United States
Environmental Protection
Agency
Office Of Air Quality
Planning And Standards
Research Triangle Park, NC 27711
EPA-454/R-00-038a
September 2000
Air
& EPA
Source Characterization For
Sewage Sludge Incinerators
Executive Summary Report
Metropolitan Sewer District (MSD)
Mill Creek Wastewater Treatment Plant
Cincinnati. OhiO US. Environmental Protection Agencr
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12th Ftoar
Chicago. II 60604-3590
-------
ERRATA
"SOURCE CHARACTERIZATION FOR SEWAGE SLUDGE INCINERATORS - FINAL
EMISSIONS REPORT - VOLUME I OF m - METROPOLITAN SEWER DISTRICT (MSD)
MILL CREEK WASTEWATER TREATMENT PLANT, CINCINNATI, OHIO"
EPA -454/R-00-038b - September 2000
Please delete and replace the following text contained in the report.
Page 1-1 1.0 INTRODUCTION
1.1 SUMMARY OF TEST PROGRAM
Delete the first and second paragraphs starting with: "The Clean Air Act Amendments"
Replace the second paragraph as follows:
This test report summarizes testing of a multiple hearth incinerator at the Metropolitan
Sewer District (MSD) Mill Creek Wastewater Treatment Plant in Cincinnati, Ohio in July,
S 1999. The emissions data collected in this program wfll be used to provide information
Q for EPA's Office of Water (OW) to determine the need for further emissions standards in
r the Section CFR 503 - Subpart E, Standards for Incineration of Sewage Sludge.
-------
ERRATA
"SOURCE CHARACTERIZATION FOR SEWAGE SLUDGE INCINERATORS -
EXECUTIVE SUMMARY REPORT - METROPOLITAN SEWER DISTRICT (MSD) - MILL
CREEK WASTEWATER TREATMENT PLANT, CINCINNATI, OHIO"
EPA -454/R-00-038a - September 2000
Please delete and replace the following text contained in the report.
Page 6 1.0 OVERVIEW
Delete the second paragraph starting with: "This executive summary report summarizes"
Replace the second paragraph as follows:
This executive summary report summarizes testing of a multiple hearth incinerator at the
Metropolitan Sewer District (MSD) Mill Creek Wastewater Treatment Plant in Cincinnati,
Ohio in July, 1999. The emissions data collected in this program will be used to provide
information for EPA's Office of Water (OW) to determine the need for further emissions
standards in the Section CFR 503 - Subpart E, Standards for Incineration of Sewage
Sludge.
-------
ERRATA
"SOURCE CHARACTERIZATION FOR SEWAGE SLUDGE INCINERATORS -
EXECUTIVE SUMMARY REPORT - METROPOLITAN SEWER DISTRICT (MSD) - MILL
CREEK WASTEWATER TREATMENT PLANT, CINCINNATI, OHIO"
EPA -454/R-00-038a - September 2000
Please delete and replace the following text contained in the report.
Page 6 1.0 OVERVIEW
Delete the second paragraph starting with: "This executive summary report summarizes"
Replace the second paragraph as follows:
This executive summary report summarizes testing of a multiple hearth incinerator at the
Metropolitan Sewer District (MSD) Mill Creek Wastewater Treatment Plant in Cincinnati,
Ohio in July, 1999. The emissions data collected in this program will be used to provide
information for EPA's Office of Water (OW) to determine the need for further emissions
standards in the Section CFR 503 - Subpart E, Standards for Incineration of Sewage
Sludge.
-------
For Review and Approval
Project No. G474001-02
t
Name
Originator
Concurrence
Approved
J Ferg
K Riggs
Initials
vfi3-
7V ^
•^y//*?
Date
$rl/OD
/ 1
*1 jcqfffr
Internal Distribution
J Ferg
K Riggs
U Jackson
Project Files
RMO
Sent Via: US MAIL + KMAIL-Riley; US
US MAIL-Clark
-1 • •/
MAJ2/-W&
ant
September 12, 2000
Mr. C. E. (Gene) Riley
U.S. Environmental Protection Agency
Emission Measurement Center
MD-19
Research Triangle Park, NC 27711
Dear Gene:
Contract No. 68-D-99-009
Work Assignment 2-01
Executive Summary Report
Enclosed for your use are 12 copies of the final Executive Summary Report (ESR) for Work
Assignment 2-01 Source Characterization for Sewage Sludge Incinerator Emissions. The
WordPerfect electronic file has also been transmitted to you.
The final DQA report will be forwarded to you next week. Battelle anticipates that this delivery
will complete Work Assignment 2-01.
If you have any immediate questions on the enclosed. ESR, please call me at 614-424-5970.
Sincerely,
'Ferg
WA 2-01 Work Assignment Leader
Atmospheric Science and Applied Technology
JAF:dlm
Enclosures
cc: Ms. Kathy Weant
Ms. Sandra Clark
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EPA-454/R-00-038a
SOURCE CHARACTERIZATION FOR SEWAGE SLUDGE INCINERATORS
EXECUTIVE SUMMARY REPORT
METROPOLITAN SEWER DISTRICT (MSD)
MILL CREEK WASTERWATER TREATMENT PLANT
CINCINNATI, OHIO
Prepared for:
Clyde E.Riley(MD-19)
Emissions, Monitoring and Analysis Division
Office of Air Quality Planning-and Standards
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
September 2000
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EPA DISCLAIMER
The information in this document has been funded wholly or in part by the United States
Environmental Protection Agency under Contract 68-D-99-009 to Battelle. It has been subject to
the Agency's review, and has been approved for publication as an EPA document. Mention of
trade names or commercial products is not intended to constitute endorsement or
recommendation for use.
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ACKNOWLEDGMENTS
This report was prepared under Contract No. 68-D-99-009, Work Assignment WA 2-01,
by Battelle and its subcontractor ETS, Inc. under the sponsorship of the U.S. Environmental
Protection Agency. Mr. Eugene Grumpier was the EPA Program Manager and Mr. C. E. (Gene)
Riley was the Work Assignment Manager. Their support on this test program was much
appreciated. We would also like to acknowledge the assistance provided by the Hamilton
County Metropolitan Sewer District and its employees, in*particular Mr. Michael W. Heitz, who
served as the MSD on-site coordinator for this test program.
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TABLE OF CONTENTS
Paoe
EPA DISCLAIMER 2
ACKNOWLEDGMENTS 3
1.0 OVERVIEW 6
1.1 Test Objectives 6
1.2 Process Description 7
1.3 Test Program 7
1.4 Summary of Content 11
2.0 SUMMARY AND DISCUSSION OF TEST RESULTS 11
2.1 Air Emissions Measurements 11
2.1.1 Toxic PCB Results 12
2.1.2 Dioxin/Furan (D/F) Results 17
2.1.3 PAH Results 17
2.1.4 Continuous Emission Monitoring Data 23
2.2 Process Sample Measurements 25
2.2.1 Scrubber Water Organic Results 25
2.2.1.1 Toxic PCB Comparison of Scrubber Water In Versus
Scrubber Water Out 25
2.2.1.2 D/F Results for Scrubber Water 25
2.2.2 Sewage Sludge Organic Results 28
2.2.3 Scrubber Water and Sewage Sludge Inorganic Results 28
3.0 DISCUSSION OF DATA QUALITY 32
3.1 QA Objectives 32
3.2 Data Evaluation 34
3.2.1 Data Quality 34
3.2.2 Data Quantity 34
3.3 Summary of Test Report Data Analysis 36
4.0 CONCLUSIONS 37
4.1 Air Emissions Measurements 37
4.1.1 Toxic PCBs 39
4.1.2 D/Fs 41
4.1.3 PAHs 41
4.1.4 Continuous Emission Monitoring 42
4.2 Process Sample Organic Measurements 43
4.2.1 Toxic PCB Comparison of Scrubber Water In Versus Scrubber
Water Out 43
4.2.2 D/F Results for Scrubber Water 43
4.2.3 Sewage Sludge Organic Results ; 44
4.3 Process Sample Inorganic Measurements 44
4.3.1 Scrubber Water 44
4.3.2 Sewage Sludge 44
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LIST OF TABLES
Table 1-1. Test Matrix 10
Table 2-1. Toxic PCB Results - Stack Gas Concentrations (ng/dscm, as measured) 13
Table 2-2. Toxic Results - Stack Gas Concentrations (ng/dscm, adjusted
to 7% O2) 14
Table 2-3. Toxic PCB Results - WHO Toxic Equivalent Stack Gas
Concentrations (ng/dscm, adjusted to 7% 02) I b
Table 2-4. World Health Organization Toxic Equivalent Factors (TEFs) for
Determining Toxic PCB TEQs 16
Table 2-5. D/F Results - Stack Gas Concentrations (ng/dscm, as measured) 18
Table 2-6. D/F Results - Stack Gas Concentrations (ng/dscm, adjusted to
7% 02) 19
Table 2-7. D/F Results - TEQ Stack Gas Concentrations (ng/dscm, adjusted
to 7% 02) 20
Table 2-8. PAH Results - Stack Gas Concentrations (ng/dscm, as measured) . . ... 21
Table 2-9. PAH Results - Stack Gas Concentrations (ng/dscm, adjusted to
7% O2 22
Table 2-10. CEM Daily Results • 23
Table 2-11. Run 2, Run 3, and Run 4 Toxic PCB Results - Comparison of
Inlet Versus Outlet Scrubber Water .26
Table 2-12. D/F Results - Comparison of Inlet Versus Outlet Scrubber Water 27
Table 2-13. Toxic PCB Results for Sewage Sludge , 29
Table 2-14. D/F Results for Sewage Sludge 30
Table 2-15. Chlorine, Percent Solids, Temperature, and pH Results - Comparison
of Inlet Versus Outlet Scrubber Water 28
Table 2-16. Chlorine and Percent Solids Results for Sewage Sludge .31
Table 2-17. Ultimate Analysis Results for Sewage Sludge 31
Table 2-18. Proximate Analysis Results for Sewage Sludge , . . 32
Table 3-1. Overall Program QA/QC Results 35
Table 4-1. Back Half Air PCB Data Corrected for Pre-Sampling Surrogate Recovery . 40
LIST OF FIGURES
Figure 1-1. Schematic Diagram of Mill Creek Wastewater Treatment
Plant Process
Figure 1 -2. Continuous Sampling System for Instrumental Methods
Figure 2-1. CO and THC Daily Test Results - Run 2
Figure 2-2. CO and THC Daily Test Results - Run 3
Figure 2-3. CO and THC Daily Test Results - Run 4
24
24
24
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1.0 OVERVIEW
The U.S. Environmental Protection Agency's (EPA) Office of Air Quality Planning and
Standards (OAQPS) is required to establish standards, which consist of general requirements,
pollutant characterization, and emission limits for sewage sludge disposal by incineration. These
standards are necessary to protect public health and the environment from any adverse effect of a
pollutant during the incineration of sewage sludge. In order for EPA to assess control
technologies and the associated strategies for cost-effective development and/or use, data on
emissions from sewage sludge incinerators are needed. While some emission data exist for
sewage sludge incinerators, data on toxic polychlorinated biphenyls (PCBs) from this source type
are scarce.
