Assessment of Emissions
of Specific Compounds
from a Resource Recovery
Municipal Refuse Incinerator
-------
ASSESSMENT OF EMISSIONS OF SPECIFIC COMPOUNDS FROM A
RESOURCE RECOVERY MUNICIPAL REFUSE INCINERATOR
by
Clarence L. Haile
Ruth B. Blair
Robert M. Lucas
Thomas Walker
TASK 61
FINAL REPORT
EPA Contract No. 68-01-5915
MRI Project No. 4901-A(6l)
Prepared for
U.S. Environmental Protection Agency
Office of Pesticides and Toxic Substances
Field Studies Branch
401 M Street, S.W.
Washington, D.C. 20460
Attn: Dr. Frederick Kutz, Project Officer
Mr. Daniel Heggem, Task Manager
-------
DISCLAIMER
This document has been reviewed and approved for publication by the
Office of Toxic Substances, Office of Pesticides and Toxic Substances, U.S.
Environmental Protection Agency. The use of trade names or commercial prod-
ucts does not constitute Agency endorsement or recommendation for use.
-------
PREFACE
This final report was prepared for the Environmental Protection Agency
under EPA Contract No. 68-01-5915, Task 61. The task was directed by
Dr. Clarence L. Haile. This report was prepared by Dr. Clarence L. Haile,
Robert M. Lucas (Research Triangle Institute), and
John S. Stanley provided technical consultation and
Mrs. Ruth B. Blair, Dr
Mr. Thomas Walker. Dr
support for PCDD and PCDF analyses. Technical support was also provided by
G. Scheil, R. Stultz, E. Olson, K. Hall, J. Pavelonis, D. Griffin,
G. Radolovich, J. Onstot, and M. Wickham.
MID'
SEARCH INSTITUTE
r.
E. Going
Program Manager
Approved:
James L. Spigarelli, Director
Analytical Chemistry Department
May 22, 1984
111
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CONTENTS
Preface iii
Figures vi
Tables vii
Abbreviations x
1. Introduction 1
2. Summary 2
3. Recommendations 3
4. Plant Description 4
5. Sampling Methods 6
Gaseous samples 6
Solid and aqueous samples 9
6. Analysis Methods 14
General analytical scheme 14
Sample compositing and extraction 14
Extract cleanup 17
Extract analysis 19
7. Field Test Data 26
8. Analytical Results 41
Target PAH and phthalates 41
PCBs 46
PCDDs 46
PCDFs 54
9. Analytical Quality Assurance Results 62
Surrogate compound recoveries 62
Blank samples 69
Standard reference materials 69
Flue gas analyte breakthrough tests 69
10. Emission Results . 74
References 81
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FIGURES
Number Page
1 Incinerator cross-sectional view 5
2 Flue gas sampling point locations - stack cross section ... 8
3 Quench pit and water recycle system 13
4 General analytical scheme 15
5 HRGC/MS-SIM chromatogram of tetrachlorodibenzo-£-dioxin
congeners on an SP-2340 column 25
6 Operating temperatures and steam flows recorded during
flue gas sampling - day 1 29
7 Combustion gas analysis results from continuous monitoring
during flue gas sampling - day 1 30
8 Operating temperatures and steam flows recorded during
flue gas sampling - day 2 31
9 Combustion gas analysis results from continuous monitoring
during flue gas sampling - day 2 32
10 Operating temperatures and steam flows recorded during
flue gas sampling - day 3 33
11 Combustion gas analysis results from continuous monitoring
during flue gas sampling - day 3 34
12 Operating temperatures and steam flows recorded during
flue gas sampling - day 4 35
13 Combustion gas analysis results from continuous monitoring
during flue gas sampling - day 4 36
14 Operating temperatures and steam flows recorded during
flue gas sampling - day 5 37
15 Combustion gas analysis results from continuous monitoring
during flue gas sampling - day 5 38
16 HRGC/HRMS-SIM chromatogram for fly ash composite A extract. . 56
vi
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TABLES
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Samples Collected, Sampling Locations, and Collection Frequencies.
Modified Method 5 Train Sample Point Locations
Time Strata for Specimen Collection
General Formulas for Determining Specimen Collection Times ....
Sampling Schedule by Media (Military Time)
Surrogate Spiking Compounds
Recoveries for Compounds Chromatographed on Silica Gel by the
Procedure Used to Clean Sample Extracts
Recovery of PCB Surogate Compounds from Sulfuric Acid Treated
Extracts
Target PAH and Phthalate Compounds
Instrument and Operating Parameters for Scanning HRGC/MS Analysis.
Instrumental Parameters and Mass Ranges Used for HRGC/MS-SIM
Analyses of PCBs
PCB Compounds Used for Quantitation Standards
Instrument and Operating Parameters for HRGC/MS-SIM Analyses
of PCDDs/PCDFs
Instrument and Operating Parameters for HRGC/HRMS-SIM Analysis
of Selected Extracts for 2,3,7 ,8-Tetrachlorodibenzo-£-dioxin . .
Daily Data Summaries for Flue Gas Sampling
Summary of Plant Background Air Volumes
ESP Operating Conditions
Proximate and Ultimate Analysis Results for Bottom Ash and Fly Ash
Page
7
7
10
10
11
16
18
18
20
20
21
22
23
24
27
28
39
40
Vll
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TABLES (continued)
Number Page
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
Target Compounds Identified in Flue Gas Samples
Target Compounds Identified in Ash Samples .
Target Compounds Identified in Aqueous Samples
Target Compounds Identified in Plant Background Air
Polychlorinated Biphenyls Identified in Flue Gas Samples
Polychlorinated Biphenyls Identified in Ash Samples
Polychlorinated Dibenzo-£-dioxins Identified in Flue Gas Samples .
Concentrations of 2,3,7 ,8-Tetrachlorodibenzo-£-dioxin in
Selected Flue Gas Samples
Polychlorinated Dibenzo-£-dioxins Identified in Ash Samples. . . .
Polychlorinated Dibenzo-£-dioxins Identified in Plant Background
Air
Polychlorinated Dibenzofurans Identified in Flue Gas Samples . . .
Polychlorinated Dibenzofurans Identified in Ash Samples
Polychlorinated Dibenzofurans in Plant Background Air
Recoveries of Surrogate Target Compounds Spiked into the
Flue Gas Samples
Recoveries of Surrogate Target Compounds Spiked into the
Plant Background Air Samples ...
Summary of Recoveries of the Surrogate Target Compounds .
Recoveries of Polychlorinated Biphenyl Surrogates Spiked
into Flue Gas Samples
Recoveries of Polychlorinated Biphenyl Surrogates Spiked
into Plant Background Air Samples ...
Summary of Recoveries of the Polychlorinated Biphenyl Surrogate
Compounds . . ...
Recoveries of Polychlorinated Dibenzo-£-dioxin Surrogates
Sniked into Flue Gas Samples
4?
44
47
49
50
52
53
54
55
57
58
60
61
63
64
65
66
67
68
70
Vlll
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TABLES (concluded)
Number Page
39 Recoveries of Polychlorinated Dibenzo-£-dioxin Surrogates
Spiked into Plant Background Air Samples 71
40 Summary of Recoveries of the Polychlorinated Dibenzo-£-dioxin
Surrogate Compounds. 71
41 Analytes Identified in Blank Samples 72
42 Results for Analysis of SRM 1649 72
43 Analytes Identified in Flue Gas Train First Impingers 73
44 Emission Rates for Target Compounds in Flue Gas 75
45 Emission Rates for Polychlorinated Biphenyls in Flue Gas 77
46 Emission Rates for Polychlorinated Dibenzo-|>-dioxins in Flue Gas . 79
47 Emission Rates for Polychlorinated Dibenzofurans in Flue Gas ... 80
IX
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LIST OF ABBREVIATIONS
acfm -- Actual cubic feet per minute
dscf -- Dry standard cubic feet
dscfm -- Dry standard cubic feet per minute
dscm -- Dry standard cubic meter
dscmra -- Dry standard cubic meter per minute
EICP -- Extracted ion current plots, constructed by computer from
scanning gas chromatography/mass spectrometry data
-- Electrostatic precipitator
-- High resolution (fused silica capillary column) gas chroma-
tography with low resolution mass spectrometry detection
-- HRGC/MS operating the spectrometer in a selected ion
monitoring mode
HRGC/HRMS-SIM -- HRGC/MS-SIM with the spectrometer operated at higher than
unit resolution (e.g., 10,000 resolution)
-- Polynuclear aromatic hydrocarbons
-- Polychlorinated biphenyls
— Polychlorinated dibenzo-£-dioxins
-- Polychlorinated dibenzofurans
-- Perfluorokerosene
— Polytetrafluoroethylene, e.g., Teflon®
-- Total hydrocarbons
ESP
HRGC/MS
HRGC/MS-SIM
PAHs
PCBs
PCDDs
PCDFs
PFK
PTFE
THC
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SECTION 1
INTRODUCTION
This study was conducted as a part of a nationwide survey to determine
organic emissions from major stationary combustion sources. The principal
compounds of interest were polynuclear aromatic hydrocarbons (PAHs) and
polychlorinated aromatic compounds, including polychlorinated biphenyls (PCBs),
polychlorinated dibenzo-j>-dioxins (PCDDs), and polychlorinated dibenzofurans
(PCDFs). This report describes an assessment of emissions from a resource
recovery municipal refuse incinerator.
Previous tests conducted under this program include a pilot study of the
variability of combustion source emissions and a nationwide survey of emis-
sions from major coal-fired utility boiler plants. The pilot study involved
21 days of testing at a utility boiler plant co-fired with coal and municipal
refuse-derived fuel and 11 days of testing at a resource recovery municipal
refuse incinerator.1 The variability of emissions (as determined from total
organic chlorine in flue gas and ash samples) among test days and between the
two plants was used to develop the sampling design for subsequent tests.2
The emissions results from the pilot study and the nationwide survey of coal-
fired utility boilers have been reported elsewhere.1'3'4
A summary of the results of the municipal refuse incinerator study is
contained in Section 2 of this report. Section 3 presents recommendations
for future work. A brief description of the incinerator is contained in
Section 4. The sampling and analysis methods as applied to the plant are de-
scribed in Sections 5 and 6. The field test data and analytical results are
presented in Sections 7 and 8. Section 9 describes the analytical quality
assurance results. The emissions results are summarized in Section 10.
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SECTION 2
SUMMARY
This study was conducted as a part of a nationwide survey to determine
organic emissions from major stationary combustion sources. The principal
compounds of interest were polynuclear aromatic hydrocarbons (PAHs) and poly-
chlorinated aromatic compounds, including polychlorinated biphenyls (PCBs),
polychlorinated dibenzo-£-dioxins (PCDDs), and polychlorinated dibenzofurans
(PCDFs). This report presents the results of emissions testing of a resource
recovery municipal refuse incinerator.
All emissions (including flue gas, fly ash, and bottom ash) were sampled
from a mass burn, refuse-fired steam generation plant. The furnace was designed
to burn ^ 125 tons/day and generated steam at 32,000 Ib/hr. Daily flue gas
samples (^ 15 m3) were collected from ports on the stack using modified EPA
Method 5 trains. Plant background air was sampled during the flue gas testing
and grab samples of ashes and quench waters were taken periodically according
to a statistically derived 24-hr schedule. The total sample collection period
was 5 days. The samples were extracted and analyzed using fused silica capil-
lary gas chromatography with mass spectrometry detection (HRGC/MS).
PAHs and phthalates were identified in flue gas, fly ash, bottom ash,
quench water, and background air samples. Naphthalene and acenaphthylene were
the most abundant PAH compounds, averaging 620 and 220 |jg/dscm, respectively,
in flue gas samples. PCBs were identified in the flue gas and ash samples.
Total PCBs in flue gas samples averaged 670 ng/dscm. Fly ash contained an
average of 41 ng/g total PCBs. PCDD and PCDF compounds were identified in
flue gas and fly ash. The mean concentrations of total PCDDs and PCDFs were
2,300 and 11,000 ng/dscm, respectively. Fly ash contained an average of 800
and 3,000 ng/g, respectively. The distribution of PCDD and PCDF homologs in
the flue gas and fly ash samples were similar. Pentachloro homologs were most
abundant.
Emission rates were determined for compounds identified in the flue gas
samples by multiplying the concentrations by the flue gas flow rates. The
emission rates calculated for PCBs, PCDDs, and PCDFs were 15, 51, and 250
mg/hr, respectively.
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SECTION 3
RECOMMENDATIONS
1. Conduct emissions testing at additional refuse incineration
facilities. Relatively few municipal refuse incineration units in the United
States have been tested for emissions of specific hazardous organics. Addi-
tional data are needed to better characterize emissions from refuse incinera-
tion and allow assessment of the risks of current incineration practices.
2. Investigate relationships between emission rates for specific com-
pounds and key plant design and operating parameters. The emissions and engi-
neering data contained in this report, reported by other researchers, and re-
sulting from testing at additional facilities should be compiled and evaluated,
possibly using multivariant statistical analysis. The results,of this analysis
may provide relational information that could be used to design more efficient
incineration units with lower emissions.
3. Determine the aqueous leaching potential of hazardous compounds
identified in incinerator fly ash. Since incinerator fly ash is typically
disposed by landfilling, information on the potential for leaching hazardous
organics from ash with high concentrations of hazardous materials is needed
to assess the potential for groundwater contamination.
4. Examine the computerized HRGC/MS data from this study for the pres-
ence of additional hazardous compounds. It is likely that the data archived
for this study contains information on compounds (in addition to the target
PAH, PCB, PCDD, and PCDF compounds) that would provide a more complete char-
acterization of refuse incinerator emissions. Reanalysis of flue gas and fly
ash extracts focusing on specific compounds could also expand the data avail-
able for examination. Target compounds should include nitropolynuclear aro-
matics, nitrogen heterocyclic aromatics, sulfur heterocyclic aromatics, and
biphenylene.5
5. Develop a more complete inventory of PCDD and PCDF isomers. The
variety of PCDD and PCDF isomers available for use as analytical standards is
limited. The availability of additional standards, especially with chlorine
in the 2, 3, 7, and 8 positions, would expand the number of isomers that could
be uniquely determined.
