United States
Environmental Protection
Agency
Office Of Air Quality
Planning And Standards
Research Triangle Park, NC 27711
EPA-454/R-00-038b
September 2000
Air
&EPA
Source Characterization For
Sewage Sludge Incinerators
Final Emissions Report
Volume I of III
Metropolitan Sewer District (MSB)
Mill Creek Wastewater Treatment Plant
Cincinnati, OhiOU.S. Environmental Protection Agency
J**ion 5. Library (P1.12J)
-------
EPA-454/R-00-038b
SOURCE CHARACTERIZATION FOR SEWAGE SLUDGE INCINERATORS
FINAL EMISSIONS REPORT, VOLUME I OF III
METROPOLITAN SEWER DISTRICT (MSD)
MILL CREEK WASTER WATER 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. £nv;ronmental Protection
x1*^ O -^ f\ cr i * L
7; -//ast j.C!,son r<0u)?varC|( j2th F»oor
Uiiwgo. it 60604-3590
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
-------
EPA DISCLAIMER
The information in this document has been funded wholly or in part by the Office of Air Quality
Planning and Standards, U.S. Environmental Protection Agency (EPA) under contract 68-D-99-
009 to Battelle. It has been subjected 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.
-------
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.
in
-------
TABLE OF CONTENTS
ACKNOWLEDGMENTS iii
1.0 INTRODUCTION 1-1
1.1 Summary of Test Program 1-1
1.2 Test Program Organization 1-3
1.3 Quality Assurance/Quality Control (QA/QC) Procedures 1-6
1.4 Description of Report Sections 1-6
2.0 SUMMARY AND DISCUSSION OF TEST RESULTS 2-1
2.1 Objectives and Test Matrix 2-1
2.2 Site-Specific Test Plan Changes and Sample Collection Problems 2-1
2.2.1 Air Emissions 2-2
2.2.2 Scrubber Water 2-4
2.2.3 Sewage Sludge 2-4
2.3 Air Organic Emissions Summary and Discussion 2-4
2.3.1 Toxic PCB Results 2-7
2.3.2 Dioxins, Furans (D/F) Results 2-12
2.3.3 PAH Results 2-16
2.4 Continuous Emissions Monitoring Summary and Discussion 2-19
2.5 Process Sample Measurements Summary and Discussion 2-21
2.5.1 Scrubber Water Organic Results 2-21
2.5.1.1 Toxic PCB Comparison of Scrubber Water In Versus
Scrubber Water Out 2-21
2.5.1.2 Toxic PCB Results for Scrubber Water In 2-21
2.5.1.3 Toxic PCB Results for Scrubber Water Out 2-24
2.5.1.4 Dioxin/Furan Results for Scrubber Water 2-24
2.5.2 Sewage Sludge Organic Results 2-24
2.5.3 Scrubber Water and Sewage Sludge Inorganic Results 2-31
3.0 SAMPLING LOCATION DESCRIPTIONS 3-1
3.1 Flue Gas Sampling Location 3-1
3.1.1 Sampling Point Determination - EPA Method 1 3-1
3.1.2 Volumetric Measurements - EPA Method 2 3-5
3.1.3 Molecular Weight Determination - EPA Method 3A 3-5
3.1.4 Flue Gas Moisture Content - EPA Method 4 3-5
3.2 Process Sampling Locations 3-6
3.2.1 Scrubber Water 3-6
3.2.1.1 Inlet Sampling Location 3-6
3.2.1.2 Outlet Sampling Location 3-6
3.2.2 Sludge Feed 3-7
IV
-------
TABLE OF CONTENTS
(Continued)
4.0 PROCESS DESCRIPTION AND OPERATION 4-1
4.1 Process Description 4-1
4.1.1 General 4-1
4.1.2 PreliminaryTreatment 4-1
4.1.3 Primary Treatment 4-1
4.1.4 Secondary Treatment 4-3
4.1.5 Tertiary Treatment 4-3
4.1.6 Sewage Sludge Thickening System 4-3
4.1.7 Sewage Sludge Digestion 4-4
4.1.8 Dewatering System 4-4
4.1.9 Incinerator Ash 4-5
4.2 Description of Incinerators 4-5
4.3 Description of Emissions Monitoring, Control and Emergency Equipment . . . 4-6
4.3.1 Emissions Control Equipment 4-6
4.3.2 Emissions Monitoring Equipment 4-6
4.3.3 Emergency Equipment 4-6
4.4 Process Operation Summary 4-7
5.0 SAMPLING AND ANALYTICAL PROCEDURES 5-1
5.1 Air Emissions 5-1
5.1.1 Air Emission Sampling 5-1
5.1.1.1 Modified Method 5 Sampling 5-1
5.1.1.2 Continuous Emission Monitoring for CO, O2, and CO2 5-9
5.1.1.3 Total Hydrocarbon Monitoring 5-13
5.1.2 Air Emission Sample Analysis 5-13
5.1.2.1 MM5 Sample Extraction 5-13
5.1.2.2 PCB Extract Cleanup and Analysis 5-16
5.1.2.3 D/F Extract Cleanup and Analysis 5-16
5.1.2.4 PAH Extract Cleanup and Analysis 5-20
5.2 Process Scrubber Water 5-21
5.2.1 Scrubber Water Sampling 5-21
5.2.2 Scrubber Water Analysis 5-23
5.2.2.1 PCB Analysis 5-23
5.2.2.2 D/F Analysis 5-25
5.2.2.3 Chlorine Analysis 5-27
5.2.2.4 pH/Temperature Determination 5-27
5.3 Process Sludge Feed 5-27
5.3.1 Sludge Feed Sampling 5-27
5.3.2 Sludge Feed Analysis 5-29
5.3.2.1 PCB Analysis 5-29
-------
TABLE OF CONTENTS
(Continued)
Page
5.3.2.2 D/F Analysis 5-31
5.3.2.3 Chlorine Analysis 5-33
5.3.2.4 Percent Solids Analysis 5-33
5.3.2.5 Ultimate/Proximate Analysis 5-34
6.0 INTERNAL QA/QC ACTIVITIES 6-1
6.1 QA/QC Checks and Issues 6-1
6.1.1 Field Sampling 6-1
6.1.1.1 MM5 Emission Sampling 6-3
6.1.1.2 Continuous Emission Monitoring 6-3
6.1.2 Sample Handling 6-5
6.1.3 Laboratory Analysis 6-8
6.1.3.1 Emission Samples 6-8
6.1.3.2 Sewage Scrubber Water Samples 6-48
6.1.3.3 Sewage Sludge Feed Samples 6-66
6.2 QA Performance Audits 6-75
6.2.1 Field Sampling Audits 6-75
6.2.1.1 Dry Gas Meter 6-75
6.2.1.2 Pitot Tube 6-75
6.2.1.3 Thermocouples 6-76
6.2.1.4 Analytical Balance 6-76
6.2.1.5 Total Hydrocarbon Analyzer 6-77
6.2.1.6 CEM Systems Audit 6-78
6.2.2 Laboratory Analysis Audit 6-78
6.3 QA/QC Performance Review 6-80
6.3.1 Program Performance Targets and Results 6-80
6.3.2 Method Specific Performance Targets and Results 6-81
6.3.2.1 Air Emissions 6-81
6.3.2.2 Scrubber Water Samples 6-85
6.3.2.3 Sludge Feed Samples 6-86
VI
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TABLE OF CONTENTS
(Continued)
LIST OF APPENDICES
Appendix A - Field Test Results
Appendix B - Raw Field Data
B-1 Stack Sampling Data
B-1-1 Methods 1 & 2 Preliminary Stack Traverse Data
B-1-2 MM-5 Sampling Raw Field Data
B-2 MM-5 Sample Recovery Field Data
B-3 Percent Isokinetic Field Calculation Form
B-4 Process Samples Field Data
Appendix C - Calibration Data for Field Equipment
C-1 Summary of Field Equipment Used During Field Program
C-2 Equipment Calibration Forms
C-2-1 Dry Gas Meter, Pitot Tube Calibrations
C-2-2 Post Test Meter Box Field Audit
C-2-3 Cylinder Gas Audits Summary Sheets
C-2-4 Cylinder Gas Audits
Appendix D - Sampling Logs and Chain-of-Custody Records
D-1 Daily Sampling Logs
D-1-1 ETS Field Sampling Log
D-2 Chain-of-Custody Records
D-3 Process Sampling Logs
D-4 Laboratory Record Book Sample Log In
D-5 Field Test Log
Appendix E - PCB Analytical Lab Raw Data Results
E-1 PCB Analytical Summaries
E-1-1 Air Samples
E-2 PCB Lab Raw Data Sheets
E-2-1 Air Samples
E-2-2 Sewage Sludge Fractions
E-2-3 Scrubber Water Inlet Fractions
E-2-4 Scrubber Water Outlet Fractions
E-3 PCB Blanks Lab Raw Data
E-3-1 Air Sampling Train
E-3-2 Sewage Sludge Blank Fractions
E-3-3 Scrubber Water Fractions
VII
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TABLE OF CONTENTS
(Continued)
Appendix F - Dioxin/Furan Analytical Lab Raw Data Results
F-1 D/F Results Summary
F-1-1 Air Sample Fractions
F-1 -2 D/F EPA Audit Sample
F-2 D/F Lab Raw Data Sheets
F-2-1 Air Emission Runs
F-2-2 EPA Audit Sample
F-2-3 Sewage Sludge
F-2-4 Scrubber Water Inlet
F-2-5 Scrubber Water Outlet
F-3 D/F Blank Lab Raw Data Sheets
F-3-1 Air Sampling Train & Proof Blanks, Lab Spikes, and Spike Dups
F-3-2 Sewage Sludge Blank Fractions
F-3-3 Scrubber Water Fractions
Appendix G - PAH Analytical Lab Raw Data Results
G-1 PAH Results Summary
G-2 PAH Blank Lab Summaries
G-3 PAH Lab Raw Data Sheets
G-4 PAH Blank Lab Raw Data Sheets
Appendix H - Chlorine Analytical Lab Raw Data Results
H-1 Chlorine Sewage Sludge Results
H-2 Chlorine Scrubber Water Inlet Results
H-3 Chlorine Scrubber Water Outlet Results
H-4 Chlorine Lab Sludge Blank Results
H-5 Chlorine Lab Water Blank Results
H-6 Chlorine Field Water Blank Results
H-7 Chlorine Lab Raw Data Sheets
Appendix I - Percent Solids Analytical Lab Raw Data Results
1-1 Total Percent Solids Results Summary
1-2 Lab Raw Data Sheets
Appendix J - Ultimate/Proximate Analytical Results
J-1 Analytical Summary
J-2 Lab Raw Data Sheets
Appendix K - Equations and Guidelines Used for Calculating Results
K-1 Stack Sampling Reference Methods 2-5 Example Calculations
K-2 Example Calculations for PCB Analysis
K-3 Relative Standard Deviation Calculation Worksheet
K-4 Gas Concentration Correction to 7% 02 Worksheet
viii
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TABLE OF CONTENTS
(Continued)
Appendix L - Continuous Emissions Monitoring (CEM) Data
L-1 CEM Test Data Summary
L-2 1-Min Data Printouts
L-3 CEM Response Time Determinations
L-4 C-4 CEM Calibration Records
L-5 CEM Calibration Gas Certifications
Appendix M - Process Field Data Sheets
M-1 Daily Process Data Summary Tables
M-2 Daily Process Data Sheets from MSD
Appendix N - Sampling and Analytical Protocols
N-1 PCB Protocols (Battelle)
N-1-1 Draft Air Emissions Method
N-1-2 Draft Sewage Sludge Method
N-1-3 Draft Scrubber Water Method
N-2 Battelle SOPs for D/F Analysis
N-3 PAH Protocols (Modified CARB Method 429)
N-4 Chlorine Protocol (Wastewater Method 4500 G, Modified ASTM D5233)
N-5 Percent Solids (Wastewater Method 2540 B)
N-6 Proximate/Ultimate Protocols (ASTM D3172, D4239, and others)
N-7 pH and Temperature (Wastewater Method 4500 H)
N-8 CO Protocol (40 CFR 60, Appendix A, Method 10A)
N-9 C02 and O2 Protocols (40 CFR 60, Appendix A, Method 3A)
N-10 Composite Sampling
Appendix O - List of Project Participants with Titles
0-1 MSD
0-2 USEPA
O-3 Battelle
0-4 ETS
O-5 Pacific Environmental
O-6 T&E Lab
0-7 Quanterra Lab
Appendix P - Post Test Summary
P-1 Post Test Summary Report
P-2 QAPP Amendment Records
P-3 SSTP Amendment Records
P-4 Corrective Action Reports
P-5 QA Officer Site Visit Checklist
IX
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LIST OF TABLES
Table 1-1. Test Matrix 1-2
Table 2-1. Toxic PCB Results - Stack Gas Concentrations (ng/dscm, as measured) . 2-8
Table 2-2. Toxic Results - Stack Gas Concentrations (ng/dscm, adjusted
To 7% 02) 2-9
Table 2-3. Toxic PCB Results - WHO Toxic Equivalent Stack Gas
Concentrations (ng/dscm, adjusted to 7% O2) 2-10
Table 2-4. World Health Organization Toxic Equivalent Factors (TEFs) for
Determining Coplanar PCB TEQs 2-11
Table 2-5. D/F Results - Stack Gas Concentrations (ng/dscm, as measured) 2-13
Table 2-6. D/F Results - Stack Gas Concentrations (ng/dscm, adjusted to
7% 02) 2-14
Table 2-7. D/F Results - TEQ Stack Gas Concentrations (ng/dscm, adjusted
to 7% O2) 2-15
Table 2-8. PAH Results - Stack Gas Concentrations (ng/dscm, as measured) .... 2-17
Table 2-9. PAH Results - Stack Gas Concentrations (ng/dscm, adjusted to
7% 02 2-18
Table 2-10. CEM Daily Results 2-19
Table 2-11. Run 2, Run 3, and Run 4 Toxic PCB Results - Comparison of
Inlet Versus Outlet Scrubber Water 2-22
Table 2-12. Toxic PCB Results - Inlet Scrubber Water 2-23
Table 2-13. Toxic PCB Results - Outlet Scrubber Water 2-25
Table 2-14. D/F Results - Comparison of Inlet Versus Outlet Scrubber Water 2-26
Table 2-15. D/F Results for Inlet Scrubber Water 2-27
Table 2-16. D/F Results for Outlet Scrubber Water 2-28
Table 2-17. Toxic PCB Results for Sewage Sludge 2-29
Table 2-18. D/F Results for Sewage Sludge 2-30
Table 2-19. Chlorine, Percent Solids, Temperature, and pH Results - Comparison
of Inlet Versus Outlet Scrubber Water 2-31
Table 2-20. Chlorine and Percent Solids Results for Sewage Sludge 2-32
Table 2-21. Ultimate Analysis Results for Sewage Sludge 2-32
Table 2-22. Proximate Analysis Results for Sewage Sludge 2-32
Table 4-1. Summary of Data from Mill Creek WWTP Control Room
Process Monitors 4-8
Table 5-1. Pre-Field Surrogate Standards 5-5
Table 5-2. Laboratory Internal Standards 5-17
Table 5-3. Standards for Laboratory Control Spike Samples 5-18
Table 5-4. Gas Chromatographic Operating Conditions for PAH Analysis 5-21
Table 6-1. Gas Stratification Check Results 6-2
Table 6-2. CEM Calibration and Linearity Check Data 6-4
Table 6-3. Response Time Check 6-4
Table 6-4. Bias and Instrument Drift Check Data 6-6
Table 6-5. Sample Transfer Schedule 6-5
-------
LIST OF TABLES
(Continued)
Page
Table 6-6. Summary of PCB Results and Standard Recoveries for Front Half
Air Samples 6-9
Table 6-7a. Summary of PCB Results and Standard Recoveries for Back Half
Air Samples 6-10
Table 6-7b. Back Half Air Data Corrected for Pre-sampling Surrogate Recovery . . . 6-12
Table 6-8a. Summary of PCB Results and Standard Recoveries for Front Half
Lab Control Spike and Spike Duplicate Samples 6-14
Table 6-8b. Summary of PCB Results and Standard Recoveries for Back Half
Lab Control Spike and Spike Duplicate Samples 6-15
Table 6-9. Summary of PCB Results and Standard Recoveries for
Background and Method Blank Samples 6-16
Table 6-10. Summary of PCB Results and Standard Recoveries for Field Blank
and Proof Blank Front Half Air Samples 6-17
Table 6-11. Summary of PCB Standard Recoveries for Field and Proof Blank
Back Half Air Samples 6-18
Table 6-12. Summary of Dioxin/Furan Results and Standard Recoveries for
Front Half Air Samples 6-20
Table 6-13. Summary of Dioxin/Furan Results and Standard Recoveries for
Back Half Air Samples 6-22
Table 6-14a. Summary of Dioxin/Furan Results and Standard Recoveries for
Front Half Lab Control Spike and Spike Duplicate Samples 6-25
Table 6-14b. Summary of Dioxin/Furan Results and Standard Recoveries for
Back Half Lab Control Spike and Spike Duplicate Samples 6-27
Table 6-15. Summary of Dioxin/Furan Results and Standard Recoveries for