This executive summary report summarizes testing of a multiple hearth incinerator at the
Metropolitan Sewer District (MSD) Mill Creek Wastewater Treatment Plant in Cincinnati, Ohio
in July, 1999. The emission data collected in this test program will be used by OAQPS and
EPA's Office of Water (OW) to support a decision about further data gathering efforts in support
of Maximum Achievable Control Technology (MACT) standards for sewage sludge incinerators.
1.1 TEST OBJECTIVES
The PCS and D/F emissions data collected from the MSD sewage sludge incinerator in
this test program will be used by EPA's OAQPS and OW to:
(1) Conduct a comprehensive assessment of the risk to human health of the emissions
of dioxin/furan/toxic PCBs from sewage sludge incinerators. This assessment is to
determine if regulations on these emissions are required to reduce any unacceptable
risk.
(2) Establish an emissions data base for toxic PCB and D/F emissions from sewage
sludge incinerators.
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1.2 PROCESS DESCRIPTION
The Mill Creek Wastewater Treatment Plant is a municipal wastewater treatment plant
designed to process 120 to 180 million gallons per day (MOD) of wastewater. Most of the
wastewater received at the treatment plant comes from sanitary sources, with approximately 20
to 25 percent from industrial sources. The sludge generated from wastewater treatment is
incinerated on site in six multiple hearth incinerators. Normally, three incinerators incinerate a
combined total of 100 dry tons of sludge per day. The incinerators operate 24 hours a day.
Natural gas and digester gas are used as auxiliary fuels. Emissions from each incinerator are
controlled by a venturi scrubber, followed by a three-tray impingement conditioning tower with a
chevron style stainless steel demister, and exit through an individual stack. Figure 1-1 details the
process flow diagram for the facility.
1.3 TEST PROGRAM
In this test program, emissions from Incinerator No. 6 were collected and analyzed for
PCB, D/F, and polycyclic aromatic hydrocarbons (PAH). Carbon monoxide (CO), carbon
dioxide (CO2), oxygen (O2), and total hydrocarbon (THC) emissions from the incinerator were
continuously monitored throughout the test. Figure 1-2 shows the continuous sampling system.
Process samples consisting of sludge feed and scrubber water into and out of the ventun
control system were also collected. Both sludge feed and scrubber water samples were analyze,!
for PCB, D/F, chlorine (C12), and percent solids. The temperature and pH of the scrubber water
were measured at the tune of sample collection. Ultimate/proximate analysis of the sludge feed
was also conducted.
A matrix of the type and location of the samples collected is presented in Table 1 -1.
-------
Domestic and Industrial
Contributors (Influent)
Primary Sludge
Wastewater
Sludge Thickening
System
Skimmings Handling
Facility
Thickened Sludge
Thickened Secondary
Wastewater
Sludge
Anaerobic Digesters
Digested.Sludge
Dissolved Air Flotation
System
Sludge Dewatering
System
Dewatered Sludge
Incinerators
Secondary
Treatment
Wastewater
Activated Sludge
(Aeration) Tanks
CD
•o
55
a>
to
Wastewater
Secondary Ciarifiers
Wastewater
Chlorination
Effluent Sludge
Ohio River
Figure 1-1. Schematic Diagram of Mill Creek Wastewater Treatment Plant Process
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Flowmeter
Stack • c=t
Heated stainless
steel probe
3-way valve
Ver-
ICZN=>-
^
>
Heated
filter
O2 analyzer
o
*«•
CO2 analyzer
CO analyzer
Heated Teflon
sample line
Condensate
Dual-pass
refrigerative
condenser.
Unheated Teflon
sample line
Data acquisition
Teflon
diaphragm
pump
To individual analyzer calibration
manifold
Figure 1-2. Continuous Sampling System for Instrumental Methods
(EPA Methods 3A and 10)
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Table 1-1. Test Matrix
Sampling
Location/
Matrix
Outlet Stack
Sludge Feed
Scrubber Water
No. of
Runs
3°
3"
3"
Continuous
Continuous
Continuous
6 Grab
Samples
(1 per
hour)
Inlet and
Outlet
6 Grab
Samples
Each (1 per
• hour)
Sample Type
Toxic PCBs
D/Fs
PAHs
CO
0,/C03
THC
Toxic PCBs
D/Fs
Chlorine
Total % Solids
Ultimate/Proximate
Toxic PCBs
D/Fs
Chlorine
Total % Solids
pH/Temp
Sampling
Method
M-0010"
M-00100
M-00106
M 10'
M3A»
M25A
Composite of
60 min grabs
Composite of
60 min grabs
Composite of
60 min grabs
Composite of
60 min grabs
Composite of
60 min grabs
Composite of
60 min grabs
Composite of
60 min grabs
Composite of
66 min grabs
Composite of
60 min grabs
60 min grabs
Sampling
Org. •
ETS
ETS
ETS
ETS
ETS
MSD
Battelle
Battelle
Battelle
Battelle
Battelle
Battelle
Battelle
Battelle
Battelle
Battelle
Sample Run'
Tim* (min)-1
360
360
360
360
360
360
360
360
360
360
360
360
360
360
360
360
.Analytical
.' Method
Draft PCB-
Emissions0
M-8290"
CARB 429*
NDIR
Chemical
Cell/ NDIR
Flame
lonization
Draft PCB
Sludge"
M-8290
M-4500 G1
M-2540 B'
ASTM
D3172,
D5373
Draft PCB
Water"
M-8290
M-4500 G
M-2540 B
M-4500-H'
Analytical
.Laboratory
Battelle
Battelle
Quanterra
NA
NA
NA
Battelle
Battelle
U.S. EPA
T&E
U.S. EPA
T&E
CT&E
Battelle
Battelle
U.S. EPA
T&E
U.S. EPA
T&E
Battelle
a SW-846, Method 0010, Modified Method 5 Sampling Train.
b Three M-0010 runs total at outlet stack, single M-0010 run will generate sample for coplanar PCB, D/F, and PAH
analysis.
c Draft Analytical Method for Determination of Toxic Polychlorinated Biphenyl Emissions from Sewage Incinerator
Stationary Sources Using Isotope Dilution High Resolution Gas Chromatography/High Resolution Mass Spectrometry.
d SW-846, Method 8290, Polychlorinated Dibenzodioxins (PCDDs) and Polychlorinated Dibenzofurans (PCDFs) by High
Resolution Gas Chromatography / High Resolution Mass Spectrometry (HRGC / HRMS).
e Air Resources Board, Method 429, Determination of Polycyclic Aromatic Hydrocarbons (PAH) Emissions from Stationary
Sources.
f 40CFR60, Appendix A, Method 10, Determination of Carbon Monoxide Emissions from Stationary Sources.
g 40CFR60, Appendix A, Method 3A, Determination of Oxygen and Carbon Dioxide Concentrations in Emissions from
Stationary Sources.
h Draft Method, Determination of Toxic Polychlorinated Biphenyls in Sewage Sludge Using Isotope Dilution High Resolution
Gas Chromatography / High Resolution Mass Spectrometry.
i Standard Methods for Examination of Water and Wastewater, Method 4500 G, DPD Colorimetric Method.
j Standard Methods for Examination of Water and Wastewater, Method 2540 B, Total Solids Dried at 103-105*C. .
k Draft Method, Determination of Toxic Polychlorinated Biphenyls in Sewage Incinerator Scrubber Water Using Isotope
Dilution High Resolution Gas Chromatography / High Resolution Mass Spectrometry.
I Standard Methods for Examination of Water and Wastewater, Method 4500 H, pH Value.
10
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1.4 SUMMARY OF CONTENT
This executive summary report consists of the following sections:
Section 1.0 provides an overview of the test program. This section includes the genera!
purpose and background of the test program, a brief overview of the facility and process tested
and the test matrix.
Section 2.0 provides a summary of test results. This section includes CEM results;
analytical results for PCBs, D/Fs, and PAHs for emission, scrubber water, and sludge feed
samples; and inorganic analysis results for scrubber water and sludge feed samples
Section 3.0 contains a discussion of the data quality and the QA objectives that were met
Section 4.0 presents conclusions about the test results by media and analyte.
Additional information and detail is contained in both the Emissions Test Report and the Data
Quality Assessment Report documents.
2.0 SUMMARY AND DISCUSSION OF TEST RESULTS
2.1 AIR EMISSIONS MEASUREMENTS
The test results for air emissions are provided for toxic PCBs in Tables 2-1 through 2-4,
for D/Fs in Tables 2-5 through 2-7, and for PAHs in Tables 2-8 and 2-9.
The toxic PCB, D/F, and PAH results for Runs 2 and 3 are almost identical for most ol
the analytes. The back half emission concentrations for Run 4 are 50 to 60 percent lou cr thar
the back half emission concentrations for Runs 2 and 3 for all the analytes. As a result, emissior
concentrations for Run 4 are approximately half of the emission concentrations for Runs 2 and 3
for all three analyte classes.
Analyte loss may have occurred during sampling, during sample handling and transport
or prior to spiking the Run 4 sample with pre-extraction internal standards. This time period is
based on a comparison of the pre-field surrogate spike recoveries to the pre-extraction internal
standard recoveries. Recoveries of the pre-field surrogate spikes for Run 4 back half samples
were approximately half of the recoveries for Run 2 and 3 back half samples for all PCB, D/F,
and PAH field surrogate spikes, whereas recoveries of the spiked pre-extraction PCB, D/F, anil
11
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PAH internal standards were comparable and generally acceptable across all three runs. Any
losses in the pre-field surrogate spikes that may have occurred in sample extraction or cleanup of
the Run 4 back half sample would have also been reflected in similar losses of the spiked pre-
extraction internal standards. Since the pre-extraction internal standard results are acceptable for
Run 4 and consistent with the other two runs, this result suggests that the field surrogate spike
and analyte losses likely occurred prior to extraction of the Run 4 emission samples.