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SECTION 4
PLANT DESCRIPTION
The incineration plant consists of two identical units fired with raw
(i.e., unprocessed) refuse. The incinerator sampled is shown diagrammati-
cally in Figure 1. The refuse collection system supplying the unit services
primarily residential urban and suburban neighborhoods. Large household
appliances and other difficult to combust items are collected separately and
disposed in a sanitary landfill.
The incinerator is charged with raw refuse from a storage pit by an
overhead crane. The refuse burns without auxiliary fuel as it travels down a
series of three inclined reciprocating grates. The residence time in the
furnace is approximately 45 to 60 min. Unburned residue is discharged into a
water-filled quench pit. Particulates removed from the flue gas with an elec-
trostatic precipitator (ESP) are also conveyed into the quench pit. The pit
is continuously dredged into a truck for landfill disposal.
The unit is designed to handle approximately 125 tons/day, producing
steam at 32,000 Ib/hr. The incineration process is somewhat susceptible to
upsets caused by wet refuse, e.g., grass clippings and refuse collected dur-
ing heavy rains. During stable operation, the firebox temperature is near
2300°F and the furnace wall temperature ranges from 1450 to 1550°F.
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u
Refuse Pit
* ESP Ash Sampling Location
** Bottom Ash Sampling Location
Electrostatic
Precipitator
.Economizers
Continuous
Monitoring
Port
\
Reciprocating Grates
Ash
Wasting
Pit
ESP Ash
Conveyor
Stack
Modified
Method Five
Sampling
Location .
Figure 1. Incinerator cross-sectional view.
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SECTION 5
SAMPLING METHODS
The general sampling methods used in this study are described in detail
elsewhere.5 This section presents an overview of the specific application of
these methods to the resource recovery incinerator.
The general sample collection scheme is shown in Table 1. The sampling
locations are indicated on the plant diagram in Figure 1. Samples were col-
lected on 5 consecutive days. Flue gases and background air were sampled
largely during daylight hours. Grab samples of ashes and quench water were
collected according to a 24-hr schedule. Feed samples, i.e., raw refuse, were
not collected due to the difficulty of obtaining representative specimens.
The rigorous collection, homogenization and selection required to obtain rep-
resentative specimens were beyond the scope of this study.
GASEOUS SAMPLES
Flue Gas
Flue gas samples were collected from two ports on the stack, located
downstream from the ESP, using modified EPA Method 5 sampling trains. The
modification consisted of a condenser to cool the gases and an adsorbent
resin cartridge to retain organic vapors placed between the filter box and
the first impinger. The cartridge was charged with 75 g of precleaned XAD-2
resin. Ice-chilled water was circulated through the condenser jacket and a
jacket around the cartridge during sample collection.
A single flue gas sample was collected on each sampling day using two
trains. The trains were operated at isokinetic sampling rates and were tra-
versed (as specified in EPA Method 5) until roughly 5 to 7.5 m3 were collected
in each train. The locations of the sampling points are presented in Table 2
and are shown on a diagram of the stack cross section in Figure 2. Each daily
sample consisted of the particulate catches, resin cartridges, and rinses (of
probe and train components forward of the first impinger) from both trains.
The contents of the first impinger in each train were also recovered to check
for analyte breakthrough.
Plant Background Air
A single plant background air sample was collected each sampling day
using a resin cartridge (identical to that used in the flue gas trains), a
pump, and a dry gas meter. The sampling system was located near the air in-
let to the furnace, on a walkway near the overhead crane over the refuse pit.
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TABLE 1. SAMPLES COLLECTED, SAMPLING LOCATIONS, AND COLLECTION FREQUENCIES
Sample type
Location
Collection
frequency
Gaseous samples
Flue gas
Plant background air
Solid samples
Bottom ash
Fly ash
Aqueous samples
Quench water effluent
Quench water influent
Ports on stack I/day
Catwalk above refuse pit I/day
Conveyor from sluice trench 6/day
Conveyor to sluice trench 6/day
Overflow weirs from sluice trench 6/day
Recycled water holding tank 2/day
TABLE 2. MODIFIED METHOD 5 TRAIN SAMPLE POINT LOCATIONS
Fraction of stack I.D.
Traverse point no. (%)
1 4.4
2 14.6
3 29.6
4 70.4
5 85.4
6 95.6
Distance from stack wall
(in.)
2.13
7.00
14.25
33.75
41.00
45.88
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00
Sample Point Locations
Figure 2. Flue gas sampling point locations - stack cross section.
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The sampling rate was maintained at 0.70 to 0.75 ft3/min (0.020 to 0.021
m3/min) until 6.5 to 7.5 m3 were collected.
Continuous Monitoring
Ports for continuous monitoring of the combustion gas composition were
located immediately upstream from the ESPs (Figure 1).
SOLID AND AQUEOUS SAMPLES
Collection Schedule
The schedule used for collection of the grab samples, i.e., fly ash, bot-
tom ash, quench water influent, and quench water effluent, was constructed
based on the variability of organic emissions observed for a two-plant study.1
The statistical analysis of emissions variability has been described elsewhere.2
The objectives of the grab sample collection schedule were:
(1) simplicity of implementation in the field, and
(2) acceptable statistical (probability sampling) methods.
To accomplish these objectives, the sampling protocol must involve acquiring
specimens from the different media at random times (because levels of target
compounds may vary over time), but have sufficient structure to assure prac-
tical application in the field. For example, because of limited field person-
nel, it is impractical to collect specimens from different media simultaneously
(or within a very short time period). The protocols Described below satisfied
the objectives.
Structure for the sampling protocols was developed by first defining an
ordering to the media. The ordering was bottom ash (BA), fly ash (FA), quench
water effluent and water influent. A one-half hour time period between spec-
imen acquisition by media was established to assure adequate time for field
personnel to properly conduct the specimen acquisition, labelling, and storage.
Proper randomization over time was accomplished in a method that was com-
patable with anticipated specimen compositing schemes and also included struc-
ture to maintance simplicity in application in the field. The sampling period
of five days was first partitioned into ten nonoverlapping periods referred
to as strata. The ten strata are defined in Table 3. To select random times,
four-hour intervals were assigned 16 time points, 15 minutes apart. For ex-
ample, 0000, 0015, 0030, ..., 0345 (military time). Fifteen (15) minute in-
tervals were judged to provide adequate time resolution because errors result-
ing from variation in the true levels of the target compounds would be small
compared to the anticipated analytical precision.
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TABLE 3. TIME STRATA FOR SPECIMEN COLLECTION
Stratum
Day
Military time'
1
2
3
4
5
6
7
8
9
10
1
1
2
2
3
3
4
4
5
5
0000-4000,
4000-8000,
0000-4000,
4000-8000,
0000-4000,
4000-8000,
0000-4000,
4000-8000,
0000-4000,
4000-8000,
8000-1200,
1200-1600,
8000-1200,
1200-1600,
8000-1200,
1200-1600,
8000-1200,
1200-1600,
8000-1200,
1200-1600,
!
1600-2000
2000-2400
1600-2000
2000-2400
1600-2000
2000-2400
1600-2000
2000-2400
1600-2000
2000-2400
a Time intervals include the left end point and exclude the right end point.
One of the 16 time points was selected at random for each stratum yield-
ing 10 random points. The specimen collection times were assigned using the
ten random points, the ordering of the media, and the 30 minute interval cri-
terion. The general formulas for determining the specimen collection times
are given in Table 4. Because each stratum consisted of three 4-hour periods,
400, 800, 1200, 1600, or 2000 (military time) had to be added to the general
formula as appropriate. Table 5 presents the detailed specimen collection
schedule by media. Because the quench water influent was anticipated to be
reasonably homogeneous, one sample per stratum was judged to be adequate.
One time period per stratum was selected randomly for collection of quench
water influent.
TABLE 4. GENERAL FORMULAS FOR DETERMINING SPECIMEN COLLECTION TIMES
Media
Formula
Bottom ash
Fly ash
Quench water effluent
Quench water influent
r.
i
r. + 30
r. + 100
i
r. + 130
a Randomly selected time for stratum i expressed as military time.
10
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TABLE 5. SAMPLING SCHEDULE BY MEDIA (MILITARY TIME)
Day Stratum
1 1
2
1
2
1
2
2 3
4
3
4
3
4
3 5
6
5
6
5
6
4 7
8
7
8
7
8
5 9
10
9
10
9
10
Bottom
ash
0215
0730
1015
1530
1815
2330
0145
0715
0945
1515
1745
2315
0000
0645
0800
1445
1600
2245
0230
0730
1030
1530
1830
2330
0330
0730
1130
1530
1930
2330
Fly
ash
0245
0400
1045
1200
1845
2000
0215
0745
1015
1545
1815
2345
0030
0715
0830
1515
1630
2315
0300
0400
1100
1200
1900
2000
0000
0400
0800
1200
1600
2000
Quench
water
effluent
0315
0430
1115
1230
1915
2030
0245
0415
1045
1215
1845
2015
0100
0745
0800
1545
1700
2345
0330
0430
1130
1230
1930
2030
0030
0430
0830
1230
1630
2030
Quench
water
influent
0345
1300
0315
1245
0130
1215
0000
1300
0100
1300
One sampling period within each stratum was selected randomly (equal
probabilities). Because the water influent was anticipated to be reason-
able homogeneous, one specimen per stratum was judged to be adequate.
11
-------
ESP Ash
Fly ash samples were collected six times each sampling day from the con-
veyor line immediately above the quench pit.
Bottom Ash
Bottom ash samples were collected six times each sampling day from the
conveyor chain used to transfer drained quench pit residue into trucks for
disposal. Relatively large items (> 4 cm) were rejected from the samples
taken. Since ESP and economizer hopper ash was also wasted via the quench
pit, bottom ash samples contained both furnace residue and fly ash.
Quench Water Effluent
The effluent from the quench pit was sampled six times each sampling day
from an overflow weir at the quench pit. The quench water recycle system is
shown diagrammatically in Figure 3.
Quench Water Influent
The influent to the quench pit was sampled twice each sampling day.
Samples were bailed from an access port between the water treatment (recycle)
system and the quench pit.
12
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Treatment &
Settling Tank
Inlet Water Sampling Location
Pump
Water Level
Overflow Water Sample Location
Figure 3. Quench pit and water recycle system.
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' SECTION 6
ANALYSIS METHODS
The general procedures for sample preparation and analysis are described
in detail elsewhere.5 This section provides descriptions of specific proce-
dures used for sample compositing, extract compositing, and extract cleanup
as well as other details related to the analyses of the samples from the re-
source recovery incinerator.
GENERAL ANALYTICAL SCHEME
Sample preparation and analysis followed the general analytical scheme
presented in Figure 4. The samples were spiked with surrogate compounds just
prior to extraction. Extracts were analyzed by fused silica capillary gas
chromatography/mass spectrometry (HRGC/MS) to provide information on the re-
covery of PAH surrogate compounds and quantitation of polynuclear aromatic
hydrocarbons, phthalates, and other major components of the sample extracts.
Extracts were analyzed for PCBs, PCDDs, and PCDFs by HRGC/MS-SIM (selective
ion monitoring). HRGC with high resolution mass spectrometry (HRGC/HRMS-SIM)
was used to confirm the identification and to quantitate tetrachlorodibenzo-
£-dioxins in selected extracts.
SAMPLE COMPOSITING AND EXTRACTION
Ash and aqueous effluent samples were composited prior to analysis to
form two individual 5-day plant composites for each sample type. The sta-
tistical design of the sampling schedule defines the appropriate statistical
analysis of the data. In order to assure that adequate information is re-
tained to properly estimate the level of input and emissions of the target
compounds and their corresponding variances, the specimen composition protocol
must be nested within the statistical design structure, namely, the strata.
Specimens collected at different time periods within each stratum can be
composited into one aliquot for chemical analysis. This will yield an esti-
mate of the level of the target compound for the stratum that have a one-to-
one correspondence with the randomly selected time points. Hence, equal
weights of samples from collection times 1, 3, and 5 were combined to form
daily composite A for each day, while 2, 4, and 6 were combined to form daily
composite B. These were further composited by combining equal weights of the
daily composites to form plant composites A and B. Equal volumes of the first
influent water sample each day formed plant composite A. Plant composite B
for influent water was similarly derived.
14
-------
EXTRACT ANALYSIS
RAW EXTRACT
Clean Up on
Silica Gel
i
Determine PAHs
by HRGC/MS
1
H2SO4
Treatment
I
Determine PCBs
by HRGC/MS-SIM
I
Fractionation
on Alumina
Determine PCDD
and PCDF Homologs
by HRGC/MS-SIM
DB-5
Selected
Extracts
Determine 2,3,7,8-TCDD
by HRGC/MS-SIM and
HRGC/H RMS-SIM
SP-2340
Figure 4. General analytical scheme.
15
-------
Immediately prior to extraction, all composite and other grab samples
prepared for extraction were spiked with the compounds listed in Table 6.
The surrogate spiking compounds were selected from commercially available
stable labeled compounds to represent specific classes of the target analytes.
NaphthaIene-d8 and chrysene-d12 were selected to represent small and large
PAH compounds. Naphthalene is the most volatile of the target analytes.
Hence, naphthalene-d8 recoveries may provide an indication of maximum losses
attributable to volatilization during extraction and extract concentration.
Chrysene-d12 is the least volatile of the surrogate compounds. General chlo-
rinated aromatics were represented by l,2,4,5-tetrachlorobenzene-13C6. Penta-
chlorophenol-13C6 was selected to represent the most polar of chlorinated
phenols. The four labeled PCS and PCDD compounds were selected to represent
those compound classes.