Lab and Method Blank Samples 6-30
Table 6-16. Summary of Dioxin/Furan Results and Standard Recoveries for
Field Blank and Proof Blank Front Half Air Samples 6-32
Table 6-17. Summary of Dioxin/Furan Results and Standard Recoveries for
Field Blank and Proof Blank Back Half Air Samples 6-34
Table 6-18. Summary of PAH Results and Standard Recoveries for Front Half
Air Samples 6-37
Table 6-19. Summary of PAH Results and Standard Recoveries for Back Half
Air Samples 6-39
Table 6-20a. Summary of PAH Results and Standard Recoveries for Front Half
Lab Control Spike and Spike Duplicate Samples 6-42
Table 6-20b. Summary of PAH Results and Standard Recoveries for Back Half
Lab Control Spike and Spike Duplicate Samples 6-44
Table 6-21. Summary of PAH Results and Standard Recoveries for Lab and
Method Blank Samples 6-46
Table 6-22. Summary of PAH Results and Standard Recoveries for Field and
Proof Blank Front Half Air Samples 6-49
XI
-------
LIST OF TABLES
(Continued)
Table 6-23. Summary of PAH Standard Recoveries for Field and Proof Blank
Back Half Air Samples 6-51
Table 6-24. Summary of PCB Results and Standard Recoveries for Scrubber
Water Inlet Samples 6-54
Table 6-25. Summary of PCB Results and Standard Recoveries for Scrubber
Water Outlet Samples 6-55
Table 6-26. Summary of PCB Results and Standard Recoveries for Lab Control
Spike and Spike Duplicate Scrubber Water Samples 6-56
Table 6-27. Summary of PCB Results and Standard Recoveries for Lab Blank
Scrubber Water Samples 6-58
Table 6-28. Summary of Dioxin/Furan Results and Standard Recoveries for
Scrubber Water Inlet Samples 6-59
Table 6-29. Summary of Dioxin/Furan Results and Standard Recoveries for
Scrubber Water Outlet Samples 6-61
Table 6-30. Summary of Dioxin/Furan Results and Standard Recoveries for Lab
Control Spike, Spike Duplicate, and Lab Blank Scrubber Water Samples 6-64
Table 6-31. Intercomparison of Total Chlorine Analyses 6-66
Table 6-32. Summary of PCB Results and Standard Recoveries for Sewage
Sludge Samples 6-67
Table 6-33. Summary of PCB Standard Recoveries for Matrix Spike, Spike
Duplicate, and Lab Blank Sewage Sludge Samples 6-69
Table 6-34. Summary of Dioxin/Furan Results and Standard Recoveries for
Sewage Sludge Samples 6-71
Table 6-35. Summary of Dioxin/Furan Results and Standard Recoveries for Matrix
Spike, Spike Duplicate, and Background Sewage Sludge Samples .... 6-73
Table 6-36. QA Results for Dry Gas Meter 6-76
Table 6-37. Total Hydrocarbon Analyzer Audit Results 6-77
Table 6-38. Results of the CEM Audit 6-78
Table 6-39. Results of the Lab Dioxin/Furan Audit 6-79
Table 6-40. Overall Program QA/QC Results 6-80
Table 6-41. Data Quality Objectives for Precision, Accuracy, and Completeness
for Field Measurements 6-81
Table 6-42. Draft PCB Emission Method Performance Target Criteria and Results . . 6-82
Table 6-43. D/F Emission Analysis Performance Target Criteria and Results 6-83
Table 6-44. PAH Emission Performance Target Criteria and Results 6-84
Table 6-45. Draft PCB Scrubber Water Method Performance Criteria 6-85
Table 6-46. D/F Scrubber Water Analysis Performance Target Criteria and Results . 6-86
Table 6-47. Draft PCB Sewage Sludge Method Performance Criteria 6-87
Table 6-48. D/F Sewage Sludge Feed Analysis Performance Target Criteria and
Results 6-88
XII
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LIST OF FIGURES
Page
Figure 1-1. Program Organization 1-4
Figure 2-1. CO and THC Daily Test Results - Run 2 2-20
Figure 2-2. CO and THC Daily Test Results - Run 3 2-20
Figure 2-3. CO and THC Daily Test Results - Run 4 2-20
Figure 3-1. Plant Process Sampling Locations 3-2
Figure 3-2. Schematic of Sampling Location Exhaust Stack for Incinerator No. 6 ... 3-3
Figure 3-3. Sampling and Traverse Points for Incinerator Stack 3-4
Figure 4-1. Schematic Diagram of Mill Creek Wastewater Treatment
Plant Process 4-2
Figure 5-1. Sampling Train for EPA Modified Method 5 5-2
Figure 5-2. Flow Chart for Emission Sample Recovery 5-8
Figure 5-3. Continuous Sampling System for Instrumental Methods
(EPA Methods 3A and 10) 5-11
Figure 5-4. Flow Chart for Extraction of MM5 Sampling Train Front Half 5-14
Figure 5-5. Flow Chart for Extraction of MM5 Sampling Train Back Half 5-15
Figure 5-6. Flow Chart for Scrubber Water Sampling 5-22
Figure 5-7. Flow Diagram for Preparation and Extraction of Scrubber
Water Samples for PCB Analysis 5-24
Figure 5-8. Flow Diagram for Preparation and Extraction of Scrubber
Water Samples for D/F Analysis 5-26
Figure 5-9. Flow Chart for Sludge Feed Sampling 5-28
Figure 5-10. Flow Diagram for Sample Preparation and Extraction of Sludge
Feed Samples for PCB Analysis 5-30
Figure 5-11. Flow Diagram for Preparation and Extraction of Sludge Feed
Samples for D/F Analysis 5-32
XIII
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ERRATA
"SOURCE CHARACTERIZATION FOR SEWAGE SLUDGE INCINERATORS - FINAL
EMISSIONS REPORT - VOLUME I OF in - 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 multin1^ 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.
-------
1.0 INTRODUCTION
1.1 SUMMARY OF TEST PROGRAM
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 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.
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, 1999.
The emission data collected in this test program will be used by EPA/OAQPS and EPA's Office
of Water (OW) plans to use these data to support a decision about further data gathering efforts
in support of MACT standards for sewage sludge incinerators.
The Mill Creek Wastewater Treatment Plant is a municipal wastewater treatment plant
designed to process 120 to 180 million gallons per day (MGD) 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 110 dry tons of sludge per day. The incinerators operate 24 hours a day and
burn natural gas auxiliary fuel. The incinerators can burn digester gas but rarely do so.
Emissions from each incinerator are controlled by a venturi scrubber followed by a three-tray
impingement conditioning tower with a chevron style demister. The controlled emissions from
each incinerator then exit through its own individual stack.
1-1
-------
Table 1-1. Test Matrix
^Matrix '••£
Outlet Stack
Sludge Feed
Scrubber Water
*•*• Runs sis*
3b
3"
3b
Continuous
Continuous
Continuous
6 Grab
Samples
(1 per
hour)
Inlet and
Outlet
6 Grab
Samples
Each (1 per
hour)
Coplanar PCBs
D/Fs
PAHs
CO
02/C02
THC
Coplanar PCBs
D/F
Chlorine
Total % Solids
Ultimate/Proximate
Coplanar PCBs
D/F
Chlorine
Total % Solids
pH/Temp
M-0010a'b
-001 Ob
M-0010"
M 10'
M 3A9
M25A
Composite of
60 min grabs
Composite of
60 mm 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
60 min grabs
60 min grabs
Sampling
*BHofa>^
ETS
ETS
ETS
ETS
ETS
MSD
Battelle
Battelle
Battelle
Battelle
Battelle
Battelle
Battelle
Battelle
Battelle
Battelle
Sample Run
360
360
360
360
360
360
360
360
360
360
360
360
360
360
360
360
^MethwiV^
Draft PCB-
Emissions0
M-8290d
CARB 429e
NDIR
Chemical
Cell/ NDIR
Flame
lonization
Draft PCB
Sludge"
M-8290
M-4500 G'
M-2540 B'
ASTM
D3172,
D5373
Draft PCB
Water"
M-8290
M-4500 G
M-2540 B
M-4500-H1
^42^-*^ '' xSt1
,yj r4&,^- -S-, •• , ™5|<-
iJAnalytical
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 Polychlormated 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.
1-2
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The test program was conducted according to the "Site-Specific Test Plan (SSTP) -
Sewage Sludge Incinerator, Metropolitan Sewer District, Cincinnati, Ohio", dated July 16, 1999.
A matrix of the type and location of the samples collected is presented in Table 1-1. This test
program included collection and analysis of stack gas from Incinerator No. 6 for polychlorinated
biphenyl (PCB), polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (D/F),
and polycyclic aromatic hydrocarbons (PAH), carbon monoxide (CO), carbon dioxide (CO2),
oxygen (O2), and total hydrocarbon (THC).
Process samples consisting of sludge feed and scrubber water into and out of the venturi
control system were also collected. Battelle analyzed both sludge feed and scrubber water
samples for PCB, D/F, chlorine (C12), and percent solids. The field team measured the
temperature and pH of the scrubber water at the time of sample collection. Battelle arranged for
ultimate/proximate analysis of the sludge feed.
Emission Measurement Center (EMC) of OAQPS coordinated emission measurement
activities. Battelle and its subcontractor ETS, Inc. (ETS) performed the field sampling. Battelle
laboratories in Columbus, Ohio, conducted the sample analysis except those noted below. EPA's
Test and Evaluation Facility (T&E) on the MSD property did the chlorine and percent solids
analyses of sewage sludge and water samples. Quanterra Environmental Services (California
Lab) analyzed the PAH samples. Commercial Testing & Engineering Co. (CT&E) conducted
the ultimate/proximate analysis of sewage sludge samples. Pacific Environmental Services
(PES) collected process control data for the EPA under a separate contract.
1.2 TEST PROGRAM ORGANIZATION
Figure 1-1 presents the test program organization, major lines of communication, and
names of responsible individuals and their functional role.
Mr. Gene Grumpier was EPA's Program Manager (PM) for this test. Mr. Gene Riley was
EPA's Work Assignment Manager (WAM). Mr. Anthony Wisbith was Battelle's Work
Assignment Leader (WAL). He was assisted by Mr. Andrew Hetz of ETS, Inc. as the Field Test
Team Leader (FTTL). Ms. Karen Lesniak served as Battelle's Laboratory Coordinator, and Ms.
Susan Abbgy as Battelle's QA Officer. Ms. Abbgy was assisted by Ms. Pamela Broadwell of
ETS, Inc. in completing QA/QC activities. Mr. Michael Heitz of MSD served as the On-Site
1-3
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MSD
On-Site Coordinator
Michael Heitz
ESD
Program Manager
Gene Grumpier
PES
Process Engineer
Dennis Falgout
U.S. EPA T&E Laboratories
Operations Manager
Paul Kefauver
EMC
Work Assignment Manager
Gene Riley
Battelle
Work Assignment Leader
Anthony Wisbith
Battelle
Laboratory Coordinator
Karen Lesniak
ETS
Field Test Team Leader
Andrew Hetz
Battelle Extraction Laboratory
and HRGC/HRMS Laboratory
Laboratory Manager
Mary Schrock
Quanterra Environmental
Services
Laboratory Manager
Patrick Rainey
Figure 1-1. Program Organization
Battelle
Management
Greg Mack
Battelle
QA Officer
Susan Abbgy
ETS
Quality Assurance Coordinator
Pamela Broadwell
Coordinator. Mr. Dennis Falgout of PES collected process operating data during the test
program.
Addresses and phone numbers for responsible individuals are provided below.
1-4
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Susan Abbgy (left Battelle 8/20/99)
Battelle
Pamela Broadwell
ETS, Inc
1401 Municipal Road
Roanoke, Virginia 24012-1409
(540) 265-0004
(540)265-0131 (fax)
Gene Grumpier
Office of Air Quality Planning and Standards
(OAQPS)
U.S. Environmental Protection Agency
Emissions Standards Division (ESD)
Mail Drop 13
Research Triangle Park, NC 27711
(919)541-0881
crumpler.gene@epa.gov
Dennis Falgout
Pacific Environmental Services, Inc.
560 Herndon Parkway
Hemdon, VA 20170
(703)471-8383
(703) 481-8296 (fax)
Mike Heitz
Metropolitan Sewer District
1600 Gest Street
Cincinnati, Ohio 45204
(513)244-5137
(513) 244-5145 (fax)
Andrew A. Hetz
ETS, Inc
1401 Municipal Road
Roanoke, Virginia 24012-1409
(540) 265-0004
(540) 265-0131 (fax)
Paul Kefauver
U.S. EPA T&E Facility
1600 Gest Street
Cincinnati, Ohio 45204
(513)569-7057
(513) 569-7707 (fax)
Karen Lesniak
Battelle
505 King Avenue
Columbus, Ohio 43201
(614)424-4028
(614) 424-3638 (fax)
lesniakk@battelle.org
Patrick Rainey
Quanterra Environmental Services
880 Riverside Parkway
West Sacramento, California 95605
(916)374-4411
(916) 372-7768 (fax)
C. E. (Gene) Riley
Office of Air Quality Planning and
Standards (OAQPS)
U.S. Environmental Protection Agency
Emissions Measurement Center (EMC)
Mail Drop 19
Research Triangle Park, NC 27711
(919)541-5239
(919)541-1039 (fax)
rilev. gene@epa. gov
Mary Schrock
Battelle
505 King Avenue
Columbus, Ohio 43201
(614) 424-4976
(614) 424-3638 (fax)
schrock(S),battelle.org
Anthony S. Wisbith
Battelle
505 King Avenue
Columbus, Ohio 43201
(614)424-5481
(614) 424-3638 (fax)
wisbitha@battelle.org
1-5
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1.3 QUALITY ASSURANCE/QUALITY CONTROL (QA/QC) PROCEDURES
QA/QC procedures implemented for this test program are described in the "Quality
Assurance Project Plan (QAPP) - Sewage Sludge Incinerator, Metropolitan Sewer District,
Cincinnati, Ohio", dated July 16, 1999. This QAPP addresses project management,
measurement and data acquisition, assessment and oversight, and data validation. Section 6 of
this report summarizes QA/QC results for the test program. Revisions to the QAPP were
documented through the use of a Quality Assurance Project Plan Amendment Record Sheet, as
described in Section A9.0 of the QAPP. Copies of the QAPP Amendment Record Sheets
generated during this test program can be found in Appendix P to this report. A Post-Test
Summary Report discussing the amendments and any other deviations from the SSTP which
occurred in field sampling can also be found in this appendix.