Another indicator that analyte losses occurred prior to sample extraction is that the PCB,
D/F, and PAH concentrations in the samples follow the same pattern as the pre-field surrogate
spikes in that all measured back half analytes were approximately one half or less for the Run 4
sample. In addition, analyte concentrations for the Run 4 front half sample were somewhat
lower than the Run 2 and 3 front half samples. This suggests that analyte levels may not have
been consistent during sampling due to some type of matrix interference inherent in incineration
systems. Prior experience with municipal and medical waste incineration have exhibited similar
low pre-field surrogate standard recoveries — the cause of which is as yet unknown.
2.1.1 Toxic PCB Results
The toxic PCB results in ng/dscm are summarized in Tables 2-1 and 2-2. Toxic PCB
results for Runs 2 and 3 are almost identical for most of the analytes. The back half emission
concentrations for Run 4 are 50 to 60 percent lower than the back half emission concentrations
for Runs 2 and 3 for all the analytes. Possible loss of PCBs may have occurred in the field as
indicated by lower pre-field surrogate recoveries for Run 4 (as discussed in Section 4.1). The
PCB data have been reviewed extensively, and no reason can be found for the data differential.
Alternatively, these lower Run 4 concentrations may be an accurate reflection of a change in
incinerator emissions on the third day of sampling. Table 2-3 presents toxic PCB results in
World Health Organization (WHO) Toxic Equivalencies which are an estimate of the
concentration of 2,3,7,8-TCDD which would produce an equivalent toxicity as the PCB. The
Toxic Equivalent Factors (TEFs) for the toxic PCBs are presented in Table 2-4.
12
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Table 2-1. Toxic PCB Results - Stack Gas Concentrations (ng/dscm, as measured!
HHHHBHHH
3,3', 4,4 '-tetrachlorobiphenyl (TCB)
(PCB-77)6
2,3, 3 ' ,4,4 '-pentachlorobiphenyj (PeCD)
(PCB-105)
2,3,4,4', 5-pentachlorobiphenyl (PeCB)
(PCB-114)
2,3',4,4', 5-pentachlorobiphenyl (PeCB)
(PCB-118)
2', 3, 4,4', 5-pentachlorobiphenyl (PeCB)
(PCB-123)
3, 3',4,4', 5-pentachlorobiphenyl (PeCB)
(PCB-126)
2,3,3',4,4',5-hexachlorobiphenyl (HxCB)
(PCB-156)
2,3,3',4,41,5'-hexachlorobiphenyl (HxCB)
(PCB- 157)
2,3',4,4',5,5'-hexachlorobiphenyl(HxCB)
(PCB-167)
3r3',4,4',5,5'-hexachlorobiphenyl (HxCB)
(PCB- 1-69)
2,2',3,3',4,4',5-heptachlorobiphenyl (HpCB)
{PCB- 170)
2,2',3,4/4',5,5'-heptachlorobiphenyl (HpCB)
(PCB-180)
2,3,3',4,41,5f5'-heptachlorobiphenyl (HpCB)
(PCB-189)
^Hg*fffHmin/mTTrii/im
HHBM
15.6
2.67
0.389
5.72
0.121
0.700
0.645
0.221
0.388
0.559
1.08
2.69
0.095
10.7
2.45
0.340
5.27
0.111
0.584
0.565
0.179
0.337
0.467
0.966
2.37
0.076
4.27
0.94&
0.137
2.2:
0.038
0.210
0.213
0.079
0 136
0.141
0 43 7
0.856
0.044
* ng/dscm; nanogram per dry standard cubic meter.
Standard conditions: temperature - 20°C; pressure - 1 atm (760 mm Hg).
b Back half extracts diluted with additional internal standard and re-analyzed to bring the reponed
concentrations within the calibration range (see Section 6.1.3.1).
13
-------
Table 2-2. Toxic PCB Results - Stack Gas Concentrations (ng/dscm, adjusted to
7% O2)
IJ^^^^^^^^CBWoTO^ii^^^^S^
3,3',4,4'-tetrachlorobiphenyl (TCB)
(PCB-77)"
2,3,3', 4,4'-pentachlorobiphenyl (PeCB)
(PCB-105)
2,3,4,4',5-pentachlorobiphenyl (PeCB)
(PCB-114)
2,3',4,4',5-pentachlorobiphenyl (PeCB)
(PCB-118)
2',3,4,4',5-pentachlorobiphenyl (PeCB)
(PCB-123)
3,3',4,4',5-pentachlorobiphenyl (PeCB)
(PCB-126)
2,3,3',4,4',5-hexachlorobiphenyl (HxCB)
(PCB-156)
2,3,3',4/4',5'-hexachlorobiphenyl(HxCB)
(PCB-157)
2,3',4,41,5,5'-hexachlorobiphenyl (HxCB)
(PCB-167)
3,3',4,4',5,5'-hexachlorobiphenyl (HxCB)
(PCB-169)
2,2',3,31,4,41,5-heptachlorobiphenyl (HpCB)
(PCB-170)
2,2',3,4,4',5,5'-heptachlorobiphenyl (HpCB)
(PCB-180)
2,3,3',4,4',5,5'-heptachlorobiphenyl (HpCB)
(PCB-189)
!|fl^5ljHjffiEEJH;g3BS£!3i
30.6
5.22
0.762
11.2
0.237
1.37
1.26
0.433
0.760
1.09
. 2.11
5.26
0.186
Jajg^gljaSsaiBlBga
18.8
4.32
0.598
9.27
0.195
1.03
0.994
0.315
0.593
0.822
1.70
4.18
0.134
7.92
1.75
0.254
4.10
0.070
0.389
0.395
0.146
0.252
0.261
0.810
1.59
0.082
ng/dscm; nanogram per dry standard cubic meter, adjusted to 7% oxygen.
Standard conditions: temperature - 20°C; pressure - 1 atm (760 mm Hg).
" Back half extracts diluted with additional internal standard and re-analyzed to bring the reported
concentrations within the calibration range (see Section 6.1.3.11.
14
-------
Table 2-3. Toxic PCB Results - WHO Toxic Equivalent Stack Gas Concentrations
(ng/dscm, adjusted to 7% O2)
3,3',4,4'-tetrachlorobiphenyl (TCB)
(PCB-77)""
1 .OE-04
3.06E-03
1.88E-03
7.92E-04
2,3,3',4,41-pentachlorobiphenyl (PeCB)
(PCB-105)
1. OE-04
5.23E-04
4.32E-04 1.75E04
2,3,4,4',5-pentachlorobiphenyl (PeCB)
(PCB-114)
5.OE-04
3.81E-04
2.99E-04 ; 1.27E-04
2,3',4,4',5-pentachlorobiphenyl (PeCB)
{PCB-118)
1 .OE-04
1.12E-03
9.27E-04 4.10E-04
2',3,4,4',5-pentachlorobiphenyl (PeCB)
{PCB-123)
1 .OE-04
2.37E-05
1.95E-05
7 04E 06
3,3',4,4',5-pentachlorobiphenyl {PeCB)
(PCB-126)
0.1
1.37E-01
1.03E-01
3.89E-02
2,3,3',4,4',5-hexachlorobiphenyl (HxCB)
(PCB-156)
5.0E-04,
6.31 E-04
4.97E-04
1.97E-04
2,3,3',4,4I,5'-hexachlorobiphenyl (HxCB)
(PCB-157)
5. OE-04
2.16E-04
1.57E-04 7 '22E-05
2,3',4,4',5,5'-hexachlorobiphenyl (HxCB)
{PCB-167)
1.0E-05
7.60E-06
5.93E-06 2 52E-06
3,3',4,4',5,5'-hexachlorobiphenyl {HxCB)
{PCB-169)
0.01
1.09E-02
8.22E-03 2 5 ' E 03
2,2',3,3',4,4',5-heptachlorobiphenyl (HpCB)
(PCB-170)
1 .OE-04
2.11 E-04
1.70E-04
8.10E-05
2,2',3,4,4',5,5>-heptachlorobiphenyl (HpCB)
(PCB-180)
1 .OE-05
5.26E-05
4.18E-05
2,3,3',4.4'.5,5f-heptachlorobiphenyl (HpCB)
(PCB-189)
1.OE-04
1.86E-05
1.34E-05
1 59E-Ob
8 15E-06
* ng/dscm; nanogram per dry standard cubic meter, adjusted to 7% oxygen.
b Back half extracts diluted with additional internal standard and re-analyzed to bring the reporte.;
concentrations within the calibration range (see Section 6.1.3.11.
e WHO TEFs - World Health Organization, Toxic Equivalent Factors.
Standard conditions: temperature - 20°C; pressure - 1 atm (760 mm Hg).
15
-------
Table 2-4. World Health Organization Toxic Equivalent Factors (TEFs) for
Determining Toxic PCB TEQs
Non-ortho
Mono-ortho
Di-ortho
r HittM 'iindanii'trfi
ifSIPPsrlEUWWHt
77
126
169
105
114
118
123
156
157
167
189
170
180
3,3',4,4'-tetrachlorobiphenyl (TCB)
2,3,3',4'5-pentachlorobiphenyl (PeCB)
3,3'(4,4',5,5'-hexachlorobiphenyl (HxCB)
2,3',3',4,4'-pentachlorobiphenyl (PeCB)
2,3,4,4',5-pentachlorobiphenyl (PeCB)
2,3',4,4',5-pentachlorobiphenyl (PeCB)
2,3,3',4,4',5-hexachlorobiphenyl (PeCB)
2,3,3',4,4',5'-hexachlorobiphenyl (HxCB)
2,3,3',4,4',5'-hexachlorobiphenyl (HxCB)
2,3',4,4',5,5'-hexachlorobiphenyl (HxCB)
2,3,3',4/4'(5,51-heptachlorobiph«nyl (HpCB)
2,2',3,3',4,4',5-heptachlorobiphenyl (HpCB)
2,2',3,4,4',5,5'-heptachlorobiphenyl (HpCB)
SiglBPHRwwSf!