TABLE 6. SURROGATE SPIKING COMPOUNDS
50 |Jg pentachlorophenol-13C6
50 |jg chrysene-d12
50 pg naphthalene-dg
50 |jg tetrachlorobenzene-13C6
100 ng 4-chlorobiphenyl-13C6
250 ng 3,3',4,4'-tetrachlorobiphenyl-13C12
400 ng 2,2',3,3',5,5',6,6'-octachlorobiphenyl-13C12
500 ng decachlorobiphenyl-13C12
100 ng 2,3,7,8-tetrachlorodibenzo-p-dioxin-37Cl4
100 ng octachlorodibenzo-£-dioxin-^3C12
Each daily flue gas sample consisted of the cyclone catch and filter
(combined in the field), adsorbent resin, and probe rinse from two modified
Method 5 trains. The surrogate compounds were spiked into one of the resins
for each sampling day and into either a filter on days 1, 3 and 5, or a probe
rinse for each day. Following separate extraction of each component, the
probe rinse and filter extracts from both trains were combined. The resin
extracts from the two trains were also combined. Hence, the flue gas extracts
consisted of a probe rinse and filter catch extract and a resin extract for
each of the five test days. The first impinger contents for each of the sam-
pling trains from days 2 and 4 were extracted and analyzed separately to test
for breakthrough of analytes from the resin.
16
-------
All solid samples, i.e., resin, particulate catch, bottom ash, and ESP
ash, were Soxhlet extracted with benzene. All aqueous samples, i.e., probe
rinse, impinger and quench waters, were batch extracted with three portions
of cyclohexane. All extracts were dried by passage through a short column of
precleaned anhydrous sodium sulfate and concentrated to ^ 5 mL using Kuderna-
Danish evaporators. The extracts were further concentrated to 1.0 ml under a
gentle stream of dry nitrogen. The concentrated extracts were then split into
two equal aliquots for subsequent analysis.
EXTRACT CLEANUP
Silica Gel Chromatography
One aliquot of each extract (except aqueous and first impinger sample
extracts) were cleaned by adsorption column chromatography prior to scanning
HRGC/MS analysis. This cleanup procedure was adapted from methods developed
by MRI for cleanup of sludge extracts.6 Twenty-gram aliquots of freshly pre-
pared silica gel (70 to 230 mesh, Soxhlet extracted with dichloromethane,
dried at 110°C and deactivated with 1% water) were slurried with hexane and
transferred tp 14.5 x 250 mm chromatography columns. Individual extracts were
added *to 2-g >aliquots of silica gel and evaporated to dryness. The extracts
were then placed at the top of the columns and eluted according to the follow-
ing scheme.
Fraction 1 = 20 mL hexane
Fraction 2 = 80 mL hexane
Fraction 3 = 50 mL 10% benzene in hexane
Fraction 4 = 50 mL 50% benzene in hexane
Fraction 5 = 150 mL 10% acetone in benzene
Fraction 6 = 40 mL methanol
Fraction 1 from each column was discarded. Fractions 2 to 5 were com-
posited prior to scanning HRGC/MS analysis. Fraction 6 was collected sepa-
rately and held to check for late elution of certain compounds. Table 7 shows
the recoveries observed for the target PAH and phthalate compounds spiked onto
silica gel and eluted according to the above scheme.
Acid Treatment
The remaining aliquot of each sample extract was cleaned by acid treat-
ment prior to HRGC/MS-SIM analysis. Each extract aliquot was diluted to 5 mL
with benzene and washed with 5 mL of concentrated sulfuric acid (preextracted
with benzene) for approximately 1 min. The phases were allowed to separate
and the organic layer was removed. The H2S04 layer was extracted with three
2-mL aliquots of fresh benzene. The benzene was removed and combined with the
original benzene fraction. If the H2S04 layer was highly colored, the treat-
ment was repeated. Finally, the benzene was back-extracted with several drops
of distilled water to remove any residual acid. The cleaned extracts were
then dried and concentrated. The recoveries for PCB surrogates spiked into
benzene and acid-extracted twice are shown in Table 8.
17
-------
TABLE 7. RECOVERIES FOR COMPOUNDS CHROMATOGRAPHED ON SILICA GEL
BY THE PROCEDURE USED TO CLEAN SAMPLE EXTRACTS
Compound
Naphthalene
Acenaphthylene
Dimethyl phthalate
Acenaphthene
Fluorene
Diethyl phthalate
Phenanthrene
Di-n-butyl phthalate
Fuoranthene
Pyrene
Butylbenzyl phthalate
Chrysene
Bis[2-ethylhexyl]phthalate
Di-n-octyl phthalate
Benzo [ g , h , i ] pery lene
« a>b
Mean '
% recovery
87
79
85
102
85
92
61
90
90
86
95
94
89
92
97
Standard
deviation
43
28
33
41
34
19
18
19
20
17
15
15
18
13
26
a Taken from three individual batches of silica gel.
b Spike level was 25 |Jg.
TABLE 8. RECOVERY OF PCB SURROGATE COMPOUNDS FROM
SULFURIC ACID TREATED EXTRACTS
Recovery
Compound (%)
Chlorobiphenyl-13C6 99
3,3',4,4'-Tetrachlorobiphenyl-13C12 100
2,2',3,3',5,5',6,6'-Octachlorobiphenyl-13C12 78
Decachlorobiphenyl-13C12 81
18
-------
Alumina Chromatography
Following PCB analyses on the acid-treated extract aliquots, the aliquots
were fractionated on microalumina columns to remove PCBs. The procedure has
been described in detail elsewhere.7 Briefly, columns were prepared by plac-
ing 1 g of aluminum oxide (Woelm Pharma, Eschwege, West Germany), W 200 basic,
activity grade super 1, in a disposable Pasteur pipet with a small plug of
glass wool. The extract (at 0.5 mL) was added to the top of the column. Each
column was eluted with 10 mL of 2% dichloromethane in hexane, and the eluent
was discarded. The column was then eluted with 10 mL of 50% dichloromethane
in hexane. The eluent was collected and concentrated to 1.0 mL for analysis.
Spiked blank columns were run each day along with samples.
EXTRACT ANALYSIS
Scanning HRGC/MS
The sample extracts were analyzed by scanning HRGC/MS to identify and
quantify PAHs, phthalates, and any chlorinated compounds that might be present.
Table 9 lists the target PAH and phthalate compounds. The gas Chromatography
and mass spectrometer instrumental parameters for the scanning HRGC/MS analy-
ses are given in Table 10. Anthracene-d10 (20 ng/pL) was added to sample ex-
tracts and standards prior to scanning HRGC/MS to serve as internal standard
for quantitation. The surrogate compound standard (50 ng/pL for PAHs) and a
25 ng/pL PAH-phthalate standard were analyzed at least once per day with the
sample extracts.
The PAHs, phthalates, and surrogate compounds were identified using three
extracted ion current plots (EICPs) for each specific compound. The criteria
for compound identification were coincident peaks in all EICPs at the appro-
priate retention time with the characteristic response ratios. Compounds
identified were quantified by comparing the EICP response for the most abun-
dant ion with the most abundant ion of the internal standard (anthracene-d10)
and using the response factor for these two ions determined from the standard
solutions.
HRGC/MS-SIM for PCBs
Extracts of grab samples, plant background air, and flue gas were ana-
lyzed for PCBs using a specialized HRGC/MS-SIM procedure, selected mass range
scan HRGC/MS. That is, the mass spectrometer was scanned over the m/e range
of the molecular cluster for each of the chlorobiphenyls. The specific oper-
ating parameters are listed in Table 11. In order to improve sensitivity,
scan ranges were switched according to a preset program during the course of
the HRGC/MS run so that only two sets of chlorobiphenyl ions were monitored
simultaneously. The specific time points for switching the ion sets were
selected based on the elution times for chlorobiphenyl compounds in a mixture
of Aroclor® 1248, 1254, and 1260. Ions for monochloro- and dichlorobiphenyl
were monitored from the initiation of the run until a time after the elution
of monochlorobiphenyl but before the elution of trichlorobiphenyl. At that
time, the ion set was switched to monitor for dichloro- and trichlorobiphenyl.
19
-------
TABLE 9. TARGET PAH AND PHTHALATE COMPOUNDS
PAHs
Phthalate esters
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Chrysene
Benzo[k]fluoranthene
Benzo[a]pyrene
Dibenz [«* ,h] anthracene
Benzo[g,h,i]perylene
DimethyIphthalate
Diethylphthalate
Di-n-butylphthalate
Butylbenzylphthalate
Bis(2-ethylhexyl)phthalate
Di-n-octylphthalate
TABLE 10. INSTRUMENT AND OPERATING PARAMETERS FOR
SCANNING HRGC/MS ANALYSIS
Instrument
Column
Column temperature
Carrier gas
Injector
Scan range
Scan rate
Mass resolution
Finnigan MAT 311-A/Incos
15-m fused silica, wall-coated with SE-54
or DB-5
80°C for 2 rain, then to 325°C at 10°C/min
Helium at 2.5 psi
J & W on-column (1 (JL injection)
m/e 32-425
1.5 sec/scan
1,000 (m/Am, 10% valley)
20
-------
TABLE 11. INSTRUMENTAL PARAMETERS AND MASS RANGES USED FOR
HRGC/MS-SIM ANALYSES OF PCBs
Instrument
Column
Column temperature
Carrier gas
Injector
Scan rate
Mass resolution
Scan ranges
No. chlorines
Finnigan 4023
15 m fused silica, wall-coated with DB-5
80°C for 2 min, then to 325°C at 8°C/rain
Helium at 2.5 psi
J&W on-column (1 |JL injection)
1 sec/scan
unit
Mass range scan (amu)
Retention time
monitored (min)a
1
2
3
4
5
6
7
8
9
10
187.5
221.5
255.5
289.5
323.5
357.5
391.5
425.5
459.5
493.5
- 188.5
- 226.5
- 262.5
- 298.5 .
- 334.5
- 366.5
- 400.5
- 434.5
- 468.5
- 502.5
13.0 -
13.0 -
13.0 -
14.5 -
16.9 -
18.2 -
20.0 -
22.2 -
23.1 -
25.0 -
14.5
14.5
16.9
18.2
20.0
22.2
23.1
25.0
26.6
26.6
Determined by analyzing a mixed Aroclor standard and scanning
HRGC/MS.
21
-------
This sequence was continued throughout each run. Hence, the last set of ions
monitored was for nonachlorobiphenyl and decachlorobiphenyl. Positive re-
sponses to any of the PCB isomers in the composite extracts were confirmed
when the peaks for the ion plots for two ions were coincident with responses
in the proper ratios. PCB isomers identified were quantitated using area
response factors for specific isomers with the same chlorine number. Stan-
dard solutions containing the isomers listed in Table 12 were analyzed at the
following concentration ranges: 25-125, 50-250, and 100-500
TABLE 12. PCB COMPOUNDS USED FOR QUANTITATION STANDARDS
4,4'-Dichlorobiphenyl
2,3,5'-Trichlorobiphenyl
2,4,2',4'-Tetrachlorobiphenyl
2,3,4,5,6-Pentachlorobiphenyl
2,3,4,2',3',4'-Hexachlorobiphenyl
2,3,4,5,6,2',5'-Heptachlorobiphenyl
2,3,4,5,2',3',4',5'-Octachlorobiphenyl
Decachlorobiphenyl
HRGC/MS-SIM for PCDDs and PCDFs
Sample extracts were also analyzed by HRGC/MS-SIM for PCDDs and PCDFs.
The instrument and operating parameters are listed in Table 13. Perfluoro-
kerosene (PFK) was used to obtain stable mass assignments during PCDD and PCDF
analyses. Analyses for the entire range of PCDDs and PCDFs required four in-
jections of each extract. Mono- through tri- PCDDs and PCDFs were determined
in the first run. Three subsequent runs were used to determine tetrachloro
compounds, penta- and hexachloro compounds, and hepta- and octachloro com-
pounds, respectively.
HRGC/HRMS-SIM Confirmation of Tetrachlorodibenzo-^-dioxins
Selected flue gas and ESP ash extracts were also analyzed by HRGC/MS-SIM
and HRGC/HRMS-SIM using an SP-2340 column to quantitate the 2,3,7,8-tetra-
chloro congener and to confirm identifications of tetrachlorodibenzo-£-dioxins
(including the 2,3,7,8-congener). The instrument and operating parameters are
listed in Table 14. An SIM chromatogram for several tetrachlorodibenzo-£-dioxin
congeners is shown in Figure 5 and illustrates the chromatographic resolution
achieved with the SP-2340 column.
22
-------
TABLE 13. INSTRUMENT AND OPERATING PARAMETERS FOR HRGC/MS-SIM ANALYSES
OF PCDDs/PCDFs
Instrument
Column
Column temperature
Carrier gas
Injector
Mass resolution
Ions measured
No. of chlorines
Finnigan MAT 311-A/Incos
15-m fused silica, wall-coated with DB-5
80°C hold 2 rain, then to 325°C at 10°C/min
helium at 2.5 psi
J&W on-column (1-pL injection)
~ 1,000 (m/Am, 10% valley)
Dioxins (m/e)
Furans (m/e)
PFK (reference)
1
2
3
4
5
6
7
8
218.0/220.0
252.0/254.0
285.9/287.9
319.9/321.9
353.9/355.9
389.8/391.8
423.8/425.8
457.7/459.7
202.0/204.0
242.0/244.0
269.9/271.9
303.9/305.9
337.9/339.9
373.8/375.8
407.8/409.8
441.7/443.7
242.9
331.0
380.8
430.7
23
-------
TABLE 14. INSTRUMENT AND OPERATING PARAMETERS FOR HRGC/HRMS-SIM ANALYSIS
OF SELECTED EXTRACTS FOR 2,3,7,8-TETRACHLORODIBENZO-£-DIOXIN
Instrument
Low resolution
High resolution
Column
Column temperature
Carrier gas
Injector
Ions measured
Reference ion
Varian MAT CH-4B/Incos operated at ~ 1,000
resolution (m/Am, 10% valley)
Varian MAT 311-A/Incos operated at •>• 8,000
resolution (m/Am, 10% valley)
60-m fused silica, wall coated with SP-2340
100°C hold 4 min, then to 240°C at 25°C/min
helium at 2.5 psi
J&W on-column (1-pl injection)
, 319.8967
321.8937
327,8847 (37Cl4-labeled surrogate)
331,9370 (13C12-labeled internal standard)
330.9793 (PFK)
24
-------
85.6-1
to
cn
329
100.0-1
322
1,4,7,8
\
I
t ^ ± :f± ^ ±f —
i
'.'H| ' II / V 1 1 1 -V 1 '
-n*>..««/h.rV«W"lv»>-%j/ryijA^-v— —*r* . - i~*~ — J V-yk^.,/ V«™._J^s.»ju^
1 1 ^~ 1 ' 1
900 1000 1100
18:19 20:21 22:23
1
I
1
^ 2,3,7,8
1,2.3.4 1'2'7'8
1 I 1,2,6,7
/I ft /
11. ,l\ A.,.
