223). Environmental Protection
Agency, Office of Solid Waste, Washington, DC. (September 1986)
7)	EPA Test Method 8240 "Gas Chromatography/Mass Spectrometry for Volatile Organics" in Test Methods for
Evaluating Solid Wastes, Volume I, SW-846 (NTIS PB88-239223). Environmental Protection Agency, Office of
Solid Waste, Washington, DC. (September 1986)
8)	EPA Test Method 3542 "Extraction of Semivolatile Organic Analytes Collected Using Modified Method 5
Sampling Train" in Test Methods for Evaluating Solid Wastes, Volume I, SW-846 (NTIS PB88-239223).
Environmental Protection Agency, Office of Solid Waste, Washington, DC. (January 1995)
9)	EPA Test Method 8270 "Gas Chromatography/Mass Spectrometry for Semivolatile Organics: Capillary
Column Technique" in Test Methods for Evaluating Solid Wastes, Volume I, SW-846 (NTIS PB88-239223).
Environmental Protection Agency, Office of Solid Waste, Washington, DC. (September 1986)
10)	Tsang, W., "Mechanisms for the Formation and Destruction of Chlorinated Organic Products of Incomplete
Combustion," Combustion Science and Technology, 74:99-116 (1990)

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ivraTV/TOT DTD to 117 TECHNICAL REPORT DATA
iNxtIViKJ_i it, 1 jr Jr ill (Please read Instructions on the reverse before compleP
1. REPORT NO. 2.
EPA/600/A-96/065
3.
4. TITLE AND SUBTITLE
Development of PIC Target Analyte List for
Hazardous Waste Incineration Processes
S. REPORT DATE
6. PERFORMING ORGANIZATION COOE
7. authoh(s) y. Ryan and P. M. Lemieux (EPA), and
C, Lutes and D. Tabor (A cur ex)
8. PERFORMING ORGANIZATION REPORT NO.
». PERFORMING ORGANIZATION NAME AND ADDRESS
Acurex Environmental Corporation
P. O. Box 13109
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-D4-0005
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Air Pollution Prevention and Control Division
Research Triangle Park, NC 27711
13. TYPE OF REPORT ANO PERIOD COVERED
Published paper; 10/94-3/96
14. SPONSORING AGENCY CODE
EPA/600/13
is.supplementary notes APPCD project officer is Jeffrey V. Ryan, Mail Drop 91, 919/541-
1437. Presented at 15th Annual Conference on Incineration and Thermal Treatment
Technologies, Savannah, GA, 5/6-10/96.
is.abstract The paper discusses experiments that were performed to generate, collect,
and characterize organic emissions from a pilot-scale rotary-kiln hazardous waste
incinerator (HWl) using a complex, surrogate hazardous waste mixture in order to
develop an analyte list representative of volatile, semivolatile, and nonvolatile or-
ganic HWI emissions that include products of incomplete combustion. Organic emis-
sions were collected and analyzed using a combination of conventional and nonconven-
tional techniques. Emphasis was placed on expanding the capabilities of existing „
methodologies, such as gas chromatography/mass spectroscopy, to identify and
quantify nontarget analytes. Analytes identified included: alkylated, chlorinated,
brominated, and mixed bromochloro aromatics, alkanes, alkenes, and alkynes;
chlorinated, brominated, mixed bromochloro, alkylated, oxygenated polyaromatic
hydrocarbons; and chlorinated, brominated, mixed bromochloro dibenzodioxins and
furans. Of the volatile and semivolatile organic species found, less than half have
been identified. Less than a quarter of those found were actual test analytes.
17. KEY WORDS AND OOCUMENT ANALYSIS
1. DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. cosati Field/Group
Pollution
Wastes
Incinerators
Organic Compounds
Kilns
Analyzing
Pollution Control
Stationary Sources
Hazardous Waste
Products of Incomplete
Compustion (PICs)
13 B
14G
07C
13	A
14	B -
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)

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