1.4 DESCRIPTION OF REPORT SECTIONS
This test report consists of the following sections:
Section 1.0 provides an introduction to the test program. This section includes the
general purpose and background of the test program, a brief overview of the facility and process
tested, and the pollutants measured. A listing of the participants, an overview of QA/QC aspects
of the test program, and this report content description are also contained in Section 1.0.
Section 2.0 provides a summary of test results. This section includes the test matrix;
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.
A summary of field sampling procedural deviations from the SSTP and QAPP is also presented
in this section.
Section 3.0 contains a description of the sampling locations for stack emissions, scrubber
water, and sludge feed, a process diagram denoting the sampling locations, and a traverse point
cross section of the stack.
Section 4.0 describes the process and facility operation, including control equipment
specifications. Process operating data were furnished by PES directly to EPA.
1-6
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Section 5.0 presents a summary of the field sampling and laboratory analysis procedures
employed. These procedures include draft methods for PCB analysis of emissions, water, and
sludge; standard methods for D/F and PAH analyses; and standard EPA methods for continuous
emission monitoring (CEM) of combustion gases and stack parameters.
Section 6.0 summarizes results of internal QA/QC activities performed in the test
program. This section lists the program and method specific performance targets and actual
results achieved.
Appendices containing the raw field and laboratory data, including QA/QC results, are
compiled in separate volumes to this report.
1-7
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2.0 SUMMARY AND DISCUSSION OF TEST RESULTS
This section provides results of the test program conducted at the Cincinnati MSD on a
sewage sludge incinerator and related processes from July 19 to July 22,1999. Test results are
provided in separate sections for air organic emissions, continuous emissions monitoring, and
process sample measurements. Included in this section are a description of the test objectives
and a discussion of changes and problems encountered during the field sampling.
2.1 OBJECTIVES AND TEST MATRIX
The overall objective of this test program was to quantify the toxic PCB, D/F, and PAH
emissions from the stack of a sewage sludge incinerator. In addition, D/F and PCB
measurements were performed on the sewage sludge feed and scrubber water. Complete test
program parameters can be found in Table 1-1, Test Matrix. A field test log showing the dates of
the sampling activities is provided in Appendix D-5.
The PCB 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.
2.2 SITE-SPECIFIC TEST PLAN CHANGES AND SAMPLE COLLECTION PROBLEMS
Field sampling modifications made to the Site-Specific Test Plan (SSTP) are summarized
in the Post-Test Summary Report and in one SSTP Amendment. Copies of the Post-Test
Summary Report and the SSTP Amendment are provided in Appendix P.
2-1
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Specific sample collection procedures are described in Section 5.0 of this report and in
the SSTP. Outstanding problems encountered during the test program are noted below for each
medium sampled.
2.2.1 Air Emissions
A calibration gas audit (pretest and post test) was performed on the total hydrocarbon
(THC) analyzer operated by the MSD during the test program. The THC calibration span gas
(124.6 ppm) used for the audit was outside of the stated SSTP range (150 to 180 ppm).
Substitution of the calibration span gas (124.6 ppm) was approved by the WAM since the total
hydrocarbon analyzer was expected to operate on the low end of its calibration curve.
During the post-test calibration on July 22, 1999, moisture condensation was observed in
the flow panel serving the analyzer. The post-test CGA revealed a slower response time and
degraded accuracy. However, the accuracy was still within the allowed 15 percent.
Condensation within the system could slow the analyzer response time and absorb some of the
water-soluble organics in the span gas audit as well as the emissions being sampled.
The carbon monoxide (CO) analyzer was calibrated to a span of 6,000 ppm although
provision was made to determine linearity up to 10,000 ppm if CO spikes above 6,000 ppm were
encountered. No such exceedances of the specified calibration span were experienced during the
test program.
The initial Proof Blank #1 was collected with an undersized nozzle since initial
information on flowrate proved inaccurate. The nozzles were concurrently cleaned and similarly
sized during the Modified Method 5 (MM5) runs such that the WAM accepted the Proof Blank
#1 as being valid.
Concern was raised by the WAM on July 20,1999, that gas stratification may be
encountered in the exhaust stack. A stratification check was performed initially but the results
were inconclusive. The WAM made a decision to traverse the same MM5 traverse point
locations, using the CEM sampling probe simultaneous with each MM5 sampling run.
The initial MM5 sampling run on July 20, 1999, was invalidated for failing to meet post-
test leak checking criteria after the midport change. As a result of this deviation, four MM5
2-2
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sampling runs were performed such that three valid sampling runs (Runs 2, 3, and 4) and
associated samples were made available for laboratory analyses.
Testing was interrupted at 105 minutes into MM5 Run 2 to troubleshoot high vacuum as
indicated by the train vacuum gauge. The MM5 sampling train was leak-checked and the high
vacuum was found to have been caused by compaction of the silica gel in the fifth impinger.
The silica gel was loosened by shaking the fifth impinger and the train was again leak-checked.
Testing resumed after a 15-minute delay, resulting in the interruption of data from 16:46-17:00
on July 20,1999.
Throughout the MM5 sampling runs, isokinetic sampling was maintained using a "K
Factor" or the ratio of the orifice meter differential pressure necessary to maintain isokinetic
sampling to the differential pitot pressure. Known variables which are used to calculate the K
factor include the orifice differential pressure during calibration (AHJ, the barometric pressure,
and the nozzle diameter. Assumed variables include sampling meter temperature, and flue gas
temperature, static pressure, and moisture.
The K factor was initially calculated for MM5 Run 1 based on preliminary sampling
performed on July 19,1999, and information obtained from Cincinnati MSD. Adjustments were
made during each sampling run as actual data were obtained and compared to assumed values.
Although acceptable, the isokinetic sampling rate during MM5 Run 2 was lower than
expected (91.7 percent), because of an incorrect assumption of flue gas moisture. The K factor
was initially calculated for MM5 Run 2, based on an estimated moisture of 10 percent; a value
measured during previous emissions tests. This estimated value was significantly higher than
the actual flue gas moisture content of 4-5 percent measured during the actual sampling program.
Although preliminary moisture measurements taken on July 19, 1999, supported the lower
moisture values, these readings were thought to be anomalous at the time.
The data from the voided MM5 Run 1 also indicated 4.7 percent moisture. However, this
value was also assumed invalid, because of suspected inleakage dilution from a failed leak check
at the midpoint of the sampling run. It is now suspected that the leak originated during removal
of the train from the sampling port and had no bearing on sample or moisture collection.
Following recovery of MM5 Run 2, the flue gas moisture of 4-5 percent was confirmed
and the K factor was recalculated for MM5 Run 3 based on this measurement.
2-3
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2.2.2 Scrubber Water
Upon review of the venturi scrubber operation during on-site activities on July 19,1999,
Mr. Eugene Grumpier, the EPA Program Manager, requested that the scrubber outlet water be
characterized for comparison with the inlet water which was to be sampled according to the
SSTP. Scrubber water samples were collected every hour as grab samples and were analyzed in
the field for pH and temperature. Six grab samples for each location were composited into two
scrubber water samples for each MM5 emission sampling run. The composited samples were
submitted for analysis of toxic PCBs, D/Fs, chlorine, and total percent solids. The SSTP had
specified a water sample collection frequency of one grab every half-hour during each MM5
sampling run. A modification was approved by the WAM to increase the sampling interval
because a single sampling technician had been designated to collect the samples and time
constraints were of a concern, as well as the addition of the outlet water sample.
2.2.3 Sewage Sludge
On July 20,1999, the EPA Program Manager decided that additional analysis of the
sewage sludge feed would be useful to evaluate the thermal characteristics of the sewage sludge
during incinerator operation. Separate aliquots were generated from the composite sewage
sludge feed samples for each of the three runs and submitted for ultimate/proximate analysis.
The sewage sludge feed samples collected for proximate/ultimate analysis were handled and
processed identically to the other sewage sludge feed samples collected.
2.3 AIR ORGANIC EMISSIONS SUMMARY AND DISCUSSION
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. Detailed analytical and
field sampling results, including front and back half fractions for each MM5 sampling run are
presented in the appendices. The PCB, D/F, and PAH analytical results can be found in
Appendices E, F, and G, respectively.
2-4
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The toxic 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 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, 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 Run 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:
Pre-field Surrogate Spike Performed Improperly. This does not seem possible in that
the PCB, D/F, and PAH spikes were done independently (three separate solutions) and
the same spiking error would have had to be made three times on the same XAD-2
2-5
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resin. The laboratory logbooks do not reflect any problem with the pre-field surrogate
spiking of the XAD-2 resin.
Analytes Not Collected Consistently During Sampling. In Run 4, PCB, D/F, and
PAH compounds in the gas stream may not have been collected consistently by the
MM5 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 3
front half samples.
XAD-2 Resin Lost After Sampling. During sample recovery, XAD-2 resin could have
been lost from the XAD-2 resin cartridge. Field logs do not indicate any problem with
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 review of the
laboratory sample check-in record book shows that the Run 4 samples were received
within the allowable <4°C. The temperatures of the coolers storing the XAD-2 resin
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.
Emissions 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. The DQA report discussion indicated higher sewage sludge
levels of PCB and D/F compounds on Run 4 which might serve to explain the lower
air sample results. This, 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.
2-6
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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.
2.3.1 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 (use Section 6.1.3 for discussion).
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.
2-7
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Table 2-1. Toxic PCB Results - Stack Gas Concentrations (ng/dscm, as measured)
•;<§v."?? ^"aSiip^ :. ' -'••.';•-' <'-'' •.•••••,- *4fe£
t^"""'' ' -v* PCB Congener • ' "^tlA -V
3,3',4,4'-tetrachlorobiphenyl (TCB)
(PCB-77)b
2,3,3',4,4'-pentachlorobiphenyl (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'/4,4',5'-hexachlorobiphenyl (HxCB)
(PCB-157)
2,3',4,4',5,5'-hexachlorobiphenyl (HxCB)
(PCB-167)
S^'^^'^S'-hexachlorobiphenyl (HxCB)
(PCB-169)
2,2',3,3',4,4',5-heptachlorobiphenyl (HpCB)
(PCB-170)
2,2',3,4,4',5/51-heptachlorobiphenyl (HpCB)
(PCB-180)
2,3,3',4,4',5,5'-heptachlorobiphenyl (HpCB)
(PCB-189)
.Concentration (ng/dscm, as measured)8
^Ru'ri 2*31*
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
S" Run 4 ' :f
4.27
0.945
0.137
2.21
0.038
0.210
0.213
0.079
0.136
0.141
0.437
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 reported
concentrations within the calibration range (see Section 6.1.3.1).
2-8
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Table 2-2. Toxic PCB Results - Stack Gas Concentrations (ng/dscm, adjusted to
7% 02)
v;? PCB Congener
3,3',4,4'-tetrachlorobiphenyl (TCB)
(PCB-77)b
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- 11 8)
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',51-hexachlorobiphenyl (HxCB)
(PCB-157)
2,3I,4,4',5,5'-hexachlorobiphenyl (HxCB)
(PCB-167)
S.S'^^'^S'-hexachlorobiphenyl (HxCB)
(PCB-169)
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',4,4',5,5'-heptachlorobiphenyl (HpCB)
(PCB-189)
" .' v - •"'-' ••*V-"^"' ".^oncenfrfrtiori
fs (ng/dscm, adjusted to
Run 2
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
-:-' Run 3 ^'
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
t^V*. " ' ^'^^^^ft* " " ~ '•
4^' ^^k'ft^^f^7:"1!
7%|p2)';£'5l
36^ Run4"y"-'':
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
a ng/dscm; nanogram per dry standard cubic meter, adjusted to 7% oxygen.
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 reported
concentrations within the calibration range (see Section 6.1.3.11.
2-9
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Table 2-3. Toxic PCB Results - WHO Toxic Equivalent Stack Gas Concentrations
(ng/dscm, adjusted to 7% 02)
'- „• " '•' * ' ' \ ^>T< *^^f ^'^-'^ -- _^ '•' -= ,
', ', . V, . PCB CongenV^JIPv*:- ,
"-<-'..'.» 'I- •' . ' ' ' "" ", -;\;.*":,'S~!i>;i~fff •"-'•
3,3',4,4'-tetrachlorobiphenyl (TCB)
(PCB-77)(bl
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',4,4',5,5'-hexachlorobiphenyl (HxCB)
(PCB-167)
3,3',4,4',5,5'-hexachlorobiphenyl (HxCB)
(PCB-169)
2,2',3,3',4,4',5-heptachlorobiphenyl (HpCB)
(PCB-170)
2,2',3,4,4',5,5'-heptachlorobiphenyl (HpCB)
(PCB-180)
2,3/31,4,4',5/5'-heptachlorobiphenyl (HpCB)
(PCB-189)
, ", • ,t\!llibWHO' Toxic Equivalencies *4|f ;%|
? (ng/dscm, adjusted to 7%02)*v:
-f i " :
WHO^S
/'.TEFsff
1 .OE-04
1.0E-04
5. OE-04
1 .OE-04
1. OE-04
0.1
5. OE-04
5.0E-04
1 .OE-05
0.01
1 .OE-04
1 .OE-05
1. OE-04
*~'Run'; ,
?
-------
Table 2-4. World Health Organization Toxic Equivalent Factors (TEFs) for
Determining Toxic PCB TEQs
!"vt'l'L*jgrf
^feflli*^
•rir^Type , -..
Compound
Non-ortho
Mono-ortho
Di-ortho
> " ,,^',%
IUPAC8
No.
77
126
169
105
114
118
123
156
157
167
189
170
180
f \:i?? •* -.:• * ^ "£•'-.*' • ;';/Cpngeneri^,;4:43 ,i£, J?4*^Vv
;- %'-" - Structure /"'•„'--* ••/ -;" -*- -'
3,3',4,4'-tetrachlorobiphenyl (TCB)
2,3,3',4'5-pentachlorobiphenyl (PeCB)
S^'^^'^B'-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)
2,3,31,4,4',51-hexachlorobiphenyl (HxCB)
2,3,3',4,4I,5'-hexachlorobiphenyl (HxCB)
2,3',4,4',5,5'-hexachlorobiphenyl (HxCB)
2/3,3',4,41,5,51-heptachlorobiphenyl (HpCB)
2,2',3,3',4,4',5-heptachlorobiphenyl (HpCB)
2,2',3,4/4',5,51-heptachlorobiphenyl (HpCB)
isS;i^'*-.- ^isH'
-^"TEF-^;
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
a 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..
2-11
-------
2.3.2 Dioxin/Furan (D/F) Results
The dioxin/furan 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 6.1.3. 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.