— * 1 -1 — F- -1- 1
i
Ljll1 1 | / \" /\ /^V ' ' '
1200 1300 1400 SCAN
24:25 26:27 23:30 TIME
Figure 5. HRGC/MS-SIM chromatogram of tetrachlorodibenzo-2-dioxin congeners on an SP-2340 column.
-------
SECTION 7
FIELD TEST DATA
This section presents summaries of the flue gas sampling data, unit oper-
ating parameters, and particulate control device operating data for the refuse
incinerator.
A summary of the daily data for flue gas sampling as calculated from the
field data sheets is presented in Table 15. The data listed are corrected to
standard conditions, i.e., 20°C and a barometric pressure of 29.92 in. (1.0
atm) of mercury. Table 16 is a summary of the plant background air sampling
data.
Plant operating conditions (temperatures and steam flows) and the contin-
uous combustion gas analysis results (02, C02, CO, and THC) are plotted for
the flue gas sampling periods in Figures 6 through 15. The operating tempera-
tures are generally fairly stable during the flue gas sampling period. The
furnace temperature was somewhat more variable than the ESP outlet temperature,
especially on Days 2 and 3 (Figures 8 and 10). The steam flows were somewhat
variable around the design steam flow of 32,000 Ib/hr on Days 1 through 4.
The steam flow was down somewhat on Day 5 (Figure 14).
The results of continuous monitoring of combustion gas composition were
quite variable. The ranges observed were approximately 2-14% for oxygen, 6-16%
for carbon dioxide, 100-3,000 ppm for carbon monoxide, and up to 300 ppm for
total hydrocarbons. The patterns of changes for C02, CO, and THC were very
similar. Oxygen followed the same patterns in the inverse direction.
Table 17 summarizes ESP operating conditions during flue gas testing.
Secondary voltage (kV), secondary current (ma), and spark rate (pulses/min)
were taken from ESP control panels. The secondary tier was not sparking
normally during the Day 5 test.
The results of proximate and ultimate fuels analysis on ashes are shown
in Table 18. On a dry basis, the bottom ash contained a larger fraction of
refractory material (ash content) than the fly ash. The fly ash samples con-
tained more volatiles, fixed carbon, and sulfur than the bottom ash and had
correspondingly higher heats of combustion on a dry basis. The fly ash also
contained more total chlorine. The large difference between the ash and
moisture free heat of combustion of the two bottom ash composites reflects
the corresponding difference in ash content.
26
-------
TABLE 15. SUMMARY OF DAILY AVERAGE DATA
Sample
Test Sampling volume
oo. location dscf
1 A
B
2 A
B
3 A
B
4 A
IsJ
^J B
5 A
B
171.28
171.45
262.53
243.85
308.408
308.460
254.063
288.143
237.509
242.887
Gas composition
Stack
temperature
dscra Oz (S) COZ «) CO (ppm) THC (ppm) (°F)
4
4
7
6
8
8
7
8
6
6
.85
6.0 13.2 1,120 56.7
.86
.43
5.5 13.5 1,230 71.5
.91
.73
7.9 11.8 888.3 41.3
.73
.19
6.5 12.7 1,451 71.5
.16
.73
6.1 13.2 965.0 37.3
.88
530
528
513
513
553
538
520
526
483
489
Dry
molecular Moisture
weight (%)
17.
30.40
18.
17.
30.36
18.
15.
30.21
15.
17.
30.19
15.
17.
29.96
17.
4
0
A
0
.8
8
.7
9
4
.3
Velocity
(ft/sec)
37.52
36.20
36.80
34.58
44.65
42.78
38.98
39.03
32.10
31.72
Flue gas flow
acfm
28,288
27,288
27,744
26,075
33,662
32,263
29,389
29,429
24,208
23,916
dscfm
12,517
12,002
12,538
11,659
15,021
14,339
13,074
13,310
11,192
10,987
d somi
354
340
355
330
425
406
370
377
317
311
Isokinetic
rate (%)
97.3
97.6
99.3
95.3
97.3
98.0
92.1
98.6
100.6
100.7
-------
TABLE 16. SUMMARY OF PLANT BACKGROUND AIR VOLUMES
Volume
Test dscf dscm
1 263.96 7.475
2 248.26 7.030
3 246.10 6.969
4 247.69 7.014
5 237.92 6.737
28
-------
1,700
1,600
1,500
1,400
u.
o
7 1.300
3
| 1,200
0)
1,100
'f
600
500
400
36,000
35,000
34,000
— 33,000
i
£ 32,000
J
^ 31,000
o
"* 30,000
29,000
28,000
27.000
-
Furnace Temperature O O O
O
0 0
° O O
"•
-
-
ESP Outlet Temperature
* • .•••".•• ... .
1 1 1 1 1 1 1
-
-
A
A A A
A A A
A A A A
A
A
-
-
1 1 1 1 1 1 1
1,300 1,400 1,500 1.600 1,700
Clock Time (h)
1,800
1,900
2,000
Figure 6. Operating temperatures and steam flows recorded during
flue gas sampling - day 1.
29
-------
—»
£
e
Q
^
S
Dioxide (%)
J
u
•£
S
<£
1
&
'x
1
1
O
|
I
i
1
1
1
g
—
I
14
12
to
8
6
4
2
16
15
14
13
12
11
10
9
g
7
3,000
2.500
2.000
1.500
1.000
500
Q
400
300
200
100
n
-
-
A '
A
A A
"A A
^
A A A .
~ A A
• AA ' ...'
A
-
1 1 1 1 1 1 1
-
" °°°o o° o °° °0°00
~. QQ 0 ° °0°0
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.
1 1 1 1 1 1 1
-
_
* • •
• * •
• • • *
..' * . .'• ".
• • • •
1 1 1 1 1 1 1
-
A A
A
A A
A A A A
A
A A A A A A A
A! AI A"AA^- i" i i
1,300 1,400 1,500 1.600 1.700 1,800 1,900 2.C
Clack Tim. (h)
Figure 7. Combustion gas analysis results from continuous
monitoring during flue gas sampling - day 1.
30
-------
1,700
1,600
1,500
1,400
u.
0
7 1,300
o
e
8. 1,200
£
-------
_
£
1
6
=
c£
*
*
1
0
a
u
I
U
<£
|
7
a
J
J
a
I
i
o
1
7
J
J
§
1
2
,2
U
12
10
8
6
4
2
Q
16
15
14
13
12
11
10
9
g
7
3,000
2,500
2,000
1,500
1,000
500
0
400
300
200
100
0
-
-
-
-
-
-
_
-
-
-
-
~
.
|-
"l
-
-
.
-
—
r-
-
^
A
A
A A A
** A* * A A
'*'* A A
A A
AA A *A
A
I t 1 1 1 1 1 1 1 1 1
O
o°° ° o°0
°O° OOn° ° °
0 00 ° ° ° 0
o 0° o °0
o
o
1
I 1 1 1 1 1 1 1 1 1 1
• •
*•• * •• *
• •
•• ••
•• • •
• * ** *
1 1 1 1 1 1 1 1 1 1 1
A
A
A A
AAAAA A
AA
A A ^A A
AIA AA 1 1 A A 1 1 A ^A | ( |
0700 0800 0900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Clack T!m. (h)
Figure 9. Combustion gas analysis results from continuous
monitoring during flue gas sampling - day 2.
32
-------
u_
o
8
g
1
a
t—
1,700
1,600
1,500
1,400
1,300
1,200
1,100
600
500
400
—
-
O Furnace Temperature
0000 °0°0
o
0 0 °°
o
00
o
o
f
' ESP Outlet Temperature
1 1 1 1 1 1 1 1 1 1 1
36,000
35,000
34,000
~ 33,000
s
~ 32,000
E 31,000
30,000
29,000
28,000
27,000
A A A A
A A
I t
2,100 7,000
I
J
0700 0800 0900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Clock Time (h)
Figure 10. Operating temperatures and steam flows recorded
during flue gas sampling - day 3.
33
-------
^
£
T
2
6
1
K
<£
i
Carbon Dioxide
c
o
j
„
I
I
X
1
1
u
j
if
i
1
£
1
1
1
a
3
14
12
10
9
6
4
2
Q
16
15
14
13
12
11
10
7
7
-
_
_
-
A
-A
-
p
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3,000r-
2,500
2,000
1,500
1,000
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400
300
200
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—
.
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—
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A A '
A A
* A A A
A A A ^ A. A ^
* A
%.' \ • .' -/•
A A
1 1 1 1 1 1 1 1 1 1 1
o°o o
o o o o o o
O O O y^O
°o 0°oo° Oo° o
° 0 ° QO 0 0 00
0
o 0 o
i i i 1 1 1 I I 1 1 O i
•* .
* *
* ** . .*•
* * • * * *
* •* ••••*** *
• * *• *
I 1 1 1 1 1 1 1 1 1*1
A
A
A
A A
A
A A A AA
A A A A
AA A A A
A A A
1 ! AA A 1 -A .AJA.«AA AT J.^A/J
0700 0800 0900 1000 1100 1200 1300 14
Clack Tim* (h)
1500 1600 1700 1800
Figure 11. Combustion gas analysis results from continuous
monitoring during flue gas sampling - day 3.
34
-------
1,700
1,600
1,500
1,400
u.
7 ''30°
| 1,200
1,100
y
600
500
400
•rW
36,000
35,000
34,000
r— i *j nn A
^ 33,000
-------
#
"-'
e
tt
OB
1
'c
11
u
,£
—
d
i
x
o
0
j
1
-------
1,700
1,600
1,500
1,400
O
7 1,300
3
I 1,200
01
1,100
*
600
500
400
36,000
35,000
34,000
C 33,000
~ 32,000
"^ 31,000
o
*" 30,000
29,000
28,000
27,000
—
-
_ Furnace Temperature Q Q
o
-0 O O °
0 °
O
-
f
X
ESP Outlet Temperature
I 1 1 1 1 1 1 1 1 1 1
-
-
-
-
-
-
-A A A A A A A
A A
- A A A A A A
-A A
1 1 1 1 1 I 1 1 1 1 1
0700 0800 0900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Clock Time (h)
Figure 14. Operating temperatures and steam flows recorded
during flue gas sampling - day 5.
37
-------
y
|
1
5
i
7
on Dioxide
1
u
1
£
7
I
|
a
-------
TABLE 17. ESP OPERATING CONDITIONS
Secondary voltage Secondary current Spark rate
(kV) (ma) (sparks/min)
Test day 1° Tier 2° Tier 1° Tier 2° Tier 1° Tier 2° Tier
1 - Average 23.3 24.0 50.0 181.7 13.6 13.1
Range 24-24 22 - 28 40 - 60 110 - 265 4-49 4-25
2 - Average 22.0 22.1 58.5 171.5 13.9 15.0
Range 21 - 24 20 - 24 40 - 110 70-270 6-44 5 - 28
3 - Average 21.8 20.8 71.5 250 14.1 14.4
Range 21-23 2-36 45 - 190 100 - 270 6-25 2-36
4 - Average 21.8 21.9 66.5 207.5 11.5 13.8
Range 21-23 20-2.35 50 - 120 110 - 270 4-38 1-35
5 - Average 21.4 21.8 92.6 270 10.5 3.83
Range 21 - 22 21 - 23 50 - 140 200 - 280 3-33 0-14
39
-------
TABLE 18. PROXIMATE AND ULTIMATE ANALYSIS RESULTS
FOR BOTTOM ASH AND FLY ASH
Bottom ash
Fly ash
Proximate analysis
Reported as received
Moisture (%)
Ash (%)
Volatile (%)
Fixed carbon (%)
Sulfur (%)
Heat of combustion (Btu/lb)
Dry basis
Ash (%)
Volatile (%)
Fixed carbon (%)
Sulfur (%)
Heat of combustion (Btu/lb)
ASM free Btu (Btu/lb)
Ultimate analysis
Dry basis
Hydrogen (%)
Carbon (%)
Nitrogen (%)
Oxygen (%)
Total chlorine (%)
25.68, 39.54
72.72, 53.08
1.52, 2.77
0.08, 4.62
0.26, 0.35
707, 436
97.85, 87.79
2.04, 4.58
0.11, 7.63
0.35, 0.58
951, 721
44,171, 5907
0.01, 0.01
5.71, 5.98
0.26, 0.29
4.18, 5.36
0.140, 0.202
0.259, 0.238
6.59, 4.70
73.71, 76.13
11.70, 10.12
7.99, 9.05
1.21, 1.31
1788, 1737
78.92, 79.88
12.53, 10.62
8.55, 9.50
1.30, 1.37
1914, 1823
9079, 9060
0.01, 0.01
13.90, 9.41
1.05, 0.21
4.83, 9.12
3.926, 4.137
4.074, 3.687
a Results from two plant composite samples.