[IffiSlaHEFJIsit?!
0.0001
0.1
0.01
0.0001
0.0005
0.0001
0.0001
0.0005
0.0005
0.00001
0.0001
0.0001
0.00001
' IUPAC = International Union of Pure and Applied Chemistry.
Note: World Health Organization (WHO) TEFs for human risk assessment based on
of the WHO consultation in Stockholm, Sweden, 15-18 June 1997 (Van der
1998).
the conclusions
Berg et al..
16
-------
2.1.2 Dioxin/Furan (D/F) Results
The D/F results are summarized in Tables 2-5 through 2-7. A detailed discussion of the
QA/QC results associated with these D/F data appears in Section 3.2. D/F results for Runs 2
and 3 are almost identical for most of the analytes. The back half emission concentrations for
Run 4 are 50 to 60 percent lower than the back half emission concentrations for Runs 2 and 3 for
all the analytes. These lower Run 4 concentrations may be due to analyte loss or an accurate
reflection of a change in incinerator emissions on the third day of sampling. The D/F data have
been reviewed extensively, and no reason can be found for the data differential.
2.1.3 PAH Results
The PAH results are summarized in Tables 2-8 and 2-9. A detailed discussion of the
QA/QC results associated with these PAH data appears in Section 4.1.3. PAH results for Runs 2
and 3 are somewhat similar for most of the analytes. The back half emission concentrations for
Run 4 are 50 to 60 percent lower than the back half emission concentrations for Runs 2 and 3 for
most of the analytes. These lower Run 4 concentrations may be due to analyte loss or an
accurate reflection of a change in incinerator emissions on the third day of sampling. The PAH
data have been reviewed extensively, and no definitive reason can be found for the data
differential (see Section 4.1).
17
-------
Table 2-5. D/F Results - Stack Gas Concentrations (ng/dscm, as measured)
2,3,7,8-TCDD
0.098
0.067
0.034
Total TCDD
3.02
3.53
0.719
1,2,3,7,8-PCDD
0.017
0.013
(0.005)
Total PCDD
0.706
0.658
0.187
1,2,3,4,7,8-HxCDD
0.015
0.015
0.006
1,2,3,6,7,8-HxCDD
0.038
0.040
0.013
1,2,3,7,8,9-HxCDD
0.039
0.035
0.018
Total HxCDD
0.606
0.584
0.324
1,2,3,4,6,7,8-HpCDD
0.204
0.202
0.093
Total HpCDD
0.459
1.45
0.237
Octa CDD
0.317
0-303
0.140
Total CDD Based on given numbers:
5.11
6.53
1.61
2,3,7,8-TCDF
1.58
1.24
0.533
Total TCDF
5.61
4.88
2.57
1,2,3,7,8-PCDF
O.V95
0.150
0.068
2.3.4,7,8-PCDF
0.389
0.283
0.123
Total PCDF
4.93
3.67
1.54
1.2,3,4,7,8-HxCDF
0.226
0.177
0.092
1,2,3,6,7,8-HxCDF
0.081
0.067
0.035
2,3,4,6,7,8-HxCDF
0.126
0.097
0.051
1,2,3,7,8,9-HxCDF
ND< 0.003
ND< 0.003
ND< 0.003
Total HxCDF
1.13
0.880
0.410
1,2,3,4,6,7,8-HpCDF
0.224
0.185
0.103
1,2,3,4,7,8,9-HpCDF
0.023
0.017
0.009
Total HpCDF
Octa CDF
0.329
0.090
0.261
0.082
0.137
0.041
Total CDF Based on given numbers:
12.1
9.77
4.69
Total CDD + CDF Based on given numbers:
17.2
16.3
6.30
1 ng/dscm; nanogram per dry standard cubic meter.
Standard conditions, pressure and temperature defined as 1 atm (760 mm Hg) and 20°C.
Note: (Below Detection Limit) values listed in parentheses; ND = Non Detect, value is detection limit.
# = value from confirmation column. Non Detect and (Below Detection Limit) values not included in
totals.
18
-------
Table 2-6. D/F Results • Stack Gas Concentrations (ng/dscm, adjusted to 7% O2)
2,3,7,8-TCDD
0.209
0.118
0.063
Total TCDD
5.92
6.22
1.33
1,2,3,7,8-PCDD
0.033
0.023
(0.009)
Total PCDD
1.38
1.16
0.348
1,2.3,4,7,8-HxCDD
0.029
0.026
0.011
1,2,3,6,7,8-HxCDD
0.074
0.069
0.024
1,2,3,7,8,9-HxCDD
0.076
0.062
0.03C
Total HxCDD
1.19
1.03
0.600
1,2,3,4,6,7,8-HpCDD
0.399
0,357
0.172
Total HpCDD
0.899
2.560
0.439
Octa CDD
0.621
0.424
0.259
Total CDD
2,3,7,8-TCDF
10.0
3.10
11.4
2.17
2.97
0.988
Total TCDF
11.00
8.58
4.76
1,2,3.7.8-PCDF
0.382
0.264
0.124
2,3,4,7.8-PCDF
0.762
0.496
0.228
Total PCDF
9.66
6.45
2.85
1,2,3,4,7,8-HxCDF
0.442
0.313
0.169
1,2,3,6,7,8-HxCDF
0.159
0.116
0.065
2,3,4,'6,7,8-HxCDF
0.247
0.171
0.095
1,2,3,7,8,9-HxCDF
ND< 0.0059
ND< 0.0053
ND<0.0056
Total HxCDF
2.20
1.55
0.760
1,2,3,4.6,7,8-HpCDF
0.437
0.324
0.189
1,2,3.4,7,8,9-HpCDF
0.043
0.030
0.017
Total HpCDF
0.642
0.459
0.252
Octa CDF
Total CDF
0.176
23.7
0.146
17.2
0,078
8.71
Total CDD + CDF
33.7
28.6
11.7
' ng/dscm; nanogram per dry standard cubic meter, adjusted to 7% oxygen. Standard conditions, pressure
and temperature defined as 1 atm (760 mm Hg) and 20°C.
Note: (Below Detection Limit) values listed in parentheses.
Non Detects and (Below Detection Limit) values not included in totals.
ND = Non detect, value is detection limit.
19
-------
Table 2-7. D/F Results - TEQ Stack Gas Concentrations (ng/dscm, adjusted to 7% 02)
2,3,7,8-TCDD
1.000
0.209
0.118
0.063
Total TCDD
1,2,3,7,8-PCDD
0.500
0.017
0.012
(0.0051
Total PCDD
1,2,3,4,7,8-HxCDD
0.100
0.003
0.003
0.001
1,2,3,6,7,8-HxCDD
0.100
0.007
0.007
0.002
1,2,3,7,8,9-HxCDD
0.100
0.008
0.006
0.003
Total HxCDO
1.2.3.4,6,7.8-HpCDD
0.010
0.004
0.004
0.002
Total HpCOD
Octa CDD
0.001
ucta CUD u.uu i
2.3,7,8-TEQ Total CDD
2,3,7,8-TCDF 0.100
0.00062
0.00053
0.00026
0.249
0.310
Total TCDF
1,2.3,7,8-PCDF
0.050
0.019
0.013
0.006
2,3,4,7,8-PCDF
0.500
0.381
0.248
0.114
Total PCDF
1,2,3,4,7,8-HxCDF
0.100
0.044
0.031
0.017
1,2,3,6,7,8-HxCDF
0.100
0.016
0.012
0.017
ND< 0.0005
0.007
0.010
ND< 0.0006
2,3.4,6,7,8-HxCDF
0.100
0.025
1,2,3,7,8,9-HxCDF
0.100
ND< 0.0006
Total HxCDF
1,2,3,4,6,7,8-HpCDF
0.010
0.004
0.003
0.002
1,2,3,4,7,8,9-HpCDF
Total HpCDF
0.010
0.000
0.000
0.000
Octa CDF
2,3,7,8-TEQ Total CDF
0.001
0.000
0.000
0.000
0.799
0.542
0.255
2,3,7.8-TEO Total CDD + CDF
1.05
0.693
0.326
* ng/dscm; nanogram per dry standard cubic meter, adjusted
and temperature defined as 1 atm (760 mm Hg) and 20°C.
Note: (Below Detection Limit) values listed in parentheses.
not included in totals.
to 7% oxygen. Standard conditions, pressure
Non Detects and (Below Detection Limit) values
20
-------
Table 2-8. PAH Results - Stack Gas Concentrations (ng/dscm, as measured)
•^HHHHH^^HBI
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a (anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Chrysene
Dibenzo{a,h)anthracene
Fluoranthene
Fluorene
Indenod ,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
BBBBSSBEIISBeiHP'pBSi
JBBBBjjffifKNMiltijffliJ
^^H^^BBBI^H^^^^^I
•BBBymBgHHIJ
UBHUiMl^mSailBjmIEZ
109
{1160}D
{144}
93.0
' 828
759
233
75.2
2390 E
71.8
2700 E
1030
244-
{309000}D,E
{22600}D,E
1810E
BI|jM^8B
HMJHH
f^^ffWRSwMMSiWR^HBi
83.6
{1290}E
{52.7}
251
662
361
134
34.1
{1340}E
48.9
{2340}
1090
166
{245000}D,E
{21200}D,E
1560E
ttfite^flMMOMKMRMUQtftek
I^IBIB
|||[BHj|lijiS|S
I^^WIWi^Wff^fl^I^»>»WW^
jj — u_aj LJ
15.5
{155}
55.5
49.0
159
93.7
50.7
NQ'
288
12.5
557
77,6
44.2
(126000}D.E
{4780JE
292
as 1 atm (760 mm Hg) and 20°C.
Note: Estimated Maximum Possible Concentration {EMPC} values listed in brackets.
D based on dilution.
E Exceeds calibration range.
NQ* d12-benzo(a)pyrene recovery in Sample Run 4 was too low to quantify the
compound. Maximum concentration of the compound is estimated by quantitation
of benzolelpyrene at 161 ng/dscm.