2-12
-------
Table 2-5. D/F Results - Stack Gas Concentrations (ng/dscm, as measured)
T-- -A-- * .-• • "•" >•? •>' . :;— ,\ , ••,,-'-
; Congener t
Concentration (ng/dscm, as measured)8
, -.^O, ,;-j. , ;," ,,; .-•; „!.-: .-if^r- '-
Run 2 Run3 i ; Run 4
- -' Dioxins ""• _T' ,'T :' ' ' -^ '• ~t,'
2,3,7, 8-TCDD #
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 Based on given numbers:
0.098
3.02
0.017
0.706
0.015
0.038
0.039
0.606
0.204
0.459
0.317
5.11
': " Furans vi'V- -
-------
Table 2-6. D/F Results - Stack Gas Concentrations (ng/dscm, adjusted to 7% O2)
%£> "'•;„ r ^"""i-' i i ~^ '!'^i^rtnfi onoi* "*«^ ~x ^^C'is^t"^* -V' ^ * <~ ~ - •
a* A,* s; r.^', i, '-Isi. WfWliywIlvl " > :!^~&f!, -*',~ -f^^ *f v^'-'i O "•;
^^ffi^-^j^^ '''^..'- • -^~ ' , ''
2,3,7,8-TCDD
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
; Cpnceritratiqh||hg/dscjri|^djuisjtf jd
-•
•oxins> 0-;!5^'l;f''f-y'|t:v-p!^: ;
0.209
5.92
0.033
1.38
0.029
0.074
0.076
1.19
0.399
0.899
0.621
10.0
",." . -,» "-:•"- UV * :, ' Furans \xf>""\ -v
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
3.10
11.00
0.382
0.762
9.66
0.442
0.159
0.247
ND<0.0059
2.20
0.437
0.043
0.642
0.176
23.7
33.7
0.118
6.22
0.023
1.16
0.026
0.069
0.062
1.03
0.357
2.560
0.424
11.4
sT>, Vf ' ^ -"'
2.17
8.58
0.264
0.496
6.45
0.313
0.116
0.171
ND<0.0053
1.55
0.324
0.030
0.459
0.146
17.2
28.6
0.063
1.33
(0.009)
0.348
0.011
0.024
0.030
0.600
0.172
0.439
0.259
2.97
T *!S' :- "* ^v
0.988
4.76
0.124
0.228
2.85
0.169
0.065
0.095
ND<0.0056
0.760
0.189
0.017
0.252
0.078
8.71
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.
2-14
-------
Table 2-7. D/F Results - TEQ Stack Gas Concentrations (ng/dscm, adjusted to 7% O2)
Congener 'I? ^J
i???/ M> ff:^\m'v^¥
2,3,7,8-TCDD
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
2,3,7,8-TEQ Total CDD
-"•'''"• ' '"'"*!! ;fV , -o '-'H' -"'v~'' '
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
2,3,7,8-TEQ Total CDF
2,3,7,8-TEQ Total CDD + CDF
:. 'Equivalence;.;
:..* • ' Factor "';-:F;'':
•-, ^wf--.
' . . : ,, -Dipxins
1.000
0.500
0.100
0.100
0.100
0.010
0.001
S*y.^.:x;>graiii:
0.100
0.050
0.500
0.100
0 100
0 100
0.100
0.010
0.010
0.001
*|.J:'\<.J*|i?'!';
'"fRun 2 ;!
;^>!>;.:t
0.209
0.017
0.003
0.007
0.008
0.004
0.00062
0.249
* -, vK.*" --
0.310
0.019
0.381
0.044
0 016
0 025
ND<0.0006
0.004
0.000
0.000
0.799
1.05
adjusteftol?^
'- -.- Run'3' -:~' .
. ^• ;,,> ,-> v^-.
0.118
0.012
0.003
0.007
0.006
0.004
0.00053
0.151
0.218
0.013
0.248
0.031
0012
O O17
ND< 0.0005
0.003
0.000
0.000
0.542
0.693
1 '", ij
•'zf^i^'''""?*!;
Run 4
;;r " ';„ •' r-,,-:.
0.063
(0.005)
0.001
0.002
0.003
0.002
0.00026
0.071
K^V^?J'S!>'
0.099
0.006
0.114
0.017
0007
Om n
ND<0.0006
0.002
0.000
0.000
0.255
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
2-15
-------
2.3.3 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 6.1.3. 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 Sections 2.3 and 6.1.3).
2-16
-------
Table 2-8. PAH Results - Stack Gas Concentrations (ng/dscm, as measured)
Compound ''vlftisP': ^* *' ' '•• *
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
^Ip.qricjsritrati
IS™"RurK2vyii
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
tifijv is ; 'Jljfi,, • jia-iJl
in (ng/uscm, as measurea/
?? •?•%.&.*:& , *a£n V^ssg ,' -• <,>^llp^ ,. f^ ^*™ *,^'^1ig8^
'>«»"" Rim^a'^il^.'
..-^ rtufl -O i],^rvsi
83.6
{1290JE
{52.7}
251
662
361
134
34.1
{1340}E
48.9
{2340}
1090
166
{245000}D,E
{21200}D,E
1560 E
Run'54 '* s ' -'
15.5
{155}
55.5
49.0
159
93.7
50.7
NQ*
288
12.5
557
77.6
44.2
{126000}D,E
{4780}E
292
ng/dscm = nanogram per dry standard cubic meter. 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.
NQ* 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 161 ng/dscm.
2-17
-------
Table 2-9. PAH Results - Stack Gas Concentrations (ng/dscm, adjusted to 7% 02)
' ." ••?'::"*> -v'- '•':, ' ' ' Compound -*: :' ' . " >Vy' -"^If
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
Indenol 1 ,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
ff Cphcentratibn '{ng/dscm aljus^e^tcS^stlo^i'K
Ife^Run 2'6'*" ':':%
214
{2280JD
{281}
182
1620
1490
455
147
4690 E
141
5290 E
2010
478
{605000}D,E
{44400} D,E
3540 E
f • "\:Ru$3$'f'
147
{2260JE
{92.8}
441
1160
636
236
60.0
{2350}E
86.0
{4110}
1920
292
{431000}D,E
{37300}D,E
2750 E
5||ijV**?- ;*>:**'?>,- ;
•S^Run*-1 •
28.8
{288}
103
90.7
294
174
94.0
NQ*
534
23.2
1030
144
81.9
{233000}D,E
{8850JE
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.
NQ* 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.
2-18
-------
2.4 CONTINUOUS EMISSIONS MONITORING SUMMARY AND DISCUSSION
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, and
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.
Appendix A (Tables A-3 through A-6) of the CEM data includes daily maximum and minimum
values, arithmetic mean, and % standard deviation for each sampling period. The THC data
presented in Appendix A were provided by MSD. THC, CO, and O2 arithmetic means are
calculated from data points collected during each sampling run as indicated from clock time.
Detailed CEM data and calibration information are presented separately in Appendix L.
Table 2-10. CEM Daily Results
CEM
C0a, ppmdv
THCb, ppmdv
CO/, % v
02a, % v
Daily Test Run Averages if il ^
Run 2
1380
70.6
5.16
13.7
Run 3
1170
54.2
5.50
13.0
::" -"Run 4;^ r/
1130
37.5
5.07
13.4
Average
1230
54.1
5.24
13.4
a CO, C02, 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 02 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 Runs
2 and 3.
2-19
-------
3!
(0
CO Concentration ( pprndv )
NJ
N>
O
^ o o o o
' —^
CO g
8
O
o s
9J 8
3
Q.
_i f?
3 8
o
1 1?
CD -^
" 2
^n o
n\ ^
U
C ro
r* <6
w o
1
5
^
^
<
i
-**
s
j
I
r
*•>
^
•>
^
•^
>
c1 THC Concentration ( ppmdv
3
* 2 8
(O
c
CO Concentration (ppmdv)
A
V 0
1° s
0
0 °
o -
D) §
3 °
a.
H g
I 8
O H o
0 3 b
D> CD o
^" pj s
(/) ^^
~ 8
w _
£. ?
(0 0
1
o
00
o
0
.
/
(
t
N)
O
f
~
f
s
f
'
\
^
•—.-
?
CD
O
<
l_
r
^m
O
o
(Q
c
to
N)
CO Concentration ( ppmdv )
^ 8
8
O
0 1
o, §
3
°- a
° H 8
^j 3 s
"^ 0§
7
f
^
1
^
3
CO
THC Concentration (ppmdv)
o
o
o
C
3
N>
THC Concentration ( ppmdv )
S 8
4-
to
o
-------
2.5 PROCESS SAMPLE MEASUREMENTS SUMMARY AND DISCUSSION
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 Appendix E and F, respectively. Appendices H, I, and J include
detailed data and information for chlorine, ultimate/proximate, and percent solids analysis,
respectively.
2.5.1 Scrubber Water Organic Results
Scrubber water samples were analyzed for PCB and D/F.
2.5.1.1 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 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.
2.5.1.2 Toxic PCB Results For Scrubber Water In
Table 2-12 compares the inlet scrubber water results for all three runs. The PCB
concentrations in the inlet scrubber water samples were generally consistent throughout the three
runs.
2-21
-------
Table 2-11. Run 2, Run 3, and Run 4 Toxic PCB Results - Comparison of Inlet Versus Outlet Scrubber Water
•^•;'^vv. .'"-rf'^^i^^4--. -. •"*''*'-
fviffii .•-''''. 'S'WPCB, Congener ~;^H'lA3&4- ',-
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',4,4',5,5'-hexachlorobiphenyl (HxCB) (PCB-167)
3,3',4,4',5,5'-hexachlorobiphenyl (HxCB) (PCB-169)
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',4,4',5,5'-heptachlorobiphenyl (HpCB) (PCB-189)
S^r'^;/^^^^ Concentration (ng/L, as measured) ;• , ,. ;: • •
-" l\ '..} ~ " ' 1 '•'•',',,'',' '">!'' • . '<< , -." 1 '• )%* , < , if X' • ( , * Y''''" "' ' '''
Run 2
SwJuly;20,.1999^J • ^i' 4 \ *" v
' ;» w < it.* t^f -it ?••»•?* , ,~z~
^i> l~A"4'^> (> V" -#-c/-i:-
^.:in« 'AM&Oufsa
0.138 2.52
0.504 0.854
0.045 0.124
1.06 1.62
0.018 0.050
0.004 0.098
0.080 # 0.236 #
0.020 # 0.083 #
0.036 0.125
(0.002) 0.098
0.078 0.298
0.177 0.653
{0.005} 0.044
Ni
W
a Re-analyzed result - see Section 6.1.3.2 discussion.
Note: # Values from second column confirmation.
-------
Table 2-12. Toxic PCB Results - Inlet Scrubber Water
: ' ~ * 4l£^ * " u' -i^i'~~5^ ' "; - IJN^ l ^-,-^f ' " - -x -^ \
•-^>MA>Pcicbrlener*': V^jpir*
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- 11 4)
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',4,4',5,5r-hexachlorobiphenyl (HxCB)
(PCB-167)
S^'^^^S.B'-hexachlorobiphenyl (HxCB)
(PCB-169)
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',4,4',5,5'-heptachlorobiphenyl (HpCB)
(PCB-189)
--"-ft Concentration (ng/L, as measured) x , ;
^ -£^ , - ,•• ^ * - >**r Si,, - ,-=^. ^ < &,. , s-- --..= x
a»Ruh'2W
0.158
0.690
0.233
1.20
0.177
0.024
0.243 #
0.166 #
0.186
0.027
0.105
0.338
0.029
0.166
0.491
0.068
1.06
0.032
0.007
0.085 #
0.285 #
0.044
0.006
0.080
0.190
0.009
4a^l
0.138
0.504
0.045
1.06
0.018
0.004
0.080 #
0.020 #
0.036
0.002
0.078
0.177
{0.005}
Re-analyzed result - see Section 6.1.3.2 discussion.
Note: {EMPC} values listed in brackets.
# Values from second column confirmation.
2-23
-------
2.5.1.3 Toxic PCB Results For Scrubber Water Out
Table 2-13 compares the outlet scrubber water results for all 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. This is discussed further in
Section 6.1.3.2.
2.5.1.4 Dioxin/Furan Results for Scrubber Water
D/F concentrations for scrubber water samples are presented in Tables 2-14 through 2-16.
The comparison of D/F concentrations in inlet versus outlet scrubber water samples in Table 2-
14 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 samples so an evaluation of inlet versus outlet concentrations is difficult to make.
As shown again in Table 2-15, most D/F concentrations in all three inlet scrubber water samples
were below detection limits. The D/F concentrations in outlet scrubber water samples as shown
in Table 2-16 were generally comparable across the three runs in that D/F congeners found at
higher levels in one run (compared to other D/F congeners) would be found at relatively higher
levels in the other two runs as well.
2.5.2 Sewage Sludge Organic Results
Sewage sludge samples were analyzed for PCB and D/F. 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 2-17 for PCBs and in Table 2-18 for D/Fs. In general, PCB
and D/F concentrations in the sludge feed are comparable across the three runs. However, the
overall higher (20% above the mean) sewage sludge D/F concentrations in Run 4 may hint at a
process variation which may have resulted in higher organic contaminant levels in the sludge
which did not result in higher PCB, D/F, and PAH emission concentrations in Run 4.
2-24
-------
Table 2-13. Toxic PCB Results - Outlet Scrubber Water
•".-;""';.'. ,-./:-#v.- '"-i^:- JSP" ' '.:vf;':" ' •„- ^\*'-%^
-" '\.?. '-»• •» Aff^ • ..-;<•" ,;«*•'' -i*. vv' •,:.,-"•: |ftt-"r :"-"-
•£*s*™Jb^f-!|F&^% *> * -•'{-!: " Hv 5ii>^™' ' ';•'<*" *: '-"-'',- %*',4t'5;£f~ . ""7 ' ' <' ,•'
.^^sT-;--.:>^ pel Corfenerf*^ ^ ^ =^;^^
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',4,4',5,5'-hexachlorobiphenyl (HxCB)
(PCB-167)
S^'^^'^^'-hexachlorobiphenyl (HxCB)
(PCB-169)
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',4,4',5,5'-heptachlorobiphenyl (HpCB)
(PCB-189)
' ' ' ^••Con'centration ^ng/lJf.as measiired}.j{;s|
""' IRuTI'Z' ,?r
4.18
0.946
0.157
1.68
0.086
0.135
0.249 #
0.119 #
0.158
0.113
0.264
0.686
0.030
" l-?Run &* f
3.63
1.87
0.155
3.52
0.065
0.118
0.413 #
0.110 #
0.164
0.081
0.414
1.00
0.024
'Vk^Rulnx4" ' *
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
a Re-analyzed result - see Section 6.1.3.2 discussion.
Note: # Values from second column confirmation.
2-25
-------
Table 2-14. D/F Results - Comparison of Inlet Versus Outlet Scrubber Water
;--;..-:,j Congener Cliy-
,-, rj-.'Sf ^4* - ,". •-,"- • •-._.'« ^5 «>*;#•%'!." -r^
, - ; , %. '. • :,: jlScrubber, Water, . Cpncjii^a|wn^ngjl>^3^*||^l(^|ij^g||^
! \ ^'tjv1!! •* '^.^fri&'^'^^S'?