40
-------
SECTION 8
ANALYTICAL RESULTS
The analytical results from this study include determinations of target
PAH and phthalate compounds by HRGC/MS and PCBs, PCDDs, and PCDFs by HRGC/MS-SIM.
TARGET PAH AND PHTHALATES
The results for the target PAH and phthalate compounds identified in the
flue gas samples are shown in Table 19. These data and all other analytical
results reported in this document are presented without correction for recov-
eries. The recoveries for surrogate spikes (presented in Section 9) were gen-
erally good so that correction for the recoveries would not significantly
change interpretation of the results. The results presented in Table 19 show
target compound concentrations in the flue gas samples attributed to the two
fractions from the sampling train, i.e., the probe rinse with associated par-
ticulate catch and the resin cartridge, as well as the sum, i.e., total, con-
centrations. However, the fractions of the total concentration measured for
the two components should not be taken to represent particulate and vaporous
fractions of the analytes. Reliable determination of particulate and vaporous
fractions for many organics in flue gases are probably not possible where par-
ticulates are collected on a heated filter. Some portion of materials that
enter the sampling system on particulates may subsequently vaporize from the
filter deposit, held at *» 145°C with a sampling flow near 20 L/min. Alterna-
tively, some portion of materials that enter the sampling system as gases may
be adsorbed by chemically active sites on carbonaceous or other solids de-
posited on the filter.
Nevertheless, all of the target PAH compounds were detected in at least
one of the flue gas samples. Naphthalene, acenaphthylene, phenanthrene,
fluoranthene, and pyrene concentrations exceeded 100 (Jg/dscm in all five flue
gas samples. Phthalate concentrations were generally variable and low.
The results for target PAH and phthalate compounds in fly ash and bottom
ash samples are shown in Table 20. Bottom ash included ESP and economizer
ash in addition to unburned residue from both units. In general, PAH concen-
trations were higher in the fly ash samples and phthalate concentrations were
higher in the bottom ash.
41
-------
TABLE 19. TARGET COMPOUNDS IDENTIFIED IN FLUE GAS SAMPLES
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Diethyl phthalate
Phenanthrene
•-
Di-n-butyl phthalate
Fluoranthene
Pyrene
Train
component
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Concentration ((Jg/dscm)
Day 1
34
600
640
14
200
220
NDb
ND
ND
0.37
13
13
ND
2.5
2.5
11
140
150
ND
12
12
7.4
98
110
9.1
110
120
Day 2
13
460
480
19
230
250
ND
3.0
3.0
2.3
12
14
ND
ND
ND
130
88
220
ND
9.7
9.7
120
45
160
180
55
230
Day 3
11
370
380
3.0
110
120
ND
1.7
1.7
0.59
8.2
8.8
ND
ND
ND
55
71
130
ND
3.5
3.5
43
35
78
46
38
84
Day 4
17
1,020
1,040
35
290
330
0.35
5.4
5.7
5.1
18
24
ND
1.8
1.8
150
99
250
ND
6.2
6.2
93
38
130
120
40
160
Day 5
2.2
560
560
9.9
170
180
ND
2.4
2.4
4.2
11
15
ND
1.5
1.5
130
72
200
ND
20
20
110
20
130
120
19
140
Mean
16 ± 12
600 ± 250
620 ± 250
16 ± 12
200 ± 68
220 ± 79
0.07 ± 0.16
2.5 ± 2.0
2.6 ± 2.1
2.5 ± 2.1
12 ± 3.8
15 ± 5.4
ND
1.2 ± 1.1
1.2 ± 1.1
95 ± 59
93 ± 27
190 ± 51
ND
10 ± 6.3
10 ± 6.3
75 ± 48
47 ± 30
122 ± 32
94 ± 67
53 ± 35
150 ± 56
(continued)
-------
TABLE 19 (concluded)
Compound
Butylbenzyl phthalate
Chrysene
Bis[2-ethylhexyl] phthalate
Benzo [ k] f luoranthene
Benzo f a ] pyrene
Dibenz[ a, h] anthracene
Benzo [g,h,i]perylene
Train
component
Probe -l- filter
Resin
, Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Concentration (pg/dscm)
Day 1
ND
0.74
0.74
ND
7.7
7-7
1.1
17
18
1.7
97
99
1.4
6.0
7.4
ND
ND
ND
4.3
4.3
4.3
Day 2
ND
ND
ND
9.9
2.0
12
34
ND
34
15
1.9
16
11
1.2
12
ND
ND
ND
ND
ND
ND
Day 3
ND
0.84
0.84
4.6
2.4
7.0
0.56
0.31
0.87
6.1
2.5
8.6
4.7
1.2
5.9
ND
ND
ND
ND
1.3
1.3
Day 4
ND
ND
ND
14
2.8
17
0.37
2.9
3.3
20
3.7
23
13
1.8
14
ND
ND
ND
ND
ND
ND
Day 5
ND
ND
ND
24
1.2
26
1.4
6.2
7.6
26
1.1
27
18
0.50
19
ND
0.14
0.14
24
1.1
25
Mean
ND
0.32 ± 0.43
0.32 ± 0.43
11 ± 9.4
3.2 ± 2.6
14 ± 7.7
7.5 ± 15
5.2 ± 6.8
13 ± 14
14 ± 10
21 ± 42
35 ± 36
9.5 ± 6.6
2.2 ± 2.2
12 ± 5.2
ND
0.027 ± 0.061
0.027 ± 0.061
4.8 ± 11
1.3 ± 1.8
6.1 ± 11
a Mean ± standard deviation for the five tests.
b Not detected, i.e., < 0.3 |Jg/dscm.
-------
TABLE 20. TARGET COMPOUNDS IDENTIFIED IN ASH SAMPLES
Concentration (|Jg/g)
Compound
Naphthalene
Acenaphthylene
Fluorene
Phenanthrene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Butylbenzyl phthalate
Chrysene
Bis [2-ethylhexyl] phthalate
Benzo [ k] f luoranthene
Composite
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
Fly ash
9.2
9.4
9.3
3.5
3.6
3.5
0.033
0.034
0.034
7.8
7.4
7.6
ND
ND
ND
6.7
6.2
6.5
5.6
5.3
5.4
ND
ND
ND
0.85
0.54
0.69
0.17
ND
0.085
0.58
0.36
0.47
Bottom ash
0.35
0.80
0.57
0.13
0.64
0.39
NDb
ND
ND
0.27
0.73
0.50
0.46
0.26
0.36
0.14
0.32
0.23
0.12
0.32
0.22
0.084
0.28
0.18
ND
ND
ND
0.56
3.6
2.1
ND
ND
ND
(continued)
44
-------
TABLE 20 (concluded)
Concentration (Mg/g)
Compound
Benzo [ a ] py rene
Benzo [ j> , h , i ] perylene
Composite
A
B
Mean
A
B
Mean
Fly ash
0.40
0.24
0.32
0.23
0.16
0.19
n
Bottom ash
ND
ND
ND
ND
ND
ND
a Includes an unknown fraction of ESP and economizer ash.
b Not detected, i.e., < 0.3 Mg/g.
45
-------
The results for target compounds in the aqueous and background air samples
are shown in Tables 21 and 22, respectively. Although most of the target PAH
compounds were identified in the quench influent and effluent samples, the
concentrations observed were low. The concentrations of target compounds in
the plant background air were quite variable. In general, higher levels were
found in samples from Days 1 and 2. The source of compounds identified in
the background air may be attributable, at least in part, to flue gas leaking
from the ductwork of either or both units and collecting in the plant building.
Smoke and haze were frequently observed on the upper floors during sample col-
lection.
PCBs
The concentrations of PCB homologs identified in the flue gas samples
are shown in Table 23. In general, PCB concentrations in the flue gas samples
were variable from day to day. The most abundant PCB homologs were dichloro
and trichloro compounds. This distribution is similar to that observed in a
previous study of a mass burn municipal refuse incinerator, although the con-
centrations were ^ 16 times higher in the present study.*
The results for PCBs in ash samples are shown in Table 24. Fly ash con-
tained significantly higher concentrations of PCB homologs than bottom ash,
although the distribution of homologs identified were similar for both sample
types and also corresponded well with the homolog distribution observed for
flue gas. In general, similar concentrations were observed for specific
homologs in the two composites for each sample type.
PCBs were not identified in any of the aqueous or background air samples.
PCDDs
The concentrations of PCDD homologs identified in the flue gas samples
are shown in Table 25. Although the concentrations varied considerably from
day to day, all tetra- through octachloro homologs were identified in at least
one component of the sample for each day. The total PCDD levels were very
similar to concentrations reported for an incinerator of a similar design8
but much higher than observed for the Chicago Northwest unit.1 All homologs
were identified. However, the homolog distribution maximized at pentachloro
compounds with considerable contribution from tetra-, hexa-, and heptachloro-
homologs. The average total PCDD concentration was 2,300 ng/dscm.
Table 26 shows the concentrations of 2,3,7, 8-tetrachlorodibenzo-j>-dioxin
in the selected flue gas samples. The total concentration in the Day 2 sample
was 8.7 ng/dscm. The fraction of the total tetrachloro homolog attributable
to the 2,3,7,8- congener was 21% for the Day 2 sample and averaged 14% for
all four sample components. These fractions are somewhat higher than the cor-
responding fraction, 6.5%, reported for the Chicago Northwest incinerator.1
46
-------
TABLE 21. TARGET COMPOUNDS IDENTIFIED IN AQUEOUS SAMPLES
Concentration (|Jg/L)
Compound
Naphthalene
Acenaphthylene
Dimethyl phthalate
Fluorene
Diethyl phthalate
Phenanthrene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Butylbenzyl phthalate
Chrysene
Composite
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A '
B
Mean
A
B
Mean
Influent
water
NDa
2.1
1.0
28
0.69
14
14
ND
7.0
ND
ND
ND
0.82
1.8
1.3
ND
2.2
1.3
13
0.97
6.9
0.63
1.0
0.82
4.4
1.1
2.8
' 5.4 '
2.3
3.9
ND
ND
ND
Effluent
water
1.6
3.0
2.3
0.46
1.9
1.2
ND
ND
ND
ND
0.33
0.22
ND
ND
ND
0.68
5.0
2.8
ND
ND
ND
0.45
1.5
0.98
0.56
1.7
1.1
ND
ND
ND
ND
ND
ND
(continued)
47
-------
TABLE 21 (concluded)
Compound
Bis [2-ethylhexyl]phthalate
Di-n-octyl phthalate
Composite
A
B
Mean
A
B
Mean
Concentration
Influent
water
ND
1.5
1.0
6.2
ND
3.2
(M8/L)
Effluent
water
1.8
1.7
1.8
ND
ND
ND
a Not detected, i.e., < 0.6 pg/L.
48
-------
TABLE 22. TARGET COMPOUNDS IDENTIFIED IN PLANT BACKGROUND AIR
Concentration (ng/dscm)
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Fluoranthene
Pyrene
Butylbenzyl phthalate
Chrysene
Bis [2-ethylhexyl] phthalate
Benzo [k] f luoranthene
Benzo [ajpyrene
Dibenz[
-------
TABLE 23. POLYCHLORINATED BIPHENYLS IDENTIFIED IN FLUE GAS SAMPLES
Homolog
Monochlorobiphenyl
Dichlorobiphenyl
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Train
component
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe = filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Concentration (ng/dscm)
Day 1
NDb
ND
ND
71
ND
71
ND
ND
ND
ND
ND
ND
ND
56
56
ND
ND
ND
ND
ND
ND
ND
ND
ND
Day 2
21
160
180
150
550
700
76
58
130
ND
25
25
ND
0.8
0.8
13
0.5
13
ND
ND
ND
ND
ND
ND
Day 3
14
190
200
23
180
200
150
170
320
27
34
61
ND
11
11
ND
6.7
6.7
ND
ND
ND
" ND
ND
ND
Day 4
45
190
230
370
150
520
53
28
81
18
ND
18
ND
19
19
ND
26
26
ND
0.7
0.7
ND
ND
ND
Day 5
6.3
85
91
36
260
300
43
17
60
ND
2.2
2.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Mean
17 ± 17
120 ± 81
140 ± 94
130 ± 140
230 ± 210
360 ± 250
65 ± 57
55 ± 67
120 ± 120
9.0 ± 13
12 ± 16
21 ± 24
ND
17 ± 23
17 ± 23
2.6 ± 5.7
6.7 ± 11
9.3 ± 11
ND
0.15 ± 0.33
0.15 ± 0.33
ND
ND
ND
(continued)
-------
TABLE 23 (concluded)
Homo log
Nonachlorobiphenyl
Decachlorobiphenyl
Total Chlorobiphenyl
Train
component
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Concentration (ng/dscm)
Day 1
ND
ND
ND
ND
ND
ND
71
56
130
Day 2
ND
ND
ND
ND
ND
ND
260
800
1,100
Day 3
ND
ND
ND
ND
ND
ND
220
580
800
Day 4
ND
ND
ND
ND
ND
ND
480
420
900
Day 5
ND
ND
ND
ND
ND
ND
86
370
450
Mean
ND
ND
ND
ND
ND
ND
220 ± 170
440 ± 270
670 ± 370
1-1 a Mean ± standard deviation for the five tests.
b Not detected, i.e., < 0.5 ng/dscm.
-------
TABLE 24. POLYCHLORINATED BIPHENYLS IDENTIFIED IN ASH SAMPLES
Homolog
Monochlorobiphenyl
Dichlorobiphenyl
Tr i chl orob ipheny 1
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Nonachlorobiphenyl
Decachlorobiphenyl
Total chlorobiphenyl
Composite
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
Concentration
a
Bottom ash
1.4
1.3
1.3
b
ND
ND
ND
0.23
ND
0.12
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND ,
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
1.7
1.3
1.5
(ng/g)
Fly ash
9.3
9.7
9.5
10
9.7
9.9
11
11
11
1.7
6.0
3.8
10
ND
5.1
ND
0.89
0.45
0.20
ND
0.10
2.5
ND
1.2
ND
ND
ND
ND
ND
ND
45
37
41
a Includes an unknown
b Not detected, i.e.,
fraction of
< 0.5 ng/g.
economizer and fly
ash.