21
-------
Table 2-9. PAH Results - Stack Gas Concentrations (ng/dscm, adjusted to 7% 02)
iMH^^^^^^^^^^^^^^M^as
Acenaphthene
Acenaphthylene
Anthracene
Benzota)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrer»e
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
lndeno(1,2,3-cd)pyrene
Naphthalene
Phenanthrene
| Pyrene
iHBiiBBigljffffKfg
^BB8lw«WS?>T!*"5**(w*BK*''iw
214
{2280}D
{281}
182
1620
1490
455
147
4690 E
141
5290 E
2010
478
{605000JD.E
{44400}D,E
3540 E
HbSflfcHH
147
{2260}E
{92.8}
441
1160
636
236
60.0
{2350JE
86.0
{4110}
1920
292
{431000}D,E
{37300}D,E
2750 E
IfflRwHBaill
28.8
{288}
103
90.7
294
174
94.0
NO"
534
23.2
1030
144
81.9
{233000}D,E
{8850}E
542
* ng/dscm = nanogram per dry standard cubic meter, adjusted to 7% oxygen. Standard conditions, pressure
and temperature defined as 1 atm (760 mm Hg) and 20"C.
Note: Estimated Maximum Possible Concentration {EMPC} values listed in brackets.
D based on dilution.
E Exceeds calibration range.
NO* d,2-benzo(a)pyrene recovery in Sample Run 4 was too low to quantify the compound.
Maximum concentration of the compound is estimated by quantitation of benzo(e)pyrene at 96.1
ng/dscm.
22
-------
2.1.4 Continuous Emission Monitoring Data
Average daily results from continuous emission monitoring of carbon monoxide (CO)
total hydrocarbons (THC), carbon dioxide (CO2), and oxygen (O2) are provided in Table 2-10
Plots of individual CO and THC data are provided in Figures 2-1,2-2, and 2-3 for Runs 2, 3, anc
4, respectively. The CO data scale appears along the left side of the plot, with the THC data
points plotted hourly along the bottom and scaled on the right-hand side of each figure
Table 2-10. CEM Daily Results
CO', ppmdv
1380
1170
1130
1230
THCb, ppnv
70.6
54.2
37.5
54
C02*,
5.16
5.50
5.07
5.24
O/, % v
13.7
13.0
13.4
13.4
* CO, COj, and 02 analyzer data calibration corrected from 1-minute averages during the 360
minute sampling run.
b THC analyzer data calibration corrected from the arithmetic average of hourly reported values
from MSD during the sampling runs.
CO, CO2, and O2 emission concentrations appear to be relatively constant across the three
runs. The THC concentrations for Run 4 are much lower than the THC concentrations for Run
2 and 3.
23
-------
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8
-------
2.2 PROCESS SAMPLE MEASUREMENTS
Test results for scrubber water and sewage sludge feed which were collected during ik
MM5 sampling runs are presented in this section.
2.2.1 Scrubber Water Organic Results
2.2.1.1 Toxic PCB Comparison of Scrubber Water In Versus Scrubber Water Out
Table 2-11 presents the PCB comparison between the inlet and outlet scrubber water
samples for Runs 2, 3, and 4, respectively. In general, the PCB concentrations in the inlet
scrubber water samples are slightly lower than PCB concentrations in the outlet scrubber water
samples, although this result varies from run to run and from PCB congener to PCB congener
The PCB concentrations in the inlet scrubber water samples were generally consisted
throughout the three runs.
The PCB concentrations in the three outlet scrubber water samples are comparable. The
Run 3 sample was re-analyzed after a laboratory error using the archived sample.
2.2.1.2 D/F Results for Scrubber Water
D/F concentrations for scrubber water samples are presented in Table 2-12. The
comparison of D/F concentrations in inlet versus outlet scrubber water samples suggests thai
outlet concentrations are higher than inlet concentrations since most D/F congeners were no!
detected in the inlet water samples. However, the detection limit for the inlet scrubber water
samples in many cases is higher than the concentration found in the outlet scrubber water
samples, so an evaluation of inlet versus outlet concentrations is difficult to make. As shown,
most D/F concentrations in all three inlet scrubber water samples were below detection limits
The D/F concentrations in the outlet scrubber water samples were generally comparable across
the three runs in that D/F congeners found at higher levels in one run (compared to other D/T
congeners) were found at the same relatively higher levels in the other two runs as well.
25
-------
Table 2-11. Run 2, Run 3. and Run 4 Toxic PCB Results - Comparison of Inlet Versus Outlet Scrubber Water
O>
a.S'AA'-tetrachlorobiphenyl ,4,4<,5'-hexachlorobiphenyl (HxCB) (PCB-157)
0.166 *
2.3',4,4',5,51-hexachlorobiphenyl (HxCB) (PCB-167)
0.186
3,3',4,4',5,5'-hexachlorobiphenyl (HxCB) (PCB-169)
0.027
2,2',3,31,4,41,5-heptachlorobiphenyl (HpCB) (PCB-1701
0.105
2,2t3,4,4',5,5'-heptachlorobiphenyl (HpCB) (PCB-180)
0.338
2,3.3',4,4',5,5'-heptachlorobiphenyl (HpCB) (PCB-189)
0.029
4.18
0.946
0.166
3.63
0.138
0.157
1.68
0.491
0.068
1.87
0.155
0.504
0.045
0.086
0.135
1.06
0.032
3.52
0.065
1.06
0.018
0.249 #
0.119*
0.007
0.085 #
0.118
0.413 #
0.004
0.080 *
0.158
0.113
0.285 *
0.044
0.110*
0.164
0.020 *
0.036
0.264
0.686
0.030
0.006
0.080
0.081
0.414
(0.002)
0.078
0.190
0.009
1.00
0.024
0.177
{0.005}
2.52
0.854
0.124
1.62
0.050
0.098
0.236 #
0.083 #
0.125
0.098
0.298
0.653
0.044
* Re-analyzed result.
Note: # Values from second column confirmation.
(Below Detection Limit) values listed in parentheses.
Estimated Possible Concentration {EMPC} values listed in brackets.
-------
Table 2-12. D/F Results - Comparison of Inlet Versus Outlet Scrubber Water
2,3,7,8-TCDD
Total TCDO
1,2,3,7,8-PCDD
Total PCDD
1,2,3,4,7,8-HxCDD
1.2,3,6.7,8-HxCDD
1,2,3,7,8,9-HxCDD
Total HxCDD
1,2,3,4,6,7,8-HpCDD
Total HpCDD
Octa CDD
Total CDD
2,3.7,8-TCDF
Total TCDF
1.2,3,7,8-PCDF
2,3,4.7,8-PCDF
Total PCDF
1, 2,3,4,7, 8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1.2.3,7,8.9-HxCDF
Total HxCDF
1,2,3,4,6,7,8-HpCDF
1, 2,3,4, 7,8,9-HpCDF
Total HpCDF
Octa CDF
Total CDF
Total CDD + CDF
ND<0.013
ND<0.029
ND< 0.027
ND< 0.046
ND<0.013
ND<0.013
ND<0.013
ND< 0.029
ND<0.033
ND<0.099
0.040
0.040
SSPsSISHlllBi
ND< 0.009
0.092
ND<0.018
ND<0.011
ND< 0.035
ND<0.014
ND<0.013
ND<0.017
ND<0.014
ND< 0.053
NO < 0.009
ND< 0.035
ND
<0.079
ND<0.047
0.092
0.132
0.009*
0.475
ND< 0.005
0.046
0.002
0.003
(0.003)
{0.029}
{0.011}
0.027
0.030
0.578
0.181 *
0.824
0.014
0.029
0.316
0.012
0.005
{0.006}
ND<0.002
0.048
0.012
ND< 0.003
0.017
0.006
1.21
1.79
ND<0.003
(0.002)
ND< 0.007
ND<0.012
ND< 0.002
ND< 0.002
ND< 0.002
ND<0.005
ND< 0.004
ND<0.013
0.012
0.012
_ iitfittij-^iiMI JiUllMli
ISSaSifflsKli
ND< 0.002
(0.002)
ND< 0.004
ND<0.002
ND> 0.006
ND< 0.002
ND<0.002
ND<0.002
' ND<0.002
ND< 0.002
0.001
ND<0.005
(0.004)
ND<0.006
0.001
0.013
0.01 3 #
0.821
ND<0.013
0.057
ND< 0.004
ND<0.004
ND< 0.004
0.054
0.025
0.053
0.059
1.040
• • mrn M^HMiMh mil
nfin
rwKwwsSwwWB
0.222 *
1.120
0.025
0.045
0.493
0.016
0.007
0.013
ND<0.005
0.080
0.020
ND< 0.008
0.029
0.010
1.73
2.78
1 ND<0.008
[ ND<0.017
ND<0.023
ND<0.039
ND< 0.006
ND< 0.006
ND< 0.006
ND< 0.004
ND<0.012
ND<0.037
. 0.016
0.016
Jlllllffll1
ND<0.005
ND<0.015
ND<0.011
ND<0.005
ND<0.019
ND<0.006
ND< 0.0006
ND<0.007
ND<0.008
ND<0.025
ND< 0.003
ND<0.013
(0.0031
MD<0.016
0.000
0.016
0.014 tt
0.277
ND< 0.004
{0.066}
0.003
0.006
0.006
0.10?
0 032
0.07'i
0.047
0.500
0.256 »
0.866
0025
0.053
0495
o.o?-.
0 ni i
0.017
ND< 0.002
O.V13
0.025
ND<0.003
{0.035s
0.008
1.48
1.98
Note: (Below Detection Limrt) values lined in parentheses and Estimated Maximum Possible Concentration {EMPC} values
listed in brackets.
ND = Non Detect, value is detection limit.
» = value from second column confirmation.
Non Detects and (Below Detection Limit) values not included m totals.
27
-------
2.2.2 Sewage Sludge Organic Results
Sewage sludge samples were analyzed for PCBs and D/Fs. Sewage sludge feed was sampled
and analyzed for PCBs and D/Fs consistent with the scrubber water. Results for sewage sludge
feed are presented in Table 2-13 for PCBs and in Table 2-14 for D/Fs. In general, PCB and D/F
concentrations in the sludge feed are comparable across the three runs. However, an overall
higher (20 percent above the mean) sewage sludge D/F concentration was measured in Run 4.
2.2.3 Scrubber Water and Sewage Sludge Inorganic Results
Table 2-15 provides analytical results for inorganic parameters (chlorine, total percent
solids, temperature, and pH) in scrubber water samples. No significant differences are apparent
between inlet and outlet, or across the three runs, for these parameters in the scrubber water.