'^?;|^flun^»!*4^
, - in: :;s. '"," ' • ' " ..' Furans "^S|^.»-;/Cs-. ,.4-. -i-*, % v%, •%. m,1;*-,?*1 '•
-' *~'*.~-v ' ! '^ !* "> ,->*>_, ^ ' . . , •-• -> ^l^sl^;1. -* ; < i^V <<">"' f% ' '^ W' ' •' ^ils ' '^ IVrJ- ' ^^'^^^.^'^
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<0.009 0.181 #
0.092 0.824
ND<0.018 0.014
ND<0.011 0.029
ND<0.035 0.316
ND<0.014 0.012
ND<0.013 0.005
ND<0.017 {0.006}
ND<0.014 ND<0.002
ND<0.053 0.048
ND<0.009 0.012
ND<0.035 ND<0.003
ND 0.017
<0.079
ND<0.047 0.006
0.092 1.21
0.132 1.79
ND<0.002 0.222 it
(0.002) 1.120
ND<0.004 0.025
ND<0.002 0.045
ND>0.006 0.493
ND<0.002 0.016
ND<0.002 0.007
ND<0.002 0.013
ND<0.002 ND<0.005
ND<0.002 0.080
0.001 0.020
ND<0.005 ND<0.008
(0.004) 0.029
ND<0.006 0.010
0.001 1.73
0.013 2.78
ND<0.005 0.256*
ND<0.015 0.866
ND<0.011 0.025
ND<0.005 0.053
ND<0.019 0.495
ND<0.006 0.025
ND<0.0006 0.011
ND<0.007 0.017
ND<0.008 ND<0.002
ND<0.025 0.113
ND<0.003 0.025
ND<0.013 ND<0.003
(0.003) {0.035}
ND<0.016 0.008
0.000 1 .48
0.016 1.98
Note: (Below Detection Limit) values listed in parentheses and {EMPC} values listed in brackets.
ND = Non Detect, value is detection limit.
it = value from second column confirmation.
Non Detects and (Below Detection Limit) values not included in totals.
2-26
-------
Table 2-15. D/F Results for Inlet Scrubber Water
»*%"ff*ft?WV":,' >"'•••??" ., jiiir \-*.vf&- >• '^^U^^1
J^fiSf^'' '-''Congener
^ V"*-^ - t ,^'4^! , , •>,-;iB|^f^" ,* - 'fett "i^^- ^V^r^g^p^.' *||I^V^ (%^ "V^'-i^^ '' S^
^yl^f.Coricentration (ng/J.f agmeasuredr^r-'?; •<
itfrtV-- • .<':, ^if^i •
•*-'^" Riur2"v •-
> «S*S->;"- ,J • ..•:,;—, .--'^ , •_..'- ,''•*'.• -«.-
" ^ .•••• _.-• - --:• - _>< "• Dioxins ^
2,3,7,8-TCDD
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
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
•;**".-::> ';%.-•• • • ",-.•.-• ' >.-;~r* -- _ IT- - , :,,
•/."•?" >¥- - >"' -A-' -:>^ - Furans/ ,;^
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<0.009
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
ND<0.009
ND<0.035
ND <0.079
ND< 0.047
0.092
0.132
IP
• ?T"/,4-' J'r-^ •;K;'.it^* ;' '
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
\.^:< f'-ru|
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
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
t*v - , - . - j
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
(0.003)
ND<0.016
0.000
0.016
Note: (Below Detection Limit) values listed in parentheses.
ND = Non Detect.
Non Detects and (Below Detection Limits) values not included in totals.
2-27
-------
Table 2-16. D/F Results for Outlet Scrubber Water
..,»..;. -1-
?'v '•"•':•/ "•' " "bongener^:t\:
!*'«K!(^s?J!^,^sai^ , > ^ ^ ^/ V' A=c« ^ sM ** ~~^- *-'~^ *^i iH ^C^V4 ^ ^^^^''^^W^t^^li
^SuBfi^f^lSSti^HiSw;-''
aS*sjj5»s,o'jf5*W'l5#;ff ,••
i*^~J*r rJHUn ~,&S. il*.? •?"•
-iSC - " •" •'"' ~"-; --- "'"'". ' Dioxins ' ^•>*"t~
2,3,7,8-TCDD
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
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
^'^ ' . v-% ' "' '- >i: eii ^f c> ' ^ -~ -.'^ ^S
0.013 #
0.821
ND<0.013
0.057
ND<0.004
ND<0.004
ND<0.004
0.054
0.025
0.053
0.059
1.04
Ife'Oi!" ''-"-. J; .•* i!
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
i^^4Xr ^ ^^^^
Hl»i Run
' """"S"-1 \,,JaJj^',' *•***(
0.014*
0.277
ND< 0.004
{0.066}
0.003
0.006
0.006
0.102
0.032
0.074
0.047
0.500
ta, -f^|" B ,- "^C V ,.
t?1 "f^sw -^i^'v^ispi1-: >.,
0.256 tt
0.866
0.025
0.053
0.495
0.025
0.011
0.017
ND<0.002
0.113
0.025
ND<0.003
{0.035}
0.008
1.48
1.98
Note: {EMPC} values listed in brackets.
ND = Non Detect, value is detection limit
n = value from second column confirmation.
Non Detects and {EMPC} values not included in totals.
2-28
-------
Table 2-17. Toxic PCB Results for Sewage Sludge
y^f*rfj:^:l#";:;i' f ' \,3#Sf
, •' ... .-,- 't;v~; "PCB Congener -" " <4Kx*
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',5I-hexachlorobiphenyl (HxCB)
(PCB-157)
2,3',4,4',5,5I-hexachlorobiphenyl (HxCB)
(PCB-167)
3,3',4,4',5,5'-hexachlorobiphenyl (HxCB)
(PCB-169)
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',4,4',5,51-heptachlorobiphenyl (HpCB)
(PCB-189)
^ , Rurf 2 /^
40.9
7.01
0.691
12.2
0.231
1.12
1.77 #
0.472 #
0.878
0.453
2.53
6.00
0.181
l^ftngl
41.1
7.39
0.674
13.5
0.276
1.21
1.88 #
0.565 #
0.968
0.601
2.57
6.78
0.198
; ,'F
45.4
7.29
0.738
12.9
0.241
1.48
1.88 #
0.536 #
0.959
0.656
2.78
6.71
0.218
Note: # Values from second column confirmation.
2-29
-------
Table 2-18. D/F Results for Sewage Sludge
• • v-^'^V^V, '
'•??•« !;'"?'"• "'•' '• Congener fe,;4i" \.^^^ •''
.:.'&'^--\ ' '•' ~.:-,--J-'\-"'
2,3,7, 8-TCDD
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
\ i't" ''-~£- " • ", ' • ••• ;..C'-V^ ' •
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
^l^>':-Con
"'i/'s.fjj * r InUv l^M*^9^,'^*^' 1^
Dioxins I
(0.003) #
0.068
ND <0.015
0.030
ND<0.005
0.015
0.027
0.128
0.229
0.431
2.51
3.17
. -Furans ?",•'; i;.vj.
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
c^entrat!o'rt|.(riil/g;J|
Ui''l%
. •-•?*•. Run 3"p:>i? •:
- ' '; - 'V , 'V'' r'^,'
(0.003) #
0.083
ND <0.017
0.023
ND<0.005
0.018
0.024
0.135
0.281
0.520
2.69
3.45
X- " X'.Swf
0.024 #
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
*i'^fe. • ^l^ftrfiri * ^^*^ili!r*'^ '??
dr^J i^^^l^^f
',-'"• 5;"'« '"i^'.'-i^^i
(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
•X''5>-Xir,'
0.035 ff
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.
ff = Value from second column confirmation.
Non Detects and (Below Detection Limit) values not included in totals.
2-30
-------
2.5.3 Scrubber Water and Sewage Sludge Inorganic Results
Table 2-19 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.
Chlorine and percent solids results for sewage sludge samples are presented in Table 2-20.
Again, results across the three runs appear generally comparable. However, in several instances
the 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 determine
thermal properties. Results from the ultimate/proximate analysis are presented in Tables 2-21
and 2-22. Laboratory data sheets for this analysis are provided in Appendix J. As shown,
ultimate/proximate results are consistent for all three runs.
Table 2-19. Chlorine, Percent Solids, Temperature, and pH Results - Comparison of
Inlet Versus Outlet Scrubber Water
Measurement
Chlorine (mg/L)
- Free
- Total
Total Percent Solids (%)
Temperature (°Fa)
pHa
Run 2
-- In • ~r;Out •
0.01 0.03
ND<0.01 0.05
0.146 0.154
87 116
7.37 6.49
Run 3 ? =
In Out
0.05 0.05
0.08 0.03
0.129 0.142
87 120
7.48 6.57
Run 4
In Out
0.03 0.01
0.05 0.02
0.146 0.158
87 123
7.43 6.51
8 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.
2-31
-------
Table 2-20. Chlorine and Percent Solids Results for Sewage Sludge
. ,>r-* • -- - - N '
-&'.•'? *?'"•"'•':. Measurement
Chlorine (mg/kg)
- Free
- Total
Total Percent Solids (%)
Run 2
18.5
ND<0.5
23.5
•C- ' :Rur£3%,;^
4.84
4.84
20.0
i-l|;':-sRun^4'-.»'."T
17.1
4.29
20.4
Note: ND = Not detected, value is detection limit.
Table 2-21. Ultimate Analysis Results for Sewage Sludge
, ".ixf^'' , '"""i-" ""--- ";-..-. ,-
1 Tuitimate Measurement
Hydrogen
Nitrogen
Oxygen
Carbon
Sulphur
Ash
",.:
Run 2
4.95
4.76
12.5
38.2
1.33
38.3
Dry Basis, % ' xr
' V. Run 3-' '&•"
4.93
4.51
15.1
37.0
1.33
37.1
, tt,t' ;Sj ' '-$**£ : J''fil;v .-si,
• ^"'/Run'4' V*1''
5.16
4.91
13.5
39.3
1.35
35.7
Table 2-22. Proximate Analysis Results for Sewage Sludge
is V -' T ^X,fe ' ' "" ,rr"tt't"
* -," *" -; Proximate ;t,>; ; ;
Measurement
Moisture, %
Volatile Matter, %
Fixed Carbon, %
Sulphur, %
BTU Content (BTU/lb)
• '1, l€,» <:>».• . ' ,':;!'.>
• -i'3*?*: Run 2 ; '
, "'ffc^As^'" Dry'^_,,
Received Basis
76.2
13.9 58.3
0.80 3.39
0.32 1.33
1630 6850
''••3 •- 'RuirT3 . -'i' \^':
; ' As /'-Hifr ,':;Dry|f',
Received - Basis
79.1
12.2 58.7
0.89 4.26
0.28 1.33
1480 7100
!::l^i';Run':4>1;"JS"=
;"' • :-' 'itt"-1', .•;'-,' ' , ^s1' .f" . .
? \jip.As vs; . I?'; bryj-ji
-------
3.0 SAMPLING LOCATION DESCRIPTIONS
Sampling locations for flue gas emissions, scrubber water, and sewage sludge feed are
indicated on the process flow diagram provided in Figure 3-1.
3.1 FLUE GAS SAMPLING LOCATION
Flue gas sampling was conducted in the exhaust stack following the venturi scrubber and
conditioning tower scrubber to control emissions from Incinerator No. 6. Figure 3-2 is a
schematic of the sampling location. As shown in Figure 3-2, the incinerator exhausts from the
scrubber through a 40-in. i.d. stack extending from the roof of the incinerator building. The stack
is constructed of 3/8-in. steel. Four ports, 3 inches in diameter and 5 inches deep are located
approximately 13 ft, 6 in. above the roof line. The sampling ports are located approximately 204
in. (5.1 duct diameters) downstream of the nearest flow disturbance (center shaft cooling air
duct). The stack exhaust end is located approximately 216 in. (5.4 duct diameters) downstream
of the sampling ports.
Sampling location flue gas characteristics were determined using individual sampling and
traverse points for measurement of flue gas velocity, flue gas composition, and the matrix
parameters listed in Table 1-1. Testing was conducted according to EPA standard methods as
described in the following paragraphs.
3.1.1 Sampling Point Determination - EPA Method 1
In accordance with EPA Method 1, a total of 24 traverse points (twelve per axis) were used for
MM5 sampling and CEM measurements. To minimize handling of the MM5 sampling train
during the sample collection, data were recorded at 5 minute intervals, however, the collection
train was only move every 15 minutes (180 minutes per each traverse). Sample collection
consisted of 12 sampling points in each of two sampling ports (port A and port B). A diagram of
the sampling points is provided in Figure 3-3.
3-1
-------
Flue Gas Sampling Location
to
Sludge Feed
Sampling Location
Scrubber Water In
Sampling Location
Scrubber Water Out
Sampling Location
Figure 3-1. Plant Process Sampling Locations
-------
-17 ft.
13ft. 6 in.
30-35 ft. to
edge of roof
40" I.D.
o
h
Sample Ports
~ 3 in. dia., 5 in. deep
Roof Line
80.5 ft. above grade
Figure 3-2. Schematic of Sampling Location Exhaust Stack for Incinerator No. 6
3-3
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PortB
--5
Port A
234
1 1 1
5 6
I 1
X
/ 7 8
-"" 1 1
9 10 1112
I III
I.D. =40"
--8
a Points 1 and 1 2 were ac
Point
1
2
3
4
5
6
7
8
9
10
11
12
% of ID
2.1
6.7
11.8
17.7
25
35.6
64.4
75
82.3
88.2
93.3
97.9
Distance from
Inside of Port
(inches)
0.8(1.0)a
2.7
4.7
7.1
10
14.2
25.8
30
32.9
35.3
37.3
39.2 (39)a
ljusted to one inch from the stack wall to com
Inside Diameter
Distance Port Downstream from Disturbance
Distance Upstream from Port Disturbance
40 in.
204 in.
216 in.
ply with EPA Method 1
3.3ft.
5.1 dia.
5.4 dia.
Figure 3-3. Sampling and Traverse Points for Incinerator Stack
3-4
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3.1.2 Volumetric Measurements • EPA Method 2
EPA Method 2 was used to determine the velocity and volumetric flow rates of the stack
gas. The gas velocity was measured using a stainless steel Type-S pitot tube. The pitot tube was
calibrated against a NIST-traceable pitot tube in accordance with Method 2. Prior to the field
test a type-K thermocouple was calibrated against know gas temperatures.
Velocity and temperature measurements were made at each of the 24 traverse points as
shown in Figure 3-3. These measurements were performed in conjunction with the MM5
sampling. Measurement data were documented on field data sheets provided in Appendix B to
this report.
3.1.3 Molecular Weight Determination - EPA Method 3A
O2 and CO2 gas measurements for determining the average molecular weight of the stack
gases were performed in accordance with EPA Method 3A. Sampling was conducted by
obtaining integrated gas samples as part of the continuous instrumental analyzer methods
discussed in Section 5.1.1.6. Sampling for carbon monoxide, oxygen, and carbon dioxide were
originally to be conducted at a single point in the centroid area of the duct. However, a gas
stratification determination performed on July 19, 1999, was inconclusive. The gas stratification
was not resolved since a single CEM system was used which did not allow for comparisons
between two CEM systems for variability. Since gas stratification was a possibility, the WAM
decided to traverse the CEM sampling probe using the same traverse points simultanous with the
MM5 sampling train.
3.1.4 Flue Gas Moisture Content - EPA Method 4
The flue gas moisture was measured in conjunction with each of the MM5 sampling runs
according to procedures outlined in EPA Method 4. The flue gas moisture for each run was
determined by volumetric analysis of the water collected in the XAD absorbent and impingers of
the MM5 sampling train. All impingers were contained in an ice bath throughout the testing to
3-5
-------
ensure complete condensation of the moisture in the flue gas stream. Any moisture not
condensed in the impingers was captured in the silica gel contained in the final impinger.