52
-------
TABLE 25. POLYCHLORINATED DIBENZO-£-DIOXINS IDENTIFIED IN FLUE GAS SAMPLES
Compound
Monodichlorodibenzo-
£-dioxin
Dichlorodibenzo-£-dioxin
Trichlorodibenzo-£-dioxin
Tetrachlorodibenzo-
£-dioxin
Cn
03 Pentachlorodibenzo-
£-dioxin
Hexachlorodibenzo-£-dioxin
Heptachlorodibenzo-
£-dioxin
Octachlorodibenzo-£-dioxin
Total chlorodibenzo-
£-dioxins
T*. n -i »1
iram
component
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum 1,
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter 1,
Resin
Sum 2,
Concentration (ng/dscm)
Day 1
NDb
13
13
ND
26
26
ND
ND
ND
75
88
160
660
420 '
100
430
310
730
190
85
270
63
30
93
400
970
400
Day 2
ND
6.5
6.5
ND
ND
ND
ND
ND
ND
34
8.0
42
270
ND
270
230
21
250
86
4.2
91
20
0.62
21
650
41
690
Day 3
0.91
4.0
4.9
38
ND
38
70
ND
70
450
5.2
450
2,800
ND
2,800
770
28
800
210
5.2
210
35
1.2
36
4,400
43
4,500
Day 4
9.1
3.2
12
130
ND
130
140
ND
140
370
ND
370
1,500
ND
1,500
540
43
590
150
17
170
32
6.8
39
2,900
70
3,000
Day 5
ND
ND
ND
ND
ND
ND
20
ND
20
110
ND
110
480
ND
480
160
6.0
160
40
2.2
42
14
0.84
15
820
9.1
830
Mean
2.0 ± 4.0
5.4 ± 5.0
7.4 ± 5.5
34 ± 57
5.3 ± 12
39 ± 54
45 ± 58
ND
45 ± 58
210 ± 190
20 ± 38
230 ± 180
1,200 ± 1,100
84 ± 190
1,200 ± 1,000
430 ± 250
81 ± 130
510 ± 280
130 ± 70
23 ± 35
160 ± 92
33 ± 19
7.9 ± 13
41 ± 31
2,040 ± 1,600
230 ± 410
2,300 ± 1,600
a Mean ± standard deviation
b Not detected, i.e., < 0.5
for the five tests
ng/dscm.
-------
TABLE 26. CONCENTRATIONS OF 2,3,7,8-TETRACHLORODIBENZO-£-DIOXIN
IN SELECTED FLUE GAS SAMPLES
Fraction of Total
Concentration Tetrachlorodibenzo-£-dioxin
Sample Train component (ng/dscm) (%)
Day 1
Day 2
Resin
Probe + filter
Resin
Sum
12
7.2
1.5
8.7
14
21
19
21
Day 4 Probe + filter 7.6 2.1
The results for PCDDs identified in ash samples are shown in Table 27.
All homologs were identified in the fly ash composite samples. The mean total
PCDD in the fly ash was 800 ng/g. The distribution of homologs in the ESP
ash was very similar to that observed in the flue gas samples, i.e., largely
pentachloro congeners with significant contributions from tetrachloro and hexa-
chloro congeners. Only the tetrachloro homolog was identified in the bottom
ash composite samples. The very low concentrations found in the bottom ash
may reflect the contribution of ESP ash to the bottom ash samples.
The concentrations of 2,3,7,8-tetrachlorodibenzo-£-dioxin identified in
the two fly ash comppsites by HRGC/HRMS-SIM were 2.9 and 1.4 ng/g. These
contributions represent 1.7 and 0.8%, respectively, of the total tetrachloro
homolog concentrations. Figure 16 is a chromatogram for a fly ash extract
showing the 2,3,7,8- congener.
Table 28 shows the results of analysis of the plant background air for
PCDDs. The very low and variable levels of PCDD homologs identified are
likely attributable, at least in part, to flue gas leaking from duct work in
the plant building. PCDDs were not identified in any of the quench water
influent or effluent samples.
PCDFs
The concentrations of PCDF homologs identified in the flue gas samples
are shown in Table 29. Considerable variation in concentrations is apparent
between days. Nonetheless, nearly all homologs were identified in all sample
components for each sampling day. The average total PCDF concentration was
11,000 ng/dscm. The homolog distribution was similar to that for PCDDs in
flue gas, i.e., largely pentachloro congeners. However, the average total
PCDF levels were over 4 times higher than the mean total PCDD concentration.
The PCDF/PCDD ratio observed in flue gas from the Chicago Northwest inciner-
ator was over 10.
54
-------
TABLE 27. POLYCHLORINATED DIBENZO-pj-DIOXINS IDENTIFIED
IN ASH SAMPLES
Homo log
Monochlorodibenzo-
£-dioxin
Dichlorodibenzo-
£-dioxin
Trichlorodibenzo-
I>-dioxin
Tetrachlorodibenzo-
p_-dioxin
Pentacbjlorodibenzo-
pj-dioxin
Hexachlorodibenzo-
jj-dioxin
Heptachlorodibenzo-
£-dioxin
Octachlorodibenzo-
p_-dioxin
Total chlorodibenzo-£-
dioxins
Composite
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
Concentration
«a
Bottom ash
NDb
ND
ND
ND
ND
ND
ND
ND
ND
0.13
0.50
0.32
ND
ND -
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.13
0.50
0.32
(ng/g)
Fly ash
2.5
1.6
2.0
21
24
22
68
43
55
170
170
170
650
420
530
50
54
52
6.3
8.4
7.4
4.1
1.1
2.6
1,000
720
800
a Includes an unknown fraction of economizer and ESP ash.
b Not detected, i.e., < 0.05 ng/g.
55
-------
83.2n
320
Ui
100.0n
322
ji
/ I'!!' ! ' " / V J
1600
20:21
1160
22:23
1200
24:25
1300
26:27
1400
28:30
1500 SCW
30:32 TIME
Figure 16. HRGC/HRMS-SIM chromatogram for fly ash composite A extract.
-------
TABLE 28. POLYCHLORINATED DIBENZO-£-DIOXINS IDENTIFIED IN PLANT BACKGROUND AIR
Concentration Qig/dscm)
Homolog Day 1 Day- 2 Day 3
Monochlorodibenzo-£-dioxin
Dichlorodibenzo-£-dioxin
Trichlorodibenzo-£-dioxin
Tetrachlorodibenzo-£-dioxin
Pentachlorodibenzo-£-dioxin
Hexachlorodibenzo-£-dioxin
Heptachlorodibenzo-£-dioxin
Octachlorodibenzo-£-dioxin
Total chlorinated dibenzo-£-
dioxins
NDb
ND
ND
ND
ND
ND
ND
0.35
0.35
ND
ND
ND
ND
ND
ND
ND
ND .
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Day 4 Day 5
ND
ND
ND
0.24
ND
ND
5.7
11
17
ND
ND
ND
ND
ND
ND
ND
ND
ND
Mean
ND
ND
ND
0.048 ±
ND
ND
1.1 ±
2.3 ±
3.5 ±
0.11
2.5
4.9
7.5
a Mean ± standard deviation for the five tests.
b Not detected, i.e., < 0.15 ng/dscm.
57
-------
TABLE 29. POLYCHLORINATED DIBENZOFURANS IDENTIFIED IN FLUE GAS SAMPLES
Homo log
Monochlorodibenzofuran
Dichlorodibenzofuran
Trichlorodibenzofuran
Tetrachlbrodibenzofuran
Ui
oo Pentachlorodibenzofuran
Hexachlorodibenzofuran
Heptachlorodibenzofuran
Octachlorodibenzofuran
Total chlorodibenzofurans
Train
component
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Concentration (ng/dscm)
Day 1
71
310
380
100
300
400
570
1,200
1,800
330
470
800
1,400
1,400
2,800
NDb
210
210
140
77
210
8
ND
8
2,600
4,000
6,600
Day 2
27
370
400
170
310
490
680
460
1,100
350
130
480
1,100
200
1,300
170
0.15
170
96
6.2
100
8.8
ND
8.8
2,600
1,500
4,100
Day 3
58
240
300
290
210
500
1,800
310
2,100
1,900
110
2,000
15,000
210
15,000
1,800
4.4
1,800
370
6.7
380
24
ND
24
21,000
1,100
22,000
Day 4
140
280
420
550
140
700
3,000
360
3,300
1,400
110
1,600
8,800
350
9,200
920
25
950
220
14
230
18
ND
18
15,000
1,300
16,000
Day 5
130
180
310
390
56
440
1,500
82
1,600
550
9.6
560
2,900
19
2,900
330
5.1
340
80
3.6
83
9.2
ND
9.2
5,900
360
6,300
Mean
85 ± 48
280 ± 72
360 ± 54
300 ± 180
210 ± 110
510 + 110
1,500 ± 980
480 ± 430
2,000 ± 830
910 ± 710
170 ± 180
1,100 ± 670
5,800 ± 5,900
430 ± 550
6,200 ± 5,700
650 ± 750
49 ± 91
700 ± 710
180 ± 120
22 ± 31
200 ± 120
14 ± 7.2
ND
14 ± 7.2
9,400 ± 8,200
1,600 ± 1,400
11,000 ± 7,700
a Mean ± standard deviation for the five tests.
b Not detected, i.e., < 0.5 ng/dscm.
-------
Table 30 shows the results for PCDFs identified in the ash samples. All
homologs were identified in the fly ash composites. As noted for PCDDs in
fly ash, the distribution of PCDF homologs is similar to that for flue gas.
The mean PCDF concentration in the ESP ash was 3,000 ng/g, over three times
the mean PCDD level. Also, the low PCDF concentration determined in the bot-
tom ash (mean of 9.3 ng/g) may reflect the ESP contribution to bottom ash
samples.
PCDFs were also identified in the plant background air samples. The
results are shown in Table 31. As noted for PCDDs, PCDF levels in background
air were very low. PCDFs were not identified in any quench water samples.
59
-------
TABLE 30. POLYCHLORINATED DIBENZOFURANS IDENTIFIED
IN ASH SAMPLES
Homo log
Monochlorodibenzofuran
Dichlorodibenzofuran
Trichlorodibenzofuran
Tetrachlorodibenzofuran
Pentachlorodibenzofuran
Hexachlorodibenzofuran
Heptachlorodibenzofuran
Octachlorodibenzofuran
Total chlorinated
dibenzofurans
Composite
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
A
B
Mean
Concentration
a
Bottom ash
0.83
1.4
1.1
0.38
0.89
0.63
NDb
ND
ND
0.88
2.0
1.4
3.5
8,9
6'.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
5.5
13
9.3
(ng/g)
Fly ash
42
40
41
69
110
90
520
580
550
350
460
410
1,800
1,800
1,800
75
91
83
8.5
11
9.5
2.2
0.57
1.4
2,800
3,100
3,000
a Includes an unknown fraction of ESP and economizer ash.
b Not detected, i.e., < 0.05 ng/g.
60
-------
TABLE 31. POLYCHLORINATED DIBENZOFURANS IN PLANT BACKGROUND AIR
Concentration (ng/dscm)
Homolog
Monodichlorodibenzofuran
Dichlorodibenzofuran
Trichlorodibenzofuran
Tetrachlorodibenzofuran
Pentachlorodibenzofuran
Hexachlorodibenzofuran
Heptachlorodibenzofuran
Octachlorodibenzofuran
Total chlorinated dibenzo-
furans
Day 1 Day 2 Day 3 Day 4 Day 5
NDb
ND
ND
1.1
3.8
ND
ND
ND
4.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.27
ND
ND
ND
ND
0.27
ND
ND
ND
0.39
ND
ND
1.5
7.1
9.0
ND
ND
ND
ND
ND
ND
ND
ND
ND
Mean
ND
ND
ND
0.35 ±
0.75 ±
ND
0.30 ±
1.4 ±
2.8 ±
0.45
1.7
0.76
3.2
4.0
a Mean ± standard deviation for the five tests.
b Not detected, i.e., < 0.15 ng/dscm.
61
-------
SECTION 9
ANALYTICAL QUALITY ASSURANCE RESULTS
The analytical quality assurance program included the use of surrogate
spiking compounds, analysis of blank samples, and analysis of a standard ref-
erence material (dust). In addition, impinger samples were analyzed to deter-
mine analyte breakthrough during flue gas sampling. These results are pre-
sented and discussed below.
SURROGATE COMPOUND RECOVERIES
The primary indicators of the performance of the analytical procedures
were the recoveries of surrogate analytes spiked into samples prior to extrac-
tion and analysis. Three classes of surrogate compounds were used for this
study: stable isotope-labeled surrogates for the target compounds, stable
isotope-labeled PCB congeners, and stable isotope-labeled PCDD congeners.
The recoveries of the surrogates for the target compounds spiked into
flue gas samples are shown in Table 32. The corresponding recoveries for sur-
rogates in plant background air are shown in Table 33. Table 34 presents the
summary of recoveries for all samples. The recoveries and standard deviations
generally indicate that the precision and accuracy were generally good for
all compounds except pentachlorophenol-13C6. Pentachlorophenol is very polar
and acidic, more polar than the target analytes. This characteristic is mani-
fested in a gas chromatographic peak shape for PCP that is generally broad
and very susceptible to changes in the activity of the column. Hence, the
recovery of pentachlorophenol-13C6 provides an indication of the maximum ap-
parent losses due to adsorption on the fused silica capillary column. Also,
the recoveries for naphthalene-dg from the flue gas resin samples were some-
what variable. This may indicate some losses for very volatile analytes.