Table 2-15. Chlorine, Percent Solids, Temperature, and pH Results - Comparison of
Inlet Versus Outlet Scrubber Water
Chlorine (mg/L).
- Free
0.01
0-.03
0.05
0.05
0.03
0.01
- Total
ND<0.01
0.05
0.08
0.03
0.05
0.02
Total Percent Solids (%)
0.146
0.154
0.129
0.142
0.146
0.15B
Temperature (°F*)
87
116
87
120
87
123
PH'
7.37
6.49
7.48
6.57
7.43
6.51
• Temperature and pH were calculated as an average of six grab samples collected during each of
the 360 minute sampling runs.
Note: ND = Non Detect, value is detection limit.
28
-------
Table 2-1.3. Toxic PCB Results for Sewage Sludge
tHSHmlli^SSSSKKfHHfK
3,3',4,4'-tetrachlorobiphenyl (TCB)
(PCB-77J
2,3,3', 4,4'-pentachlorobiphenyl (PeCB)
(PCB-105)
2,3,4,4', 5-pentachlorobiphenyl (PeCB)
(PCB- 11 4)
2,3',4,41, 5-pentachlorobiphenyl (PeCB)
(PCB-1 1 8)
2',3,4,4', 5-pentachlorobiphenyl (PeCB)
(PCB-1 23)
3,3',4,4',5-pentachlorobipheny! (PeCB)
(PCB-1 26)
2,3,3',4,4',5-hexachlorobiphenyl (HxCB)
(PCB- 156)
2.3,3',4,4',51-hexachlorobiphenyl (HxCB)
(PCB- 157)
2,3',4,4l,5,5f-hexachlorobiphenyl (HxCB)
(PCB-1 67)
S.S'^^B.S'-hexachlorobiphenyl (HxCB)
(PCB-1 69)
2,21.3,3',4,4',5-heptachlorobiphenyl (HpCB)
(PCB-1 70)
2.2', 3,4,4', 5,5'-heptachlorobiphenyl (HpCB)
(PCB- 180)
a.S.S'^^'AS'-heptachlorobiphenyl (HpCB)
(PCB- 189)
BBBBfflBjajBBBBte8B!SSSB|BBSSBBj8BS^^
40.9 41.1 45.4
7.01 7.39 729
0.691 0.674 0,738
12.2 13.5 1? 9
0.231 0.276 0.24-
1.12 • 1.21 1.48
1.77# 1.88# 1.88*
0.472 # 0.565 # 0.536 #
0,878 0.968 0.959
0.453 0.601 0.655
2.53 2.57 7 7<
6.00 6.78 . 6.7' i
0.181 0.198 0.218
Note: # Values from second column confirmation.
29
-------
Table 2-14. D/F Results for Sewage Sludge
Ui^^35|^^^^fej^^^^H.^M^J*t^^fetifej^^g^^ij^j^.^gfc3| G§;j|tjES§lL*)
2,3,7,8-TCDD
I Total TCDD
1,2,3,7,8-PCDD
Total PCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
Total HxCDD
1,2,3,4,6,7,8-HpCDD
Total HpCDD
Octa CDD
Total CDD
2,3,7,8-TCDF
Total TCDF
1,2,3,7,8-PCDF
2,3,4,7,8-PCDF
Total PCDF
1,2,3,4,7.8-HxCDF
1,2,3,6,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
Total HxCDF
1,2,3,4,6.7.8-HpCDF
1 ,2,3,4,7,8,9-HpCDF
Total HpCDF
Octa CDF
Tout CDF
Total CDD + CDF
(0.003} tt
0.068
ND <0.015
0.030
ND<0.005
0.015
0.027
0.128
0.229
0.431
2.51
3.17
£'• -_-rtr'->--3-»fc • 'rfS-JSA'fe*
0.021 #
0.076
ND<0.008
0.008
0.030
0.014
ND<0.005
0.006
ND< 0.006
0.098
0.132
ND<0.012
0.239
0.313
0.756
3.92
(0.003) tt
0.083
ND <0.017
0.023
ND< 0.005
0.018
0.024
0.135
0.281
0.520
2.69
3.45
^iiSiililliSiail
0.024 It
0.096
ND< 0.008
0.009
0.095
0.019
0.006
0.008
ND< 0.007
0.117
0.159
ND<0.013
0.284
0.340
0.932
4.38
(0.005) #
0.095
ND<0.017
0.030
0.008
0.031
0.040
0.020
0.384
0.702
3.69
4.53
Mi^^^^Sl^Bl3^A"tTel®
iBBaMH
0.035 It
0.120
0.013
0.013
0.163
0.030
0.010
0.013
ND<0.007
0.171
0.222
ND<0.013
0.377
0.441
1.27
5 80
Note: (Below Detection Limit) values listed in parentheses.
ND «= Non Detect, value is detection limit.
9 = Value from second column confirmation.
Non Detects and (Below Detection Limit) values not included in totals.
30
-------
Chlorine and percent solids results for sewage sludge samples are presented in Table 2-16
Again, results across the three runs appear generally comparable. However, in two instances *J
free chlorine values exceed the reported total chlorine values. The explanation for this is
indeterminent.
Ultimate/proximate analysis was also performed on the sludge feed samples to determim
thermal properties. Results from the ultimate/proximate analysis are presented in Tables 2-1 ~
and 2-18. As shown, ultimate/proximate results are consistent for all three runs.
Table 2-16. Chlorine and Percent Solids Results for Sewage Sludge
Chlorine (mg/kg)
- Free
18.5
4.84
4.84
20.0
17 1
4.29
20.4
- Total
ND<0.5
Total Percent Solids (%)
23.5
Note: ND = Not detected, value is detection limit.
Table 2-17. Ultimate Analysis Results for Sewage Sludge
Hydrogen
Nitrogen
4.95
4.76
12.5
4.93
4.51
5.16
4.91
Oxygen
Carbon
Sulphur
Ash
15.1
37.0
1.33
37.1
13.5
39.3
1.35
35.7
31
-------
Table 2-18. Proximate Analysis Results for Sewage Sludge
^. fMimatc
te-'-^PIiuiea surement'' v>£;
..*
Moisture, %
76.2
13.9
Volatile Matter, %
Fixed Carbon, %
0.80
0.32
1630
Sulphur, %
BTU Content (BTU/lb)
3.0 DISCUSSION OF DATA QUALITY
3.1 QA OBJECTIVES -
The seven steps of the DQO process described in the QAPP are summarized and
reviewed below. The objectives of the data collection effort have not changed, thus the specified
DQOs are still applicable.
Step 1. State the Problem
The objective of the data collection effort was to characterize the concentration of D/Fs,
toxic PCBs, and PAHs in air emissions, sewage sludge, and scrubber water.
Step 2. identify the Decision
No specific decision was to be made based on these data. Rather, the results of this test
program provide preliminary information regarding levels of pollutants and associated health
risks. In combination with additional future data collection efforts, EPA may assess the need for
regulations on sewage sludge incinerator emissions. The results from Run 4 have been
evaluated, and this run has been determined to not be a statistical outlier.
32
-------
Step 3. Identify the Inputs to the Decision
Measurements of analytes were obtained from stack emissions, sewage sludge, and
scrubber water. See Table 1-1 in Section 1 for a concise description of all data collected Tiu
data collected are consistent with the objective specified in Step 1.
Step 4. Define the Boundaries of the Study
Budget constraints implied restrictions on the quantity of data to be collected, narnei >
three days of sampling from one incinerator under one test condition without duplicate samphm
trains. The DQA assessed if this design was adequate or if more resources were necessary in
future tests in order to meet the characterization objective.
Step 5. Develop a Decision Rule
The DQA sought to statistically answer the question "Was Run 4 an outlier?" by formal I
testing if the Run 4 air emissions measurements were statistically significantly different fron: :'•:
Run 2 and 3 air emissions measurements for the following compounds: toxic polychlonnatecl
biphenyls (PCBs), dioxins/furans (D/F), and polyaromatic hydrocarbons (PAHs). Note
that there is no one definition of an outlier. Various methods may be devised to test this question
under diverse definitions. Here, we will conclude that Run 4 was an outlier if the Run 4
concentration of the measured analytes was significantly different from the average of the Ri,r.
and 3 concentrations.
Step 6. Specify Tolerable Limits on Decision Errors
The determination of whether or not Run 4 was an outlier was formally tested using &.
analysis of variance (ANOVA) of the standardized stack air emission PCB, D/F and PAH data,
as well as of the CEM data.
The ANOVA model used for the PCB, D/F and PAH analyses was
33
-------
where z,j is the standardized measurement for the i* run and the j* compound, as is the mean for
the r* run, and e^ is the error term. The error terms are assumed to be independent across
compounds and normally distributed within each run.
As mentioned above, we concluded that Run 4 was an outlier provided the mean
concentration of the measured analytes was significantly different than the average of the Run 2
and 3 mean concentrations. That is, we tested the null hypothesis H0: (a2 + aJ/2 = a< versus the
alternative hypothesis H,: (a2 + a^/2 * a4. According to our definition of an outlier, these
hypotheses were equivalent to H# Run 4 was not an outlier and H,: Run 4 was an outlier.
Residuals from the model were used to visually inspect the normality assumption for the
errors.
3.2 DATA EVALUATION
3.2.1 Data Quality
Table 3-1, reproduced from the Emissions Test Report, illustrates the data quality, as
measured by precision, accuracy, and completeness. In almost all cases, the performance targets
were met. The DQA concluded that Run 4 mean concentrations of measured analytes were a
statistical outlier on the basis of an analysis of variance test.
3.2.2 Data Quantity
The quantity of data collected was determined by budgetary constraints. While the goal
of data collection was characterization of the mean concentrations, no limits on the acceptable
variability of these means were specified. Computation of the relative standard error (RSE) of
the mean, defined as RSD divided by the square root of the sample size, was carried out along
with a study examining the reduction in RSE with an increase hi the number of days of sampling.