3.2 PROCESS SAMPLING LOCATIONS
3.2.1 Scrubber Water
Scrubber water samples were collected at two locations: (1) inlet sample - the main
header supplying the venturi and three-tray impingement scrubber on level 1 of the incinerator
building, and (2) outlet sample - from the bottom of the ash tank located at the bottom of the
venturi scrubber. Both sources were located in the center of the far north side of the incinerator
building.
3.2.1.1 Inlet Sampling Location
Inlet water samples were collected from a 6-in. nonpotable water supply pipe used to feed
the venturi scrubber. Water pressure in the pipe was at 10 psig. A 0.5-in. pipe valve located on
the side of the feed pipe was used to drain the sample. This sampling site was located on level 1
of the incinerator building. Prior to collecting a sample the valve would be opened and allowed
to purge for 3 minutes. The sample collection container would then be filled twice and then
dumped. The third filling was retained as a valid grab sample.
3.2.1.2 Outlet Sampling Location
Scrubber water from the venturi scrubber was collected from a drain valve located at the
bottom of the ash collection tank. The tank was located in the basement of the incinerator
building just below the impinger trays. The drain valve was left partially open to allow a
constant flow of water from the drain. This was done to prevent plugging. When collecting a
sample, the sample container would be filled twice and dumped. A third filling would then be
retained as a valid grab sample.
3-6
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3.2.2 Sludge Feed
Sludge feed samples were collected from the screw conveyor transferring the sludge from
the sludge feed hopper to Hearth No. 1 of the incinerator. Samples were taken from an open end
of the screw conveyor.
3-7
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4.0 PROCESS DESCRIPTION AND OPERATION
4.1 PROCESS DESCRIPTION
4.1.1 General
The Mill Creek Wastewater Treatment Plant is a municipal waste water treatment plant
that incinerates sewage sludge in six multiple hearth incinerators. The facility can treat from 120
to 180 million gallons per day (MOD) of wastewater. It currently processes about 140 MGD.
The Authority serves a population of approximately 750,000. Residential and light commercial
sources contribute most of the wastewater received at the treatment plant. Approximately 20 to
25 percent by volume (containing 40 percent of the received solids) comes from industrial
sources. Figure 4-1 is a schematic diagram of the process.
4.1.2 Preliminary Treatment
Wastewater entering the plant first passes through a screening process to remove any
large objects. It then moves through grit tanks that allow the heavy, untreatable inorganic
materials, called grit, to settle from the wastewater. Next, the wastewater flows through fine
screens that remove small, fibrous material. The Mill Creek WWTP sends all solid materials
collected during the preliminary treatment steps to a landfill.
4.1.3 Primary Treatment
Wastewater then flows to the primary clarifiers. Here, these clarifiers hold the
wastewater under quiescent conditions to allow the heavy solids and floatable solids to separate
from the wastewater. Afterwards, the wastewater goes to the secondary treatment process and
the primary sludge goes to the sludge thickening system. The skimmings go to special
skimmings handling facilities.
4-1
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Domestic and Industrial
Contributors (Influent)
Primary Sludge
Sludge Thickening
System
Wastewater
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
O)
TJ
_3
CO
T3
£
CO
Wastewater
Secondary Clarifiers
Wastewater
Chlorination
Effluent Sludge
Ohio River
Figure 4-1. Schematic Diagram of Mill Creek Wastewater Treatment Plant Process
4-2
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4.1.4 Secondary Treatment
Wastewater entering the secondary treatment process contains colloidal particles and
soluble organic material. This wastewater flows into the activated sludge tanks. These tanks
contain a large population of microscopic organisms that digest the organic material using it for
energy and incorporating it into new cellular material. The contents of the tank (wastewater,
returned activated sludge and air) are maintained and mixed in the tank for 6 to 8 hours. This is
sufficient time for the microorganisms to extract the colloidal particles and soluble organic
material from the water. The discharge from the aeration tanks flows to the secondary clarifiers.
Most of the resulting secondary sludge (composed of microorganisms) returns to the head
of the aeration tank to resume consumption of organic material from the wastewater. The
aeration tanks produce more activated sludge than the organic material in the incoming
wastewater can support. Pumps send the excess activated sludge (EAS) to the sewage sludge
thickening facility.
4.1.5 Tertiary Treatment
Tertiary treatment consists of chlorination to approximately 3 ppm. Chlorination
consumes approximately 3,000 pounds of chlorine per day. The treated wastewater is then
discharged into the Ohio River.
4.1.6 Sewage Sludge Thickening System
The primary sewage sludge that enters the sludge thickening facility is approximately 0.5
to 1 percent solids. Circular basins that allow settling under quiescent conditions thicken the
sewage sludge to a solids content to approximately 8 percent. The thickened sludge flows to the
anaerobic digesters.
A dissolved air flotation (DAF) system thickens the secondary sewage sludge. The DAF
combines the excess activated sludge with a pressurized, supersaturated solution of air in water.
Release of the pressure allows the excess air to leave the solution. This air forms small bubbles
4-3
-------
that attach to particles of sludge, causing them to float to the surface. Pumps remove the sludge
blanket and pump the sludge, now about 6 percent solids, to the anaerobic digesters.
4.1.7 Sewage Sludge Digestion
Anaerobic digestion, as the name infers, allows anaerobic bacteria to digest the mixture
of primary and secondary sludges in air-tight tanks. The digestion process includes two heaters.
The first heater raises the temperature of the material entering the digesters to about 95 °F; the
second maintains the temperature throughout the 30- to 40-day digestion period. Higher
temperature enhances the rate of consumption of the sewage sludge solids by the anaerobes. The
anaerobes partially reduce the organic matter in the sewage sludge to carbon dioxide, water and
methane.
The resulting digester gas has a high enough heat content to fuel the digestion process
heaters and the sewage sludge incinerators. Flares bum the excess digester gas during
nonoperational periods. The digested sludge flows to the dewatering system. The facility plans
to stop the digested sewage sludge burning process in the future, but was burning digested
sewage sludge during these tests.
4.1.8 Dewatering System
The dewatering system consists of 16 belt filter presses. These increase the solids content
of the sludge to approximately 22-26 percent solids. Mill Creek has begun replacing the belt
filter presses with centrifuges. The centrifuges will increase the solids content of the dewatered
sewage sludge to 27-29 percent. Belt filter presses provided all of the dewatered sewage sludge
burned during these tests. Dewatered sludge travels to the incineration facility via conveyor
belts.
4-4
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4.1.9 Incinerator Ash
Incinerator ash is slurried and pumped into ash lagoons for storage. The operators
periodically dredge the ash from the lagoons and send it to a landfill.
4.2 DESCRIPTION OF INCINERATORS
Mill Creek has six multiple hearth incinerators. Four of the units were installed in 1959.
Mill Creek rehabilitated the four original incinerators in 1973 and again in 1992. The plant
added two additional incinerators in 1990. The incinerators operate 24-hours a day. Design
capacity is 18,000 wet pounds per hour of sludge for each incinerator. Permitted capacity is 303
dry tons of sewage sludge per day. Normal operating capacity is 14,000 to 16,000 wet pounds
(at 22 percent solids) per hour per incinerator. The plant usually operates three incinerators at a
time, incinerating a total of approximately 110 dry tons per day of sewage sludge.
Mill Creek began operation of incinerators 5 and 6 in 1990. Grouse Combustion
Systems, Inc. designed the units and began construction. MMR/Wallace with Combustion
Systems took over design and construction after the bankruptcy of Crouse. University
Mechanical/Zack took over and completed the construction after the bankruptcy of the second
design/construction team. The units have no single manufacturer or model numbers. They are
22-ft 3-in. outside-diameter, nine hearth multiple hearth incinerators.
A positive displacement, screw conveyor delivers sewage sludge to the incinerator. Plant
operators have calibrated the delivery of the screw conveyors and calculate the rate of wet sludge
burning based upon the revolutions per minute of the feed screw. This system provides an
accurate measurement of the rate of delivery of sewage sludge. The system also provides a
steady rate of delivery of fuel to the incinerator.
The incinerator can bum either natural gas or digester gas, though the operators rarely use
digester gas.
4-5
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4.3 DESCRIPTION OF EMISSIONS MONITORING. CONTROL AND EMERGENCY
EQUIPMENT
4.3.1 Emissions Control Equipment
Incinerators 5 and 6 have variable throat Venturi contractors and three-tray impingement
tray scrubbers with a stainless steel, chevron-style demister. Design pressure drop for the
Venturi is 15 in. to 20 in. of water; design pressure drop for the tray scrubbers is 6 in. to 10 in. of
water. The plant uses chlorinated final effluent as scrubber water. (Note: The Daily Reports
contained in Appendix M list the pressure drop across the venturi portion of the scrubber system,
not across the entire system.) The incinerator complies with its permit limit of 100 ppm THC (@
7% O2, Dry, 30-day average) without using the detached afterburner. The afterburner, when last
used in 1996, operated at approximately 1050 °F.
4.3.2 Emissions Monitoring Equipment
Continuous emission monitors record the stack-gas concentrations of O2, and THC
continuously. The concentration of THC in the stack gas must be expressed in parts per million
with the concentration adjusted to 7 percent O2 dry gas. The emission monitoring computer
calculates the moisture concentration in the stack gas by assuming saturation and using a lookup
table of percentage moisture vs. temperature. This conservative assumption will cause a slight
overestimation of the calculated emission rate of THC. The assumption of saturation is
conservative because the shaft cooling air, which is unsaturated, heated ambient air, is combined
with the saturated scrubber exhaust upstream of the thermocouple stack temperature
measurement location.
4.3.3 Emergency Equipment
Emergency bypass stacks protect the scrubber from overheating in case of a process
upset. These stacks can route the incinerator exhaust gas directly to the atmosphere. The
Programmable Logic Controllers (PLC) will shut down sludge and auxiliary fuel flows and open
4-6
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the bypass dampers should any of the following occur: (1) disruption in building services (e.g.,
trouble with scrubber water levels, compressed air), (2) disruption in electric services,
(3) disruption in communications between the PLC systems, (4) loss of an ID fan, and (5) excess
temperature in the system. Each of these events has the potential to cause the incinerator to burn
out of control and endanger the plant operators.
4.4 PROCESS OPERATION SUMMARY
At approximately 11:45 a.m. Wednesday, July 21, 1999, the upper hearths (2, 3,4) of
incinerator 6 overheated. This caused premature burning and generation of excess THC
emissions. The instantaneous THC concentration hit a peak of 228 ppm. The operator reduced
the rate of recycling of shaft cooling air to the lower hearths to remove some heat from the
incinerator. This procedure reestablished control within a few minutes. This was the only
process disruption of any sort during any of the test runs.
The incinerator operated without upset for the remainder of the test. In fact, the operation
was stable for 24-hours per day for the entire test program period. An on-line terminal displayed
the levels of the various parameters on a computer monitor for the benefit of the EPA and PES
representatives. The terminal could plot trends for any previous time interval specified. The
EPA/PES representatives observed that, with few exceptions, no temperatures or concentrations
(THC, oxygen) deviated from their set points. All traces remained level. The operators
maintained all parameters at constant, steady-state conditions.
During the test the venturi throat operated at approximately 22 inches of water pressure
drop and 1,300 gallons per minute flow. Plant operators stated that the pressure drop across the
impingement tray scrubber was an additional 6 inches of water.
Table 4-1 presents average values for specific parameters that were monitored during the
three successful test runs and for the aborted run (Run Number 1). Appendix M contains Process
Data Summary Tables and copies of MSD Daily Data Reports that Mill Creek provided for the
four day emissions test program. These reports contain hourly averages of values for
approximately 50 operating parameters. The EPA/PES representatives monitored portions of
these data operations during the testing to ensure steady-state operation of the incinerator.
4-7
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Table 4-1. Summary of Data from Mill Creek WWTP Control Room Process Monitors
-
_ 5-
Date
July 20, 1999
July 20, 1999
July 20, 1999
July 21, 1999
July 21, 1999
July 22, 1999
July 22, 1999
Run
Number
1*
2
Entire Day
3
Entire Day
4
Entire Day
Total Hydrocarbons, ppm
j. i « < ^ . •»
'„ Corrected,
' Uncorrected 7% O2, dry
34.8 57.9
41.0 70.6
35.4 60.6
31.8 54.2
32.5 55.3
21.5 37.5
23.1 40.1
»
Stack Gas
Oxygen, %
12,1
12.5
12.5
12.3
12.3
12.6
12.5
% ^
Stack Gas
Moisture, %
3.1
3.1
3.1
3.2
3.1
3.3
3.3
" ," 5
Sewage t
Sludge
Feed Rate,
dry tons/hr-
1.7
1.7
1.7
1.4
1.4
1.53
1.54
* Run 1 aborted for failure to pass mid-test leak check.
4-8
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5.0 SAMPLING AND ANALYTICAL PROCEDURES
5.1 AIR EMISSIONS
5.1.1 Air Emission Sampling
All emission sampling followed U.S. EPA published methods located in Title 40, Part 60,
Appendix A of the Code of Federal Regulations (40 CFR 60); Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods (EPA SW-846); or other methods approved for this project
by the U.S. EPA. The following specific methods were used:
• EPA Method 1 for determining sampling and traverse points;
• EPA Method 2 for determining flue gas velocity and volumetric flow rate;
• EPA Method 3A for determining flue gas composition and molecular weight (including
measurements of flue gas oxygen and carbon dioxide content);
• EPA Method 4 for determining flue gas moisture content;
• EPA Method 10 for determining carbon monoxide emissions;
• EPA Modified Method 5 for determination of PCBs, D/Fs, and PAHs; and
• EPA Method 25A for total hydrocarbon (THC) emissions.
5.1.1.1 Modified Method 5 Sampling
Emission sampling for determination of PCBs, D/Fs, and PAHs was conducted in general
accordance with EPA Modified Method 5 (MM5) procedures.
Sampling Train Description. Figure 5-1 illustrates the MM5 sampling train. The train
employs a borosilicate glass nozzle and probe for sample withdrawal. The nozzle opening is
appropriately sized to maintain isokinetic sampling. Particulate matter and semi-volatile organic
compounds are removed from the gas stream and passed through a heated glass filter supported
on a Teflon frit.
5-1
-------
"fmer Temperature
Measurement
Therm ometer
S tack
Glass
nozzle
/
/
Heated glass probe
"- Thermocouple
Pilot tubes
PL
Inclined"""--^^
manometer I'M
V
Empty Water Empty Silica
2-lite r (1 00 m I each gel
im pinger im pinger)
Vacuum
lin e
Therm o m eters
erm o m e
By-pass
Vacuum
gauge
•«-
Coarse
D ry gas m eter
Vane pump
Figure 5-1. Sampling Train for EPA Modified Method 5
After particulate removal, the sample gas passes into a water-cooled glass condenser, then
into an XAD-2 sorbent trap. The sorbent trap is packed with precleaned, quality control checked
amberlite XAD-2 resin. Coolant water maintained at wet-ice temperature is continuously
recirculated through the assembly using a submersible water pump. The condenser cools the
sample gases and condenses the stack moisture. The cooled gases and condensate flow down
through the XAD-2 resin, which retains the organic compounds.
5-2
-------
After passing through the sorbent trap, the sample gases enter a chilled impinger train to
remove any remaining moisture. The impinger train consists of five glass impingers packed in
ice water. The first modified (short stem) impinger is left empty to facilitate collection of the
majority of condensate that passes through the XAD-2 sorbent trap. The second and third
impingers each contain 100 mL of high performance liquid chromatography (HPLC) grade water.
The fourth impinger is left empty, and the fifth impinger contains approximately 300 g of 6-16
mesh indicating silica gel. Temperature measurements were taken at the probe, filter holder, inlet
to XAD-2 sorbent trap, outlet of the silica gel impinger, and inlet and outlet of the dry gas meter.
All components from the nozzle to the fourth impinger were made of glass; excluding the
Teflon probe union and filter frit. All connections from the probe to the exit stem of the fourth
impinger were sealed with Teflon O-rings. Sealing grease was not used on any connections
before the fifth impinger.
Sampling Train Preparation. All glass and Teflon components of the MM5 sampling
train were precleaned before use. The following cleaning procedures were used:
(1) Verify that there is no grease on any of the fittings
(2) Wash with hot water and detergent
(3) Rinse with tap water three times
(4) Rinse with deionized, distilled water three times
(5) Rinse with pesticide-grade hexane three times
(6) Rinse with pesticide-grade toluene three times
(7) Rinse with pesticide-grade acetone three times
(8) Bake at 400° F for three hours*
(9) Cap glassware with hexane-rinsed aluminum foil, wrap externally with Teflon tape.
*Note: Probe liner was brushed and rinsed as specified and allowed to air dry.
After cleaning, all glassware was sealed using Teflon tape or hexane-rinsed aluminum
foil, and placed in protective containers for transport to the test site.
Precleaned XAD-2 resin was purchased from Supelco. The XAD-2 resin was purified
again prior to use in the field. The XAD-2 resin was extracted with methylene chloride for at
least 24 hours using Soxhlet apparatus. After extraction, the XAD-2 resin was transferred to a
clean Pyrex drying column. The drying column has sufficient space for fluidizing the XAD-2
5-3
-------
bed, while generating a minimum resin load at the exit of the column. The resin was dried by
passing high-purity nitrogen through the bed. The nitrogen was purified by passing it through a
charcoal trap between the nitrogen cylinder and the column. The rate of nitrogen flow through
the column was set to agitate the bed gently to remove the residual solvents. After drying, the
XAD-2 resin was transferred to a clean jar ready for packing into sorbent traps.
The glass fiber filters were Soxhlet extracted with toluene, followed by extraction with
methylene chloride and dried under nitrogen. The clean filters were placed individually in clean
glass petri dishes. The clean filters were then labeled and wrapped with precleaned aluminum
foil, then in bubble wrap, for shipment to the sampling site.
Prior to packing the XAD-2 resin into the sorbent traps, 40 g of XAD-2 resin and one
filter were extracted and analyzed together to determine background levels of PCBs, D/Fs, and
PAHs. The PCB, D/F, and PAH concentrations in this background check sample were below the
maximum acceptable levels listed in the QAPP. Analytical results from the PCB, D/F, and PAH
background check are provided in Appendices E, F, and G, respectively.
The sorbent traps were cleaned by detergent water and rinsed with tap water, distilled
water, and methanol. The clean sorbent traps were then placed in an oven at 450°C for 12 hours
to remove any trace amounts of organic contaminants. Each clean sorbent trap was packed with
approximately 40 g of clean XAD-2 resin. Each packed XAD-2 sorbent trap was spiked with the
pre-field surrogate standards listed in Table 5-1. After spiking, both ends of the sorbent trap
were sealed with pre-cleaned aluminum foil and Teflon tape. The packed XAD-2 sorbent traps
were labeled and wrapped with pre-cleaned aluminum foil, then bubble wrap, and placed in
coolers with frozen blue ice for shipment to the sampling site. Once the XAD-traps were spiked
with the pre-field surrogate solutions, they were maintained at <4°C.
Once in the field and prior to each test run, the MM5 sampling train was assembled and
leaked-checked in a clean room at the test site. The sampling train was then separated into at
least four sections for transport to the test platform: 1) the probe; 2) the filter and condenser;
3) sorbent trap assembly; and 4) the impinger train. To prevent contamination, the ends of each
section was sealed with hexane-rinsed aluminum foil or Teflon tape. At the test platform, the
train was reassembled and leak-checked prior to sampling.
5-4
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Table 5-1. Pre-Field Surrogate Standards
Standard Type
D/F
PCB
PAH
Standard Contents
37CI4-2,3,7,8-TCDD
13C1 2-2,3,4,7, 8-PeCDF
13C12-1,2,3,4,7,8-HxCDF
13C12-1,2,3,4,7,8-HxCDD
13C1 2-1, 2,3,4,7,8,9-
HpCDF
13C12-PCB-81
13C12-PCB-111
13C-Fluorene
Spike Amount
8000 pg
8000 pg
8000 pg
8000 pg
8000 pg
2000 pg
10,000 pg
200,000 pg
?%;.,, "*} " '^X^'^a-iSP-K'wWj-ftr •> - ->'" , 5 "
;? - 1*1' ,4* Comments ; ;; -;
XAD samples
Purchased as a mixture
(Cambridge Isotope
Laboratories EDF-4054)
Purchased as a mixture
(Cambridge Isotope
Laboratories EDF-4054)
Purchased as a mixture
(Cambridge Isotope
Laboratories EDF-4054)
XAD samples
Purchased as a mixture
(Cambridge Isotope
Laboratories EC-4062)
XAD samples
Preliminary Measurements. Prior to the test program, preliminary measurements were
made to facilitate isokinetic sampling. Preliminary measurements included a traverse of the 24
sampling points discussed in Section 3.1.1.1, measuring velocity, temperature, and the cyclonic
flow angle at each sampling point. Preliminary measurements of flue gas moisture and flue gas
static pressure were conducted at a single point in the gas stream. These measurements were
used to determine the nozzle size and K factor used in operation of the MM5 sampling train.
Additionally, independent measurements of stack diameter, port depth, and distances to
nearest upstream and downstream disturbances were verified to confirm compliance with
Method 1 specifications and to ensure the accuracy of the dimensions supplied in Figure 3-1.
Sampling Train Operation. Sampling was performed in general accordance with Method
5 procedures and specifications, including leak checking, isokinetic sampling rate, and stack
traversing.
5-5
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Prior to each sampling run, the train was assembled at the sampling platform, and the
probe heater, filter heating element, and condenser coil recirculating pump switched on. Once
the probe and filter housing temperature reached 248 + 25°F, the train was leak checked. The
pre-test leak check was acceptable if a leak rate of less than 0.02 fWmin was observed at a
vacuum of 15 in. Hg.
Additional leak checks were conducted during each port change and at the completion of
each test run. These leak checks were considered acceptable if a leak rate of less than 0.02
ftVmin was observed at the highest vacuum recorded during the test run. At the port change of
the first sampling run, the leak check was deemed to be unacceptable. The WAM was notified,
and after discussion, it was determined that the sampling run should be invalidated. Sampling
was discontinued, the sampling train was recovered using the stated procedures in the SSTP and
the sample archived. Three additional sampling runs were performed, so that three valid
sampling runs were available for laboratory analyses.
Sampling was performed for 15 minutes at each of the 24 traverse points, yielding a 360-
minute test per run. Pressure and temperature measurements and isokinetic sampling rate
adjustments were made at 5-minute intervals. Sample volumes of 206.52, 219.66, and 256.60
dry standard cubic feet were obtained for the respective three test runs.
During sampling, the probe and filter temperatures were maintained at 248 ± 25°F. The
temperature of the sorbent trap and the final impinger exit were maintained at or below 68° F.
These temperatures were monitored and recorded at five-minute intervals during each sampling
run.
Sample Recovery and Cleanup. At the completion of each test, the probe, filter
assembly, condenser, and sorbent trap were removed from the train. All open ends of the
sampling train components, including the impingers, were sealed with Teflon tape or
hexane-rinsed aluminum foil and transported to a clean room for recovery. All wash bottles and
funnels were composed of Teflon or glass because polyethylene or other plastics may contain
organic contaminants. A flow chart illustrating the MM5 sample recovery procedures is shown
in Figure 5-2.
Sample recovery proceeded as follows:
5-6
-------
(1) Filter (Container No. 1): The filter was removed from the housing with Teflon tweezers
and placed into a precleaned glass petri dish. The dish was sealed externally with Teflon
wrapping tape.
(2) Front-Half Rinse (Container Nos. 2 and 3): The nozzle/probe and front half of the filter
holder were rinsed three times with acetone and brushed between rinses using a Teflon-
fiber probe brush. The acetone rinse was followed by three rinses with methylene
chloride, that were recovered into the same sample container (Container No. 2).
Following the methylene chloride rinses, the front-half glassware was rinsed three times
with toluene. The toluene rinses were recovered separately (in Container No. 3). All
rinses were recovered into precleaned amber glass bottles fitted with Teflon-lined screw
caps. The liquid level in each bottle was marked on the bottle and then the cap wrapped
with Teflon tape.
(3) Filter to XAD Sorbent Trap (Container Nos. 4 and 5): The back half of the filter
holder and all connecting glassware from the filter to the sorbent trap were soaked/rinsed,
and treated as in (2) above, with the exception that brushing was not done on the acetone
rinse. The acetone and methylene chloride soak/rinses were recovered separately from
the toluene soak/rinse and recovered into precleaned amber glass bottle with a Teflon-
lined screw cap (Container No. 4). The toluene rinse was also recovered into a separate
container (Container No. 5). All liquid levels were marked on the bottles and the caps
wrapped in Teflon tape.
(4) Sorbent Cartridge (Container No. 6): The sorbent trap assembly was weighed to the
nearest 0.5 g for determining moisture gain, capped with hexane-rinsed aluminum foil,
and sealed externally with Teflon tape. The XAD-2 sorbent material was transported to
the laboratory within the glass sorbent trap. The sorbent trap was wrapped with hexane-
rinsed aluminum foil, and kept at <4°C to protect it from light and heat.
5-7
-------
CJl
00
Step 1
Step 2
Remove
filter
l
Plac
glass
di
Rinse / brush front (probe) half
with acetone 3 times
r
Rinse front (probe) half
with methylene chloride
3 times
e in
petri
sh i r i
Seal with
Teflon tape
i
r 1
Place in
Container
r
2
Rinse front (probe) half
with toluene 3 times
l
r
Place in
Container 3
r i '
Sample Sample
Container 1 Container 2
Sample
Container 3
Step 3 Step 4 Step 5
Soak /rinse back half
with acetone 3 times Remove XAD-2
sorbent trap
Recover liquid
from impingers
l,2,3,&4
Soak / rinse back half Weigh sorbent trap
with methvlene chloride
3 times
T ^ '
Place in
Container 4
Cap with foil and seal
with Teflon tape
Soak /rinse back half
with toluene
3 times
+
r
Place in Place in
Container 5 Container 6
1 ' V 1
r i
Measure vo ume
Place in Container 7
Rinse impingers 3
times with acetone
Place in Container 8
Rinse impingers 3
times with
methlene chloride
Place in
Container 8
r V V
Sample Sample Sample Sample
Container 4 Container 5 Container 6 Container 7
Sample
Container 8
Step 6
Remove silica gel from 5
impinger and place in
original container
Seal container
Weigh container
Figure 5-2. Flow Chart for Emission Sample Recovery
-------
(5) Impingers 1-4 Recovery (Container Nos. 7 and 8): The condensate collected in
impingers 1-4 was transferred to a graduated cylinder and the volume recorded. The
liquid was then transferred to a precleaned amber glass bottle fitted with a Teflon-lined
screw cap (Container No. 7). The impingers were then rinsed three times with acetone,
followed by three rinses with methylene chloride. The rinses were collected into a
separate bottle (Container No. 8). All liquid levels were marked on the bottles and the
caps wrapped with Teflon tape.
(6) Silica Gel (Container No. 9): The silica gel in the fifth impinger was transferred into its
original plastic container, sealed, and weighed to the nearest 0.5 g. The percent of silica
gel spent, based on the color change, was documented before transferring.
Sample Storage and Transport. Immediately upon recovery, all samples including
liquid rinses, filters, and sorbent traps were placed into insulated coolers and packed with frozen
blue ice to protect them from light and heat. Battelle transferred all samples requiring off-site
analysis at the end of each test day or the following morning. Emission samples were packed
separately from sludge and water samples.
While in the custody of field personnel or on-site storage, the temperatures inside the
coolers were measured every 8 to 12 hours to ensure that the samples did not exceed 4°C. The
samples remained inside the coolers during transport to Battelle. Upon arrival at Battelle's
Laboratories, the samples were refrigerated to maintain their temperatures at or below 4 °C.
5.1.1.2 Continuous Emission Monitoring for CO. O2, and CO?
Instrumental monitoring of the stack gases was performed as follows:
5-9
-------
Gas Reference Method Instrument Type Range
CO MethodlO TECO Model 48 NDIR 0-6000 ppmdv
CO Analyzer
O2 Method 3A Teledyne Model 320A 0-25%dv
Chemical Cell Portable
O2 Analyzer
C02 Method 3A HORIBA Model PIR-2000 0-20%dv
NDIR CO2 Analyzer
Each of the above analyzers measure gas concentrations on a dry volume basis.
Sampling System Description. An integrated, remote instrumental system housing the
CO analyzer, as well as the diluent gas (O2 and CO2) monitors, was used. Figure 5-3 outlines the
general schematic of the system. The design incorporates a dry extractive system. All of the
instruments were housed in a temperature-controlled trailer located at ground level.
The sampling system consisted of a heated stainless steel probe situated at the stack port
location. A heated glass fiber filter was attached to the probe for particulate removal. A short
section of heated Teflon sample line delivered the sample to an ice-cooled condenser designed to
remove the flue gas moisture. The liquid and ice volumes in the condenser were checked every
hour. The dry gas sample from the stack port location was transported through an unheated
Teflon sample line via the instrumental system sample pump. The gas sample was then pumped
through individual Teflon sample lines to the CO, CO2, and O2 monitors.
Data Acquisition System. The response outputs of the continuous monitors were
recorded digitally by a Campbell Scientific Model CR10WP multi-channel data acquisition
system. The system sampled at a rate of 60 Hz, and stored one-minute average values for each
gas measured. At the end of each test a hardcopy of the data was printed.
Calibration. At the beginning of each test day, the O2 and CO2 monitors were zeroed,
using zero nitrogen, and spanned, using EPA traceability protocol gases with a concentration of
80 to 100 percent of the instrument span. Following calibration, a mid-range gas (40 to 60
percent of the instrument span) was introduced to each monitor. The mid-range response error
did not exceed two percent of the instrument span, as required by EPA Method 6C.
5-10
-------
Stack
Flowmeter
Heated stainless
steel probe
3-way valve
Vent
Heated
filter
O2 analyzer
o
••
Heated Teflon
sample line
CO2 analyzer
CO analyzer
I
Condensate
Dual-pass
refrigerative
condenser
Unheated Teflon
sample line
Data acquisition
Teflon
diaphragm
pump
To individual analyzer calibration
manifold
Figure 5-3. Continuous Sampling System for Instrumental Methods
(EPA Methods 3A and 10)
5-11
-------
The CO monitor was zeroed, using zero nitrogen, and spanned, using a known
concentration of CO in nitrogen. Following calibration, the CO monitor was challenged with two
additional gas concentrations corresponding to approximately 60 percent and 30 percent of
instrument span.
After calibrating the CO, O2, and CO2 monitors, a Teflon calibration line was used to
introduce calibration gas remotely through the probe to verify the absence of sampling system
bias. The bias error did not exceed five percent of the instrument span, as required by EPA
Method 6C.
After each test run, zero nitrogen and either a mid- or high-range calibration gas was
introduced remotely through the sampling system to each monitor to check for calibration drift
error. The calibration drift did not exceed the three percent of the instrument span for valid test
runs required by Method 6C.
The following EPA traceability protocol calibration gases (Reference Standard) were used
during the test program. Gas certification sheets and data are presented in Appendix L.
Instrument
02
C02
CO
THC
Zero (all instruments)
Allowable Standard
10-15%
20-25%
8-12%
16-20%
-900 ppm
-1800 ppm
-3000 ppm
-6000 ppm
60-90 ppm
150-180 ppm
Nitrogen
Reference
Standard
11.5%
21.0%
1 1 .0%
18.0%
915 ppm
1809 ppm
3000 ppm
5971 ppm
86.6 ppm
124.6 ppm*
High calibration gas used was accepted by WAM since
analyzer range was low during the test program.
5-12
-------
5.1.1.3 Total Hydrocarbon Monitoring
Total hydrocarbon (THC) emissions were monitored during the test program with a
Horiba Model MPA-510 total hydrocarbon analyzer. The total hydrocarbon analyzer was
operated by MSD staff. Data from the total hydrocarbon analyzer were collected by PES under a
separate contract with the U.S. EPA. THC data contained in this report were provided by MSD.
MSD operated the THC analyzer consistent with procedures for operation of continuous
emission monitors for continuing compliance demonstration. However, during routine operation,
Method 25A data validation procedures were not observed.
To ensure the data validity, a two-point calibration gas audit (CGA) was performed on the
hydrocarbon analyzer prior to and following the test program by ETS staff. The CGA was
performed in accordance with the procedures of 40 CFR 60, Appendix F, Section 5.1.2. Results
of this audit can be found in Section 6.2.1.5.
During the post-test calibration on July 22, 1999 moisture condensation was observed in
the flow panel serving the analyzer. The post-test CGA revealed a slower response time and
some degraded accuracy. However, the accuracy was still within the allowed 15 percent
specification. Condensation within the system could slow the analyzer response time and absorb
some of the water-soluble organics in the span gas audit as well as in the emissions being
sampled. This moisture problem may account for the observed lower THC results on Run 4.
5.1.2 Air Emission Sample Analysis
5.1.2.1 MM5 Sample Extraction
MM5 emission samples collected in the field and associated quality control samples were
extracted and each extract was split into three aliquots as shown in Figure 5-4 for front half
extracts and Figure 5-5 for back half extracts. One aliquot (equivalent to 50 percent of the
extract) was used for toxic PCB determination, a second aliquot (equivalent to 25 percent of the
extract) for D/F analysis, and the final aliquot (equivalent to 25 percent of the extract) for PAH
5-13
-------
Sample Container
2
Front Half Rinse
Acetone / MeCh
Sample
Container
1
Particulate Filter
Sample
Container 3
Front Half Rinse
Toluene
Filter; Add Filter
to Particulate Filter
Soxhlet extract with
MeCh for 16 hours
CJl
Combine, concentrate,
dry, and split into three
fractions for PCB/ PAH/
DF
Add toluene rinse to filter soxhlet.
Re-extract filter using toluene
Divide extract into
two fractions
25 % for
D / F analysis
25 % for
D / F analysis
Combine extracts
PCB clean up
50 %
PAH clean up
25 %
D / F clean up
75 % Archived
Analysis by
GC-HRMS
Analysts by
GC-HRMS
Analysis by
GC-HRMS
Figure 5-4. Flow Chart for Extraction of MM5 Sampling Train Front Half
-------
Sample Container
7
Impinger Liquid
Sample Container
8
Impinger Rinse
Acetone / MeCl2
Sample Container
4
Back Half Rinse
Acetone / MeCl2
Sample Container
6
XAD-2
Sorbent Trap
Combine, neutralize with 0.1 N NaOH.
Solid phase extraction.
Sample Container
5
Back Half Rinse
Toluene
Combine concentrate
and XAD-2 in Soxhlet
apparatus
Soxhlet extract
with MeCl2 for
16 hours
Concentrate
Combine dry, and
concentrate extract
Add toluene rinse to XAD-2
Soxhlet. Re-extract using
toluene
01
i
01
Split into three fractions
forPCB,PAH,andD/F
analysis
Split into two fractions
25 % D / F and 75 % archived
PCB clean up
50%
PAH clean up
25 %
D/F clean up
Archived
75%
Figure 5-5. Flow Chart for Extraction of MM5 Sampling Train Back Half
5-15
-------
specified in Table 5-2. Laboratory control spike samples were also spiked with native analytes at
the levels specified in Table 5-3.
5.1.2.2 PCB Extract Cleanup and Analysis
Cleanup and PCB analysis of emission sample extracts were conducted following
procedures given in the draft method, "Determination of Toxic Polychlorinated Biphenyls
Emissions from Sewage Incinerator Stationary Sources Using Isotope Dilution High Resolution
Gas Chromatography/High Resolution Mass Spectrometry" (July 20, 1999, version). Any
revisions to the draft method are detailed in the QAPP Amendment/Corrective Action Records
which are included in Appendix P.
5.1.2.3 D/F Extract Cleanup and Analysis
Cleanup of emission sample extracts for D/F analysis were conducted according to EPA
Method 8290 with revisions described in Battelle Standard Operating Procedures (SOP) Nos.
SOP0802-01-01 and SOP0802-02-01. D/F analysis of emission samples was conducted
according to EPA Method 8290 with revisions described in these two Battelle SOPs and
modifications from EPA Method 23 "Determination of Polychlorinated Dibenzo-p-dioxins and
Polychlorinated Dibenzofurans from Stationary Sources" to accommodate the use of Method 23
D/F standards for calibration and spiking. A copy of Battelle SOP Nos. SOP0802-01-01 and
SOP0802-02-01 are provided in Appendix N of this report. Cleanup and D/F analysis of emission
samples followed EPA Method 8290 with the following modifications:
Sample Cleanup
• Method 23 pre-sampling surrogate standards were spiked into the back-half XAD traps
before shipping to the field. Method 23 internal standards were used for all samples
rather than the internal standards in Method 8290. Use of the Method 23 standard
scheme provided better monitoring of sampling efficiency for source emissions.
5-16
-------
Table 5-2. Laboratory Internal Standards
';i, i.Standa'rd.'v ,t~t.
-IfliitType •••••••*%
PCDD/PCDF
PCB
PAH
Jt^S't'isj|!Ji^ 1 - 'fciSffifH* " • ' - '*"3S"^frs^^R?*'>'',-""*'^
'v :".ss--*-' '"' Standard Contents ^ • >4pP
13C12-2,3,7,8-TCDF
13Cl2-2,3,7,8-TCDD
13C12-1, 2,3,7, 8-PeCDF
13C12-1,2,3,7,8-PeCDD
13C,2-1,2,3,6,7,8-HxCDF
13C12-1,2,3,6,7,8-HxCDD
'3C12-1 , 2,3,4,6, 7,8-HpCDF
13C12-1 ,2,3,4,6,7,8-HpCDD
13C12-OCDD
13C12-PCB-77
13C12-PCB-105
13C12-PCB-118
13C12PCB-126
13C12-PCB-156
13C12-PCB-157
13C12-PCB-167
13C12 PCB-169
13C12-PCB-180
13C12 PCB-189
13C12-PCB-209
d8-Naphthalene
ds-Acenaphthylene
d,0-Acenaphthene
d10-Fluorene
d10-Phenanthrene
d,0-Pyrene
d,0-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d,2-Benzo(b)fluoranthene
d12-Benzo(k)fluoranthene
d12-Benzo(a)pyrene
d,2-Perylene
d12-lndeno(1 ,2,3,-cd)pyrene
d14-Dibenz(a,h)anthracene
d12-Benzo(g,h,i)perylene
^** Spik0jpK'"
r Amount ^
8000 pg
8000 pg
8000 pg
8000 pg
8000 pg
v w v v f*y
8000 pg
8000 pg
W V V W |^^
8000 pg
V *r V V J^*3
1 6000 pg
4000 pg
4000 pg
4000 pg
4000 pg
4000 pg
4000 pg
4000 pg
4000 pg
4000 pg
4000 pg
8000 pg
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
r-"-;^^sCornmirfts^v>\ '• *"
All samples
Purchased as a mixture
(Cambridge Isotope
Laboratories EDF-4053)
All samples
Purchased as a mixture
(Cambridge Isotope
Laboratories EC-4064)
All samples
5-17
-------
Table 5-3. Standards for Laboratory Control Spike Samples
; Standard
: tv* Type ':. •"•.
PCDD/PCDF
PCB
PAH
, • "U':A •",' :~ ' . , r • . •, 4 r '. . '";"'•'
•- ; -\'V:vr Standard Contents >=xk- :' ^
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDF
PCB-77
PCB-105
PCB-114
PCB-118
PCB- 123
PCB- 126
PCB-156
PCB- 157
PCB- 167
PCB- 169
PCB- 170
PCB- 180
PCB- 189
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Pyrene
Fluoranthene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Perylene
Indenod ,2,3,-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
''•'Amount"*
800 pg
4000 pg
4000 pg
4000 pg
4000 pg
4000 pg
8000 pg
o r\f\
800 pg
4000 pg
4000 pg
4000 pg
4000 pg
4000 pg
4000 pg
4000 pg
8000 pg
0.8 ng
40 ng
40 ng
40 ng
40 ng
4 ng
40 ng
40 ng
40 ng
8 ng
8 ng
40 ng
8 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
200 ng
I'lComrrieWts' -
LCS/LCSD samples
Purchased as a mixture
(Cambridge Isotope
Laboratories EDF-7999)
LCS/LCSD samples
Purchased as a mixture
(Cambridge Isotope
Laboratories EDF-7999)
5-18
-------
For the front-half air samples, 37C14- 2,3,7,8-TCDD was utilized as a cleanup standard
following procedures in Method 1613 to monitor analyte recovery through the
cleanup process. This was not used in the cleanup of back-half air samples as 37C14-
2,3,7,8-TCDD was added to XAD as a pre-sampling surrogate.
Reduced volumes of acid, base, and salt solutions were used for the acid/base
partitioning cleanup step with no adverse impact upon internal standard recoveries.
Silica/alumina column cleanup procedures were modified to utilize a stacked column
approach which decreases sample preparation time and solvent usage with no adverse
impact on internal standard recoveries.
The carbon column cleanup was modified to use a 20% mixture of Carbopack-
C/Celite which is adapted from Method 1613, Section 13.5.
The final extract concentration procedure was modified to enhance extract transfer to
the GC autosampler vials.
Sample Analysis
• GC/HRMS was calibrated using Method 23 calibration solutions since the Method 23
pre-sampling surrogate and internal standard scheme was used for these samples.
• Only 1 /uL of solution/extract was injected on-column per run as opposed to 2 /uL
(split-splitless mode) specified in Method 8290.
• The GC temperature program was modified to permit the solvent peak to elute more
slowly so as to not trip the source ion gauge. In addition, the final temperature was
reduced to 320 °C to accommodate the upper temperature limit of the GC column.
• The ion masses monitored and the quantification relationships used for calculations
follow Method 23 since the Method 23 standard scheme was used for these samples.
Any revisions to the procedures stated above are detailed in the QAPP Amendment/Corrective
Action Records which are included in Appendix P.
5-19
-------
5.1.2.4 PAH Extract Cleanup and Analysis
Extracts from the emission samples designated for PAH analysis were shipped to Quanterra for
analysis. Cleanup and PAH analysis of emission samples were conducted following the
procedures in California Air Resources Board, Method 429, "Determination of Polycyclic
Aromatic Hydrocarbons (PAH) Emissions from Stationary Sources" with the following
revisions:
• Spiking volumes and concentrations. The concentration of the internal standard daily
spiking solution was 1 ng/,uL for all analytes and was spiked at 200 ng per sample.
The concentration of the surrogate and alternate standards was 1 ng/yuL for all
analytes and was spiked at 200 ng per sample. The concentration of the recovery
standard was 1 ng//uL for all analytes and was spiked at 50 ng per sample extract.
Spike analytes and amounts are listed in Table 5-3.
• Sample extract cleanup. Silica gel was used for extract cleanup. The amount of
packing material used and the elution profile differ from that referenced in the
method.
• Analysis. Column specifications, split time, and instrument temperatures differed
from CARB Method 429 as shown in Table 5-4. Assignment of recovery standards
for internal standard calculations and internal standards for native analyte calculations
were modified by the substitution and addition of standards provided by the analyzing
laboratory.
• Sample reporting. A reporting limit convention was used which includes a limit of
detection (LOD) defined as five times the blank result or 10 ng/split, whichever is
greater. All detectable levels in emission samples or laboratory QC samples above
the reporting limit were reported.
A copy of CARB Method 429 is provided in Appendix N to this report.
5-20
-------
Table 5-4. Gas Chromatographic Operating Conditions for PAH Analysis
-:_ - „•> Operating Parameter '. w"-
Column Type
Length (m)
ID (mm)
Film Thickness (/urn)
Helium Linear Velocity
(cm/sec)
Injection Mode
Splitless Time (sec)
Initial Temperature (°C)
Initial Time (min)
Program Rate (°C)
Final Temperature (°C)
Final Hold Time (min)
Injector Temperature (°C)
.. ; ."'.;-* *.t-\v~* "•*'S»sS,,, -
Used for Analyses^? *:»
DB-5
60
0.32
0.25
30
Splitless
60
85
4
8
300
14
260
^•=0. <^? ,,-
-------
01
fO
First Hour
Collect sample in
lOOOmL
collection jar
[let
Measure pH
Discard
Measure water
temperature
^
r
Collect sample in
1000 mL
collection jar
3
Second Hour
Collect sample in
1000 mL
collection jar
lecticn
Collect sample in
1000 mL
collection jar
Seal place
in rnrilpr
„
Seal place
Composite samples into
10-L composite container
ecfii
Measure water
temperature
Measure pH
Discard
Note: Water samples
were collected every
hour throughout
the test
4.
1000 mL sample
to
Battelle
for
PCB analysis
Mix composite sample and
remove
5 aliquots as shown below
^ ^
1000 mL sample
to
Battelle
for
D/F analysis
r
1000 mL sample
to
Battelle
for
archiving
4
250 mL sample
to
T&E
for
chlorine analysis
4
250 mL sample
to
T&E
for
% solids analysis
Figure 5-6. Flow Chart for Scrubber Water Sampling
-------
The second container used to collect scrubber water was a 1000 mL collection jar. To
collect water into this container, the jar was filled twice with scrubber water and each collection
discarded. After the second filling was discarded, the actual sample (third filling) was taken.
The jar was filled to the brim to eliminate any head space, sealed, and placed into a cooler and
maintained at approximately 4°C until the end of the test. Collection jars were rinsed with
distilled water and then acetone before each sample was collected. Any other glassware used,
including the composite container, were rinsed with distilled water, followed by acetone between
uses. After all six water samples were collected in the collection jars, the contents of each jar
was emptied into a precleaned composite container and the combined contents were gently
stirred, not shaken. Five aliquots were removed and placed in five separate containers for PCB
analysis, D/F analysis, chlorine analysis, percent solids analysis, and archiving as shown below:
PCB analysis: 1000-mL amber glass j ar
D/F analysis: 1000-mL amber glass j ar
Chlorine analysis: 1000-mL amber glass j ar
Percent solids analysis: 1000-mL amber glass j ar
Archiving: 1000-mL amber glass j ar.
Immediately upon recovery, all samples were placed into insulated coolers packed with
frozen blue ice to protect them from