The recoveries for the surrogate polychlorinated biphenyls from flue gas
and background air samples are shown in Tables 35 and 36, respectively. The
summary of recoveries for all samples is presented in Table 37. Recoveries
of the PCB surrogates were generally low for flue gas, fly ash, and bottom
ash samples, especially in the case of the monochloro compound. This may be
partially attributable to the high levels of extractable organics in these
extracts. Even following cleanup, the flue gas, fly ash, and bottom ash ex-
tracts required dilution prior to analysis. Higher spike levels may have been
appropriate for those samples. Nonetheless, recoveries were generally good
for the background air and quench water samples.
62
-------
TABLE 32. RECOVERIES OF SURROGATE TARGET COMPOUNDS SPIKED INTO THE FLUE GAS SAMPLES
U>
Surrogate
Naphthalene-d8
Chrysene-d12
1,2,4 , 5-Tetrachlorobenzene- 1 3C6
Pentachlorophenol- 13C6
Train
component
Probe + filter
Resin
Probe + filter
Resin
Probe + filter
Resin
Probe + filter
Resin
Recovery (%)
Day 1
50
140
29
110
26
83
0
0
Day 2
83
29
66
80
47
69
0
0
Day 3
90
21
59
66
48
58
0
0
Day 4
80
68
66
100
44
85
0
0
Day 5
55
31
69
94
28
80
0
0
-------
TABLE 33. RECOVERIES OF SURROGATE TARGET COMPOUNDS SPIKED
INTO THE PLANT BACKGROUND AIR SAMPLES
Recovery (%)
Surrogate
Day 1 Day 2 Day 3 Day 4 Day 5
Naphthalene-d8
Chrysene-d12
1,2,4,5-Tetrachlorobenzene-13C6
Pentachlorophenol-13C6
77 92
93 85
76 65
2.1 0
83
82
51
0
86
102
71
2.0
96
81
51
0.80
64
-------
TABLE 34. SUMMARY OF RECOVERIES OF THE SURROGATE TARGET COMPOUNDS
Ln
% Recovery
Sample type Naphthalene-dg
Flue gas, probe
+ filter
Flue gas, resin
Plant background air
Fly ash
Bottom ash
Quench influent
Quench effluent
72 +
58 ±
87 ±
80,
64,
60,
70,
18a
49
8
79b
88
97
65
Chrysene-d12 1>2,
58 ±
90 ±
89 ±
64,
82,
73,
68,
17
17
9
37
74
98
93
4 , 5-Tetrachlorobenzene- 13C6 Pentachlorophenol- 13C6
39 ±
75 ±
63 ±
78,
72,
65,
48,
11 0
11 0
11 0.98 ± 1.0
80 0, 0
21 0, 0
67 0, 43
73 0, 0
a Mean ± standard deviation for the five tests.
b From analysis of two spiked composites.
-------
TABLE 35. RECOVERIES OF POLYCHLORINATED BIPHENYL SURROGATES SPIKED INTO FLUE GAS SAMPLES
Surrogate
4-Chlorobiphenyl- 13C6
3 , 3 ' , 4 , 4 ' -Tetrachlorobiphenyl- 13C12
2,2' ,3,3' ,5,5' ,6,6'-Octachlorobiphenyl-13C12
Decachlorobiphenyl-13C12
Train
component
Probe + filter
Resin
Probe + filter
Resin
Probe + filter
Resin
Probe + filter
Resin
Recovery (%)
Day 1
0
0
33
0
37
15
15
43
Day 2
0
0
72
27
27
45
12
30
Day 3
0
0
0
23
27
50
16
37
Day 4
0
0
17
43
32
23
18
34
Day 5
0
0
19
57
53
44
20
33
-------
TABLE 36. RECOVERIES OF POLYCHLORINATED BIPHENYL SURROGATES SPIKED
INTO PLANT BACKGROUND AIR SAMPLES
Recovery (%)
Surrogate Day 1 Day 2 Day 3 Day 4 Day 5
4-Chlorobiphenyl-13C12 93 0 73 82 0
3,3',4,4'-Tetrachlorobiphenyl-13C12 69 75 65 66 61
2,2' ,3,3',5,5',6,6'-Octachloro-
biphenyl-13C12 53 73 63 73 53
Decachlorobiphenyl-13C12 55 61 70 82 30
67
-------
TABLE 37. SUMMARY OF RECOVERIES OF THE POLYCHLORINATED BIPHENYL SURROGATE COMPOUNDS
Sample type
Flue gas, probe
+ filter
Flue gas, resin
Plant background air
Fly ash
Bottom ash
ON
oo Quench water influent
Quench water effluent
4-Chlorobiphenyl-13C6
0
0
45 ± 46
o, ob
0, 0
54, 58
57, 67
3,3',4,4'-Tetrachloro-
biphenyl-13C12
28 ± 27a
30 ± 22
67 ± 5.7
0, 26
33, 67
54, 48
44, 74
2,2' ,3, 3', 5, 5' ,6,6'-Octa-
chlorobiphenyl-13C12
35 ± 11
36 ± 15
63 ± 10
45, 45
37, 58
52, 63
68, 76
Decachloro-
biphenyl-13C12
16 ± 3.2
35 ± 4.9
60 ± 19
38, 37
0, 48
46, 66
150, 170
a Mean ± standard deviation for five samples.
b Determinations from two composite samples.
-------
Tables 38 and 39 show the polychlorinated dibenzo-j>-dioxin surrogate
recoveries for flue gas and background air samples, respectively. Table 40
summarizes the recoveries for all samples. Recoveries were generally good
for both compounds from flue gas, background air, and the quench water samples.
However, the octachloro compound was inexplicably poorly recovered from ashes.
Typically, low recoveries for octachlorodibenzo-£-dioxin may be attributable
to poor chromatography sometimes enhanced by its long elution time.
BLANK SAMPLES
The levels of analytes determined in blank samples were not detectable
or were negligible relative to concentrations determined in the corresponding
samples. Table 41 shows the analytes identified in blank samples.
STANDARD REFERENCE MATERIALS
Standard Reference Material 1649, "Urban Dust/Organics" was analyzed (in
duplicate) in parallel with and by the same methods used for ESP ash analysis.
The National Bureau of Standards has certified concentrations for five poly-
nuclear aromatic hydrocarbons in SRM 1649. These are fluoranthene, benz[a]-
anthracene, benzo[ajpyrene, benzo[g,h,iL]perylene, and indeno[l ,2,3-cd]pyrene.
The certified values were derived from analytical results from highly specific
gas chromatographic and liquid chromatographic methods. Only two of the certi-
fied compounds, benzo[jg,h,ijperylene and f luoranthene, are uniquely determined
by the more broadly applicable HRGC/MS method used in this study. Indeno-
[l,2,3-cd]pyrene was not a target analyte. Benzta]anthracene and benzo[a]-
pyrene co-elute with their isomers and cannot be distinguished from them by
mass spectrometry. Table 42 shows the certified values and the analysis
results for the two compounds. These results indicate good correspondence
with the certified values.
FLUE GAS ANALYTE BREAKTHROUGH TESTS
The results of analyses of the first impinger contents from flue gas
sampling on Days 2 and 4 are shown in Table 43. These results indicate that
breakthrough was only a negligible fraction of the analytes identified.
69
-------
TABLE 38. RECOVERIES OF POLYCHLORINATED DIBENZO-£-DIOXIN SURROGATES SPIKED INTO FLUE GAS SAMPLES
Surrogate
2,3,7, 8-Tetrachlorodibenzo-£-dioxin-37Cl4
Octachlorodibenzo-£-dioxin-13C12
Train
component
Probe + filter
Resin
Probe + filter
Resin
Recovery (%)
Day 1
79
75
98
85
Day 2
53
84
60
44
Day 3
90
68
65
95
Day 4
77
81
56
170
Day 5
82
67
51
110
-------
TABLE 39. RECOVERIES OF POLYCHLORINATED DIBENZO-p_-DIOXIN SURROGATES
SPIKED INTO PLANT BACKGROUND AIR SAMPLES
Recovery (%)
Surrogate
2,3,7, 8-Tetrachlorodibenzo-£-
dioxin-37Cl4
Octachlorodibenzo-£-dioxin-13C12
Day 1
88
56
Day 2
74
37
Day 3
89
0
Day 4
83
120
Day 5
75
84
TABLE 40. SUMMARY OF RECOVERIES OF THE POLYCHLORINATED
DIBENZO-£-DIOXIN SURROGATE COMPOUNDS
Recovery (%)
2,3,7 , 8-Tetrachlorodibenzo- Octachlorodibenzo-
Sample type £-dioxin-37C!4 £-dioxin-13C12
Flue gas, probe + filter
Flue gas, resin
Plant background air
Fly ash
Bottom ash
Quench water influent
Quench water effluent
76 ±
77 ±
82 ±
55,
43,
77,
79,
143
7.5
7.2
45
80
76
88
66 ±
100 ±
59 ±
5,
10,
59,
58,
19
47
45
0
100
38
62
a Mean ± standard deviation for the five tests.
b Determinations for two composite samples.
71
-------
TABLE 41. ANALYTES IDENTIFIED IN BLANK SAMPLES
a
Concentration
Compound
Naphthalene
Diethylphthalate
Phenanthrene
D i -n-buty Iphtha late
Fluoranthene
Pyrene
Butylbenzy Iphtha late
Bis [ 2-ethylhexyl ] phthalate
Di-n-octylphthalate
Flue gas resin
(Mg/dscm)
0.23
0.07
0.02
0.28
0.02
0.02
0.09
0.05
0.46
Flue gas probe + filter
(ng/dscm)
0.20
0.72
NDb
0.39
0.03
0.02
0.12
ND
0.79
a Calculated assuming a typical sample size.
b Not detected.
TABLE 42. RESULTS FOR ANALYSIS OF SRM 1649
Compound
Concentration (jJg/g)
Certified value Analysis results
Fluoranthene
Benzo[j>,h,.i]perylene
7.1 ± 0.5
4.5 ± 1.1
6.3, 10.8'
5.3, 6.2
a Results from duplicate determinations.
72
-------
TABLE 43. ANALYTES IDENTIFIED IN FLUE GAS TRAIN FIRST IMPINGERS
Compound
Naphthalene
Fluorene
Chrysene
Benzo [ a ] py rene
Concentration
((Jg/dscm)
Day 2 Day 4
0 . 65 . 1.0
ND 0.01
0.01 0.02
ND 0.01
Breakthrough
(%)
Day 2
0.1
0
0.08
0
Day 4
0.1
0.04
0.1
0.07
a Concentration in the first irapinger divided by the concentration in the
total sample, expressed as percent.
73
-------
SECTION 10
EMISSION RESULTS
The emission rates determined for the target PAH and phthalate compounds
in flue gases for the resource recovery municipal incinerator are presented
in Table 44. Emission rates were calculated from the concentrations deter-
mined in each sample (presented in Section 8) and the flue gas volume flow
rates (presented in Section 7). Emission rates were not similarly derived
for the ash samples because ash production rates for the furnace could not
be reliably estimated.
The highest emission rates of the target compounds were determined for
naphthalene (average of 13,000 mg/hr) and acenaphthylene (average of 4,700
mg/hr). Average emission rates over 1,000 mg/hr were also determined for
phenanthrene, fluoranthene, and pyrene. As indicated in Section 8, the frac-
tions of analytes found on the two principal flue gas sampling train compo-
nents should not be interpreted as reliable indications of "particulate" or
"vaporous" fractions. This is the case for the target compounds, PCBs, PCDDs,
and PCDFs.
The emission rates for PCB compounds in flue gas are shown in Table 45.
The mean total PCB emission rate was 15 ± 8.5 mg/hr. The lowest total PCB
emissions were determined on Days 1 and 5 (2.6 and 5.8 mg/hr, respectively).
The emission rates for PCDDs and PCDFs in flue gas are shown in Tables 46
and 47, respectively. The average total PCDD emission rate was 51 ± 40 mg/hr.
The emission rate was highest on Day 3 (110 mg/hr) and lowest on Days 2 and 5
(14 and 16 mg/hr, respectively). The relative order of total PCDF emissioji
rates was very similar, lowest on Days 2 and 5 (83 and 120 mg/hr, respectively)
and highest on Day 3 (550 mg/hr). The average total PCDF emission rate was
250 ± 200 mg/hr.
74
-------
TABLE 44. EMISSION RATES FOR TARGET COMPOUNDS IN FLUE GAS
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Diethylphthalate
Phenanthrene
Di-n-butylphthalate
Fluoranthene
Train
component
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Day 1
700
13,000
13,000
290
4,200
4,500
NDb
ND
ND
7.7
270
270
ND
52
52
230
2,900
3,100
ND
240
240
150
2,000
2,200
Day 2
270
9,500
9,800
390
4,800
5,200
ND
62
62
48
240
290
ND
ND
ND
2,700
1,800
4,500
ND
200
200
2,400
930
3,300
Emission
Day 3
280
9,200
9,400
76
2,800
2,900
ND
43
43
15
210
220
ND
ND
ND
1,400
1,800
3,100
ND
88
88
1,100
880
1,900
rate (mg/hr)
Day 4
390
23,000
23,000
780
6,600
7,300
7.8
120
130
120
410
530
ND
41
41
3,400
2,200
5,600
ND
140
140
2,100
850
2,900
Day 5
41
11,000
11,000
190
3,200
3,400
ND
45
45
78
200
280
ND
29
29
2,400
1,400
3,700
ND
380
380
2,100
370
2,500
Mean
340 ± 240
13,000 ± 5,700
13,000 ± 5,800
340 ± 270
4,300 ± 1,500
4,700 ± 1,800
1.6 ± 3.5
54 ± 43
56 ± 46
53 ± 45
260 ± 87
320 ± 120
ND
25 ± 24
25 ± 24
2,000 ± 1,200
2,000 ± 570
4,000 ± 1,100
ND
210 ± 110
210 ± 110
1,600 ± 940
1,000 ± 610
2,600 ± 560
(continued)
-------
TABLE 44 (concluded)
Compound
Pyrene
Butylbenzylphthalate
Chrysene
Bis [2-ethylhexyl]phthalate
Benzo f luo ranthene
Benzo[a]pyrene
Dibenz [ a , h] anthracene
Benzo [g,h,]L]perylene
Train
component
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Day 1
190
2,300
2,500
ND
15
15
ND
160
160
23
340
370
35
2,000
2,100
29
130
160
ND
ND
ND
ND
89
89
Day 2
3,700
1,100
4,800
ND
ND
ND
200
41
240
700
ND
700
300
39
340
220
25
250
-,- ND
k- ND
ND
ND
ND
ND
Emission
Day 3
1,100
960
2,100
ND
21
21
120
59
170
14
7.7
22
150
61
210
120
31
150
ND
ND
ND
ND
33
33
rate (mg/hr)
Day 4
2,600
890
3,500
ND
ND
ND
310
62
380
8.3
66
74
440
83
520
280
41
320
ND
ND
ND
ND
ND
ND
Day 5
2,200
360
2,600
ND
ND
ND
460
23
480
27
120
140
500
22
520
340
9.4
350
ND
2.6
2.6
450
20
470
Mean
2,000 ± 1,400
1,100 ± 730
3,100 ± 1,100
ND
7.3 ± 10
7.3 ± 10
220 ± 180
69 ± 53
290 ± 140
150 ± 300
110 ± 140
260 ± 280
280 ± 190
440 ± 880
730 ± 750
200 ± 130
46 ± 46
240 ± 94
ND
0.52 + 1.2
0.52 ± 1.2
91 ± 200
28 ± 37
120 ± 200
a Mean ± standard deviation for the five tests.
b Not detected.