Calculation of the RSE, and its reduction with an increase in the number of days of sampling,
was carried out under two possible scenarios:
34
-------
Table 3-1. Overall Program QA/QC Results
LiQCType/
-Parameter
Precision
Accuracy*1
Completeness
. Analyte
D/Fs
PAHs
Toxic PCBs
D/Fs
PAHs
Toxic PCBs
D/Fs
PAHs
Toxic PCBs
Program Targets**'
< 50% RSD
< 50% RSD
< 50% RSD
40%- 135%
50% - 1 50%
70% - 130%
100%
100%
100%
Achieved Result1"
<50% for all 2,3,7,8 isometers
but 2,3,7,8-TCDD and
1,2,3,7,8-PCDD
Not met on any analyte, range
62.30-144.86% RSD.
Corrected recoveries for Run 4
would put all <50% excep
perylene and benzo(a)pyrene
< 50% for all but PCB 169
126, -77
Met (79-134%) except for 3
analytes
All within range except as
specified on Quanterra's repor,
and surrogate spike in field
blanks.
84-128% except for PCB-1 14
100%
100%
100% j
For emission testing only.
-------
this mean with 20 percent precision. Based on Scenario 1, such precision would require nine
days of sampling. Perhaps nine days of sampling would be too costly and 25 percent precision
would be sufficient. Then only six days of samp ling would be required. The present level of
effort (three days of sampling) yields 34.3 percent precision.
3.3 SUMMARY OF TEST REPORT DATA ANALYSIS
In the following, the three test runs are referred to as Runs 2, 3, and 4. The main findings
of the DQA are:
There may have been a process "shift" starting around noon of the day of Run 3.
Prior to the shift, higher pollutant levels were observed in emissions and lower levels
in sewage sludge feed samples. After the shift, lower levels were observed in
emissions and higher levels in the sludge.
It is possible that no "shift" occurred, but that there were matrix interference problems
with the data collection during Run 4. This issue is also discussed in the Emissions
Test Report. Conclusive evidence has not been found to distinguish between a
change in the process and a problem with the sample data collection (low pre-field
surrogate standard recoveries caused by matrix interferences).
The data collected were of the appropriate type for characterization of the mean
pollutant concentrations: multiple direct measurements of the quantities of interest.
As shown in Table 3-1, the data are of adequate precision, accuracy, and
completeness, indicating that the quality of the data collected was adequate for
characterization of the mean pollutant levels. Note, however, that these estimates are
highly variable, being derived from only three sampling runs.
Additional discussion of the test report data is contained in the separate Data Quality Assessment
Report, developed as part of this work assignment.
36
-------
4.0 CONCLUSIONS
4.1 AIR EMISSIONS MEASUREMENTS
The organic PCB, D/F, and PAH results for Runs 2 and 3 are almost identical for most of
the analytes. The back half emission concentrations for Run 4 are 50 to 60 percent lower than
the back half emission concentrations for Runs 2 and 3 for all the analytes. As a result, emission
concentrations for Run 4 are approximately half of the emission concentrations for Runs 2 and 3
for all three analyte classes.
Analyte loss may have occurred during sampling, during sample handling and transport,
or prior to spiking the Run 4 sample with pre-extraction internal standards. This time period is
based on a comparison of the pre-field surrogate spike recoveries to the pre-extraction internal
standard recoveries. Recoveries of the pre-field surrogate spikes for Run 4 back half samples
were approximately half of the recoveries for Runs 2 and 3 back half samples for all PCB, D/F,
and PAH field surrogate spikes, whereas recoveries of the spiked pre-extraction PCB, D/F, and
PAH internal standards were comparable and generally acceptable across all three runs. Any
losses in the pre-field surrogate spikes that may have occurred in sample extraction or cleanup of
the Run 4 back half sample would have also been reflected in similar losses of the spiked pre-
extraction internal standards. Since the pre-extraction internal standard results are acceptable for
Run 4 and consistent with the other two runs, this result suggests that the field surrogate spike
and analyte losses likely occurred prior to extraction of the Run 4 emission samples.
Another indicator that analytes losses occurred prior to sample extraction is that the PCB,
D/F, and PAH concentrations in the samples follow the same pattern as the pre-field surrogate
spikes in that all measured back half analytes were approximately one half or less for the Run 4
sample. In addition, analyte concentrations for the Run 4 front half sample were somewhat
lower than the Runs 2 and 3 front half samples. This suggests that analyte levels may not have
been consistent during sampling rather than a loss of analyte from the collected sample.
After review of sampling and analysis records, a definite explanation for the lower Run 4
emission concentrations could not be determined. Possible causes of the lower Run 4
concentrations and/or lower pre-field surrogate spikes that were considered include the
following:
37
-------
• Pre-field Surrogate Spike Performed Improperly. This does not seem possible in thai
the PCB, D/F, and PAH spikes were done independently (three separate solutions) an
the same spiking error would have had to be made three times on the same XAD-2
resin. The laboratory logbooks do not reflect any problem with the pre-field surrogate
spiking of the XAD-2 resin.
• Analvtes Not Collected Consistently During Sampling. In Run 4, PCB, D/F, and PAE
compounds in the gas stream may not have been collected consistently by the MM 5
sampling train. This event would affect both the Run 4 front half and back half
samples and is substantiated by emission concentrations for the Run 4 front half
samples which are somewhat lower than emission concentrations for the Run 2 and ;
front half samples.
• XAD-2 Resin Lost After Sampling. During sample recovery, XAD-2 resin could hav>
been lost from the XAD-2 resin cartridge. Field logs do not indicate any problem witi-
the XAD-2 resin cartridge during Run 4 sample recovery so this is probably not the
case.
• Temperature of XAD-2 Not Maintained During Sampling. -The XAD-2 resin cartridge
must be maintained at 20 °C or lower temperature to avoid decomposition or
volatilization of organic compounds. If the MM5 sampling train or XAD-2 resin
portion thereof was exposed to ultraviolet light, high temperature, or other forms of
energy, this might account for the low levels. A check of the field data sheet showed
that the XAD-2 trap temperature was maintained below the required 20°C throughout
Run 4. A review of the field log does not indicate any problems in recovering the
MM5 sampling train at the completion of Run 4.
• XAD-2 Temperature Not Maintained During Sample Transportation. A reviev, of the
laboratory sample check-in record book shows that the Run 4 samples were received
within the allowable s4°C. The temperatures of the coolers storing the XAD-2 resii.
traps as received from the test team for transport to Columbus were also within this
limit.
• XAD-2 Temperature Not Maintained During Storage Prior to Extraction. All air
emission samples were stored in the same locked refrigerated storage unit in the
laboratory prior to extraction. The temperature control records for this period do not
indicate any elevated temperatures.
• ^missions Concentrations During Run 4 Were Actually Lower. Lower Run 4
concentrations may be an accurate reflection of a change in incinerator emissions on
the third day of sampling. This cause, however, does not explain why the field
surrogate spike recoveries were low.
• Run 4 XAD-2 Resin Lost Prior to Transfer to Soxhlet Extractor. This event would
result in a volume loss of analytes including the pre-field surrogate spikes. However,
laboratory record books do not collaborate such an event.
38
-------
Incorrect Sample Volume Used in Calculations. If an incorrect sample volume was
used to calculate emission concentrations in ug/dscm, Run 4 emission concentrations
could be affected. This would affect both front and back half results for Run 4. A
check of field data reduction does not indicate any calculation error.
Improper Spiking of Laboratory Internal or Recovery Standards. An incorrect amount
of internal or recovery standards could have been added to the Run 4 samples.
However, since native PCB concentrations are quantified against pre-extraction
internal standards and PCB pre-field surrogate spikes are quantified against the pre-
analysis recovery standard, this cause would require incorrect spiking on multiple
occasions which is unlikely.
Matrix Interference Resulting in Low Standard Recoveries. Incineration systems have
been known to produce matrix interferences from unknown causes. These could
explain the low pre-field surrogate spike recoveries and resultant emissions.
4.1.1 Toxic PCBs
Toxic PCB results for Runs 2 and 3 are almost identical for most of the analytes. The
back half emission concentrations for Run 4 are 50 to 60 percent lower than the back half
emission concentrations for Runs 2 and 3 for all the analytes. Possible loss of PCBs may have
occurred in the field as indicated by lower pre-field surrogate recoveries for Run 4. Internal
standard recoveries give an indication of how well analytes were extracted from the medium and
retained during extract cleanup. For the front half air samples, recoveries of all internal standards
were within the method specified limits of 30-150 percent and ranged from 35-77 percent.
Internal standard recoveries in the back half air samples were also within the 30-150 percent
limits and ranged from 49-84 percent. These internal standard recoveries indicate analytes were
well recovered during laboratory extraction and were retained during the extract cleanup process.
13C12-PCB-81 and 13C]2-PCB-111 were added as cleanup standards in processing the front half air
samples and as pre-sampling surrogate standards spiked into XAD resin before shipping to the
field in the back half air samples. Method-specified recovery ranges for these standards were
from 10-150 percent for !3C12-PCB-81 and 20-130 percent for I3C,2-PCB-111. Recovery of the
cleanup standards in the front half air samples were within the limits and ranged from 53-65
percent for I3C12-PCB-81 and from 41-57 percent for l3Cj2-PCB-l 11 indicating that analytes were
well retained through the extract cleanup procedures. Recoveries of the pre-sampling surrogates
39
-------
in the back half air samples were also within the limits and ranged from 21-61 percen t fa. C
PCB-81 and from 28-52 percent for 13C12-PCB-111. The pre-sampling surrogate recove. a-
indicate how well analytes are retained from field sampling through laboratory analysis WTii,
all the pre-sampling surrogate recoveries were within the target recovery range, the pre-sampling
surrogate recoveries in Run 4 (21 percent, 28 percent) were approximately half of the recoverie.'
for the surrogates in Runs 2 and 3 (51-61 percent). Since all internal standard recoveries fo.
Runs 2,3, and 4 were acceptable and similar between the three runs (indicating that laboratorv
extraction and cleanup were not a source of analyte loss), the low pre-sampling surrogate
recovery in Run 4 suggests loss of this standard during sampling, handling, and/or transport k
the laboratory prior to the sample extraction process. A discussion of what might ha\ e resuheo
in the lower Run 4 results is provided in Section 4.1 above. Since PCB concentrations are ncr
corrected for pre-sampling surrogate recoveries, the lower PCB emission concentrations in Run 4
may be attributed to these possible analyte losses. If the concentrations for Runs 2, 3 and 4 art
adjusted for the pre-sampling surrogate concentrations as shown hi Table 4-1, then the results
between the three runs agree well within the <50 percent RSD precision QA/QC requirement for
the analytes with actual RSDs ranging from 5-24 percent.
Table 4-1. Back Half Air PCB Data Corrected for Pre-sampling Surrogate Recovery
^••--s't,"-'^ - T-V'-^yftM^:^
»£.?. .a*!™ J,-ife. ,V.T.'RII»,9'iiiS*safiS«l
ANALYTES-
T ->• .T - .V««i yrsiM^-x*
--.', -r-'RUN72 4-^*1^W
PCB-77 .
PCB-123
171000
1256
117600
1172
114200
....930...
55800
134267
1119
..31.857.
169
15
PCB;118
PCB-114
60800
56400
57667
.2730
333
4120
3640
3480..
23600
3747
9
9
'b
9
1.2.
i;
PCfrl.26.
PCB-167
PCB:156.
PCB:1.57.
PCB-169
28200
.26200..
26000
7660
6420
4160
3640
6860
6080
.5660.
.3.500.
5380
•—
6580
.2307..
1010
3767
6107
..Z^P...
223
PCBJ80.
PCB:170.
PCB-189
2360
6040
..1932.
5140
2111
3680
4953
29000
11660
1016
.26000.
..1.0540.
818
22400
11520
1110
..25800.
1J240.
981
Jt91..
3305
_610.
149
£ = Estimated value since calibration range exceeded.
40
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4.1.2 D/Fs
The D/F results are summarized in Tables 2-5 through 2-7 in Section 2. A discussion of
the QA/QC results associated with these D/F data is summarized below. The initial calibration
met the requirement for response factors having less than 20 percent relative standard deviation
(RSD) for native analytes and less than 35 percent RSD for labeled analytes (actual range = <13
percent for native analytes and < 19 percent for labeled analytes). The continuing calibrations
met the requirement for response factors being within 20 percent of the initial calibration
response factors for native analytes and being within 30 percent of the initial calibration response
factors for labeled analytes for all D/F but for the native OCDF. Native OCDF response factors
in the middle and last of the three continuing calibrations which bracketed the emission sample
analyses were higher than the 20 percent criteria which is derived from Method 8290.
Internal standard recoveries give an indication of how well analytes were extracted from
the medium and retained during extract cleanup. For the front half air samples, recoveries of all
internal standards were within the method specified limits of 40-135 percent and ranged from
54-98 percent. Internal standard recoveries in the back half air samples were also within the
40-13 5 percent limits and ranged from 47-95 percent. These internal standard recoveries
indicate analytes were well recovered during laboratory extraction and were retained during the
extract cleanup process. Since all internal standard recoveries for Runs 2, 3, and 4 were
acceptable and similar between the three runs (indicating that laboratory extraction and cleanup
were not a source of analyte loss), the low pre-sampling surrogate recovery for D/F in Run 4
suggests loss of this standard during sampling, handling, and/or transport to the laboratory prior
to the sample extraction process.
4.1.3 PAHs
The PAH results are summarized in Tables 2-8 and 2-9 in Section 2.0. A discussion of
the QA/QC results associated with these PAH data appears in summary below. Acceptable
recoveries (64-124 percent) for the recovery standards were established in the FH and BH
samples. These data suggest that there were no significant sample matrix effects on the native
acenaphthene and pyrene in the resulting sample extracts for GC/MS analysis. However, the
41
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possible sample matrix effect on other relatively more reactive target PAH compounds canno; bi
discounted.
Quantitative recoveries (>70 percent) of all the internal standards except benzo[a]pyrerx
dl2 and perylene-d]2 were obtained in the FH samples. Recoveries of benzo[a]pyrene-d,2 and
perylene-d,2 ranged from 17 to 22 percent and from 18-32 percent, respectively. The low
recoveries of these two internal standards could be explained by either loss through the sampk
preparation process and/or through sample matrix effects. The internal standards
benzo[a]pyrene-d12 and perylene-d12 are relatively more reactive PAH compounds as compared to
other internal standards. Thus, it is assumed that the sample matrix effects could contribute
significantly to the loss experienced by these two internal standards. Surrogate standards were
not used in the FH samples, thus no recovery data were reported.
Acceptable recoveries (>50 percent) of 10 out of 14 internal standards were obtained in
the BH samples. The four internal standards with low recoveries in the BH samples were
acenaphthylene-dg, benz[a]anthracene-d,2, benzo[a3pyrene-d12, and perylene-d,2. These fou:
internal standards are relatively more reactive as compared to other remaining internal standards
As described above, the loss of the internal standards was possibly due to the combination of
sample preparation loss and sample matrix effects. Matrix effect variations between the FH and
BH samples could be explained by more internal standards being located in the BH samples with
lower than 50 percent recovery. For the same reason discussed before, the internal standard
benzo[k]fluoranthene-d12, was used for the quantification of benzo[e]pyrene level. Lov.
recoveries (13-24 percent) were obtained for the surrogate standard (field spike) in the BK
samples. The loss of the surrogate standards are believed to be from either field handling 01
sample matrix effects. Acceptable recovery standard results were obtained in the BH samples.
ranging from 64-87 percent. PAH Results for Runs 2 and 3 are somewhat similar for most of the
analytes.
4.1.4 Continuous Emission Monitoring
Average daily results from continuous emission monitoring of carbon monoxide (CO)
total hydrocarbons (THC), carbon dioxide (COj), and oxygen (O^ are provided in Table 2-10
Plots of individual CO and THC data are provided in Figures 2-1,2-2, and 2-3 for Runs 2, 3, and
42
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4, respectively. The CO data scale appears along the left side of the plot with the THC data
points plotted hourly along the bottom and scaled on the right-hand side of each figure. Run 2
THC levels were the highest encountered during the test program with Run 4 THC levels the
lowest, at roughly half the Run 2 concentration. These variations do not appear to reflect
significant process changes in incinerator operation according to the process data collected.
4.2 PROCESS SAMPLE ORGANIC MEASUREMENTS
Test results for scrubber water and sewage sludge feed which were collected during the MM5
sampling runs are presented in this section. Detailed PCB and D/F analytical data for these
matrices are provided in Section 2 and Appendix E and F, respectively of the Emissions Test
Report.
Scrubber water samples collected at the inlet and outlet of the scrubber were analyzed for
PCB and D/F.
4.2.1 Toxic PCB Comparison of Scrubber Water In Versus Scrubber Water Out
Table 2-11 presents the PCB comparison between the inlet and outlet scrubber water
samples for Run 2, 3, and 4 respectively. In general, the PCB concentrations in the inlet scrubber
water samples are slightly lower than PCB concentrations in the outlet scrubber water samples
although this result varies from run to run and from PCB congener to PCB congener. The PCB
concentrations in the three outlet scrubber water samples are comparable. The Run 3 outlet
sample was re-analyzed after a laboratory error using.the archived sample.
4.2.2 D/F Results for Scrubber Water
D/F concentrations for scrubber water samples are presented in Table 2-12. The
comparison of D/F concentrations in inlet versus outlet scrubber water samples in Table 2-12
suggests that outlet concentrations are higher than inlet concentrations since most D/F congeners
were not detected in the inlet water samples. However, the detection limit for the inlet scrubber
water samples in many cases is higher than the concentration found in the outlet scrubber water
43
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samples so an evaluation of inlet versus outlet concentrations is difficult to make. As showr,
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TECHNICAL REPORT DATA
(Please read Instructions on reverse before completing}
i REPORT NO EPA-454/R-00-038a
4 TITLE AND SUBTITLE
Source Characterization For Sewage
Executive Summary Report
Metropolitan Sewer District (MSD)
Cincinnati, Ohio
2
Sludge Incinerators
Mill Creek Wasterwater Treatment Plant
7. AUTHOR®)
Clyde E. Riley, USEPA Anthony S. Wisbith, Battelle
Jeffery A. Ferg, Battelle Dennis A. Falgout, PES
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle
505 King Avenue
Columbus, Ohio 43201-2693
12. SPONSORING AGENCY NAME AND ADDRESS
Emissions, Monitoring and Analysis Division
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 2771 1
3. RECIPIENTS ACCESSION NO
5. REPORT DATE
September 2000
6. PERFORMING ORGANIZATION CODE
1. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO 68-D-99-009
13. TYPE OF REPORT AND PERIOD COVERED
Final; January 99 to September 2000
14 SPONSORING AGENCY CODE
EPA/200/04
15 SUPPLEMENTARY NOTES
16 ABSTRACT
The Clean Air Act Amendments of 1990 require the U.S. Environmental Protection Agency's
(EPA) Office of Air Quality Planning and Standards (OAQPS) to establish standards of performance for sewage sludge
incineration. These standards are necessary to protect public health and the environment from any adverse effects of pollutant
emissions from sewage sludge incineration. The regulations will contain general regulatory requirements, pollutant
characterization, and emission limits. To assess control technologies as well as associated strategies for cost-effective standards,
EPA requires data on PCB, D/F, and PAH emissions from sewage sludge incinerators . While some emission data exist for sewage
sludge incinerators, data on coplanar polychlorinated biphenyls (PCBs) from sewage sludge incinerators are very limited.
The test report summarizes- testing of a multiple hearth incinerator at the Metropolitan Sewer
District (MSD) Mill Creek Wastewater Treatment Plant in Cincinnati, Ohio in July, 1 999. The emission data collected in this test
program will be used by EPA/OAQPS and EPA's Office of Water (OW) to support a decision about further data gathering efforts
in support of M ACT standards for sewage sludge incinerators. During the testing, a second EPA contractor monitored and
recorded the process and emission control system operating parameters, and prepared Section 4.0, Process Description And
Operation of the report. The report consist of five documents: Executive Summary Report; Volume I-Main Report; Volume II-
Appendices A-J; Volume Ill-Appendices K-P; and a Data Quality Assessment Report.
17.
KEY WORDS AND DOCUMENT ANALYSIS
(.DESCRIPTORS
PCBs
PAHs
Dioxins/furans
It DISTRIBUTION STATEMEhTT
Release Unlimited
. * ' '
b. IDENTIFIERS/OPEN ENDED TERMS
Air Pollution control
19. SECURITY CLASS (Xtpon)
Unclassified
20. SECURITY CLASS Iffgel
Unclassified
c. COSATI
Field/Group
21. NO. OF
PACES
22. PRICE
EPA Fecnt 222*-I OUr. 4-77)
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