-------
TABLE 45. EMISSION RATES FOR POLYCHLORINATED BIPHENYLS IN FLUE GAS
Homolog
MonochlorobiphenyL
Dichlorobiphenyl
Trichlorobiphenyl
Tetrachlorobiphenyl
Pentachlorobiphenyl
Hexachlorobiphenyl
Heptachlorobiphenyl
Octachlorobiphenyl
Train
component
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Emission rate (mg/hr)
Day 1
NDb
ND
ND
1.5
ND
1.5
ND
ND
ND
ND
ND
ND
ND
1.2
1.2
ND
ND
ND
ND
ND
ND
ND
ND
ND
Day 2
0.42
3.2
3.7
3.0
11
14
1,6
1.2
2.8
ND
0.51
0.51
ND
0.017
0.017
0.26
0.011
0.27
ND
ND
ND
ND
ND
ND
Day 3
0.34
4.6
4.9
0.58
4.4
5.0
3.8
4.2
8.1
0.67
0.84
1.5
ND
0.28
0.28
ND
0.17
0.17
ND
ND
ND
ND
ND
ND
Day 4 Day 5
1.0
4.2
5.2
8.2
3.4
12
1.2
0.63
1.8
0.41
ND
0.41
ND
0.43
0.43
ND
0.59
0.59
ND
0.017
0.017
ND
ND
ND
(continued)
0.12
1.6
1.7
0.69
4.9
5.6
0.81
0.33
1.1
ND
0.042
0.042
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Mean
0.38 ± 0.39
2.7 ± 1.9
3.1 ± 2.2
2.8 ± 3.2
4.8 ± 4.1
7.6 ± 5.3
1.5 ± 1.4
1.3 ± 1.7
2.8 ± 3.1
0.22 ± 0.31
0.28 ± 0.38
0.49 ± 0.61
ND
0.38 ± 0.47
0.37 ± 0.47
0.053 ± 0.12
0.15 ± 0.25
0.21 ± 0.24
ND
0.0033 ± 0.0075
0.0033 ± 0.0075
ND
ND
ND
-------
TABLE 45 (concluded)
Homo log
Nona chlo rob ipheny 1
Decachlorobiphenyl
Total chlorobiphenyl
Train
component
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Emission rate (mg/hr)
Day 1
ND
ND
ND
ND
ND
ND
1.5
1.2
2.6
Day 2
ND
ND
ND
ND
ND
ND
5.3
16
22
- Bay 3
ND
ND
ND
ND
ND
ND
5-4
15
20
Day 4
ND
ND
ND
ND
ND
ND
11
9.3
20
Day 5
ND
ND
ND
ND
ND
ND
1.6
6.9
8.5
Mean
ND
ND
ND
ND
ND
ND
4.9 ± 3
9.6 ± 6
15 + 8
.8
.1
.5
a Mean ± standard deviation for the five tests.
oo
b Not detected.
-------
TABLE 46. EMISSION RATES FOR POLYCHLORINATED DIBENZO-£-DIOXINS IN FLUE GAS
T> J _
Homo log
Monochlorodibenzo-£-dioxin
Dichlorodibenzo-ja-dioxin
Trichlorodibenzo-£-dioxin
TetrachIorodibenzo-£-dioxin
Pentachlorodibenzo-£-dioxin
Hexachlorodibenzo-£-dioxin
Heptachlorodibenzo-
£-dioxin
Octachlorodibenzo-£-dioxin
Total chlorodibenzo-
£-dioxins
j. A. aj-u.
component Day
Probe +
Resin
Sum
Probe +
Resin
Sum
Probe +
Resin
Sum
Probe +
Resin
Sum
Probe +
Resin
Sum
Probe +
Resin
Sum
Probe +
Resin
Sum
Probe +
Resin
Sum
Probe +
Resin
Sum
filter ND
0.
0.
filter ND
0.
0.
filter ND
ND
ND
filter 1.
1.
3.
filter 14
8.
22
filter 8.
6.
15
filter 3.
1.
5.
filter 1.
0.
1.
filter 29
20
49
1
28
28
55
55
6
8
4
7
9
4
9
8
6
3
63
9
Day 2
ND
0.13
0.13
ND
ND
ND
ND
ND
ND
0.69
0.16
0.85
5.6
ND
5.6
4.8
0.44
5.2
1.8
0.087
1.9
0.42
0.013
0.43
13
0.84
14
Emission rate (mg/hr)
Day
0
0
0
0
ND
0
1
ND
1
11
0
11
71
ND
71
19
0
20
5
0
5
0
0
0
110
1
110
3
.023
.099
.12
.95
.95
.7
.7
.13
.69
.2
.13
.3
.87
.031
.90
.1
Day
0
0
0
3
ND
3
3
ND
3
8
ND
8
34
ND
34
12
0
13
3
0
3
0
0
0
65
1
67
4
.20
.072
.27
.0
.0
.1
.1
.2
.2
.97
.4
.38
.7
.73
.15
.88
.6
Day 5
ND
ND
ND
ND
ND
ND
0.38
ND
0.38
2.1
ND
2.1
9.0
ND
9.0
2.9
0.11
3.1
0.76
0.042
0.80
0.27
0.016
0.28
15
0.17
16
Mean
0.045 ±
0.12 ±
0.16 ±
0.78 ±
0.11 ±
0.89 ±
1.0 ±
ND
1.0 ±
4.8 ±
0.43 ±
5.2 ±
27 ±
1.7 ±
28 ±
9.6 ±
1.7 ±
11 ±
3.0 ±
0.48 ±
3.5 ±
0.72 ±
0.17 ±
0.88 ±
47 ±
4.8 ±
51 ±
0.089
0.10
0.12
1.3
0.24
1.2
1.3
1.3
4.7
0.79
4.4
27
3.9
26
6.5
2.6
7.0
1.8
0.73
2.1
0.41
0.26
0.65
41
8.6
40
a Mean ± standard deviation
b Not detected.
for the
five tests.
-------
TABLE 47. EMISSION RATES FOR POLYCHLORINATED DIBENZOFURANS IN FLUE GAS
00
Homo log
Monochlorodibenzofuran
Dichlorodibenzofuran
Trichlorodibenzofuran
Tetrachlorodibenzofuran
Pentachlorodibenzofuran
Hexachlorodibenzofuran
Heptachlorodibenzofuran
Octachlorodibenzofuran
Total chlorodibenzofurans
Tfa -i n
1 ITclj.Il
component
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Probe + filter
Resin
Sum
Emission rate (mg/hr)
Day* 1
1.5
6V5
8.0
2.1
6.3
8.4
12
25
37
6.9
9.7
17
30
29
58
NDb
4.4
4.4
2*9
1.6
4.5
0.17
ND
0.17
55
83
140
Day 2
0.56
7.6
8.2
3.6
6.4
10
14
9.4
23
7.2
2.6
9.8
22
4.1
26
3.5
0.0030
3.5
2.0
0.13
2.1
0.18
ND
0.18
53
30
83
Day 3
1.5
6.0
7.4
7.1
5.3
12
45
7.6
52
47
2.8
50
370
5.2
370
46
0.11
46
9.3
0.17
9.5
0.60
ND
0.60
520
27
550
Day 4
3.1
6.2
9.4
12
3.2
16
67
8.0
75
32
2.5
35
200
7.8
210
21
0.55
21
4.9
0.32
5.3
0.41
ND
0.41
340
29
370
Day 5
2.4
3.4
5.8
7.3
1.1
8.4
29
1.5
31
10
0.18
11
54
0.37
55
6.3
0.095
6.4
1.5
0.068
1.6
0.17
ND
0.17
110
6.7
120
Mean
1.8 ± 0.99
5.9 ± 1.6
7.8 ± 1.3
6.5 ± 4.0
4.5 ± 2.3
11 ± 3.1
33 ± 23
10 ± 8.9
44 ± 20
21 ± 18
3.6 ± 3.6
24 ± 17
130 ± 150
9.3 ± 11
140 ± 150
15 ± 19
1.0 ± 1.9
16 ± 18
4.1 ± 3.2
0.46 ± 0.65
4.6 ± 3.2
0.31 ± 0.19
ND
0.31 ± 0.19
220 ± 210
35 ± 28
250 ± 200
a Mean ± standard deviation for the five tests.
b Not detected.
-------
REFERENCES
1. Haile, C. L. , J. S. Stanley, R. M. Lucas, D. K. Melroy, C. P. Nulton,
and W. L. Yauger, Jr., "Comprehensive Assessment of the Specific Com-
pounds Present in Combustion Processes. Volume 1, Pilot Study of Com-
bustion Emissions Variability," Report from Midwest Research Institute
to EPA/EED/OTS/Washington, D.C., EPA Contract No. 68-01-5915, Report No.
EPA-560/5-83-004, June 1983.
2. Lucas, R. M., D. K. Melroy, "A Survey Design for Refuse and Coal Com-
bustion Process," Report from Research Triangle Institute to EPA/EED/OTS/
Washington, DC, EPA Contract No. 68-01-5848, June 1981.
3. Haile, C. L., J. S. Stanley, T. Walker, G. R. Cobb, and B. A. Boomer,
"Comprehensive Assessment of the Specific Compounds Present in Combustion
Processes. Volume 3, National Survey of Organic Emissions from Coal-
Fired Utility Boiler Plants," Report from Midwest Research Institute to
EPA/EED/OTS/ Washington, DC, EPA Contract No. 68-01-5915, September 1983.
4. Lucas, R. M., and G. W. Kircher, "National Estimates of Emission of
Selected POMs from Coal-Fired Utility Boiler Plants," Report from
Research Triangle Institute to EPA/EED/OTS/Washington, DC, EPA
Contract No. 68-01-5848, March 1983.
5. Stanley, J. S., C. L. Haile, A. M. Small, and E. P. Olson, "Sampling and
Analysis Procedures for Assessing Organic Emissions from Stationary Com-
bustion Sources in Exposure Evaluation Division Studies," Report from
Midwest Research Institue to EPA/OPTS/Washington, DC, under Contract
No. 68-01-5915, Report No. EPA-560/5-82-014, August 1983.
6. Haile, C. L., and V. Lopez-Avila, "Development of Analytical Test Proce-
dures for the Measurement of Organic Priority Pollutants in Sludge,
Report from Midwest Research Institute to EPA/EMSL, Cincinnati, Ohio,
under EPA Contract No. 68-03-26-5, August 1981.
7. Mieure, J. P., 0. Hicks, R. G. Kaley, and P. R. Michael, "Determination
of Trace Amounts of Chlorodibenzo-£-dioxins and Chlorodibenzofurans in
Technical Grade Pentachlorophenol," Journal of Chromatographic Science,
15:275-277 (1977).
8. Tiernan, T. 0., M. L. Taylor, J. H. Garrett, G. F. VanNess, J. G. Solch,
D. A. Deis, and D. J. Wagel, "Chlorodibenzodioxins, Chlorodibenzofurans,
and Related Compounds in Effluents from Combustion Processes," Chemosphere
12:595-606 (1983).
81
-------
9- Redford, D. P., C. L. Haile, and R. M. Lucas, "Emissions of PCDDs and PCDFs
from Combustion Sources," in Human and Environmental Risks of Chlorinated
Dioxins and Related Compounds, R. E. Tucker, A. L. Young, and A. P. Gray,
Eds., Plenum Press, New York, 1983.
82
-------
S027'.-ioi
REPORT DOCUMENTATION : »•. REPORT NO. 2.
PAGE 1560/5-84-002 ! __
4. Title and Subtitle Assessment of Emissions of Specific
Compounds from A Resource Recovery Municipal'Refuse
Incinerator
7? AuVhc^slcTarence ~L .~Haile, Ru7th; B ;""Blaif7~Th'6maS
Walker (MRI); Robert M. Lucas (RTI)
3. Recipient's Accession No.
• 5. Report Date
i 'June, 1984
9. Performing Organization Name and Ac-dress
Midwest Research Institute
425 Volker Boulevard
Kansas City, Missouri 64110
8. Performing Organization Rept. No.
12. Sponsoring Organization Name and Address
Field Studies Branch, BED, TS-798
USEPA
401 M Street, S.W.
Washington, DC 20460
IS. Supolcmentary Notes
Frederick W. Kutz, Project Officer
Daniel T. Heggem, Task Manager
j 10. Project/Task/Wo'k Unit No.
! Task. _61
j 11. Conlract(C) or Crant(G) No.
1(0 68-01-5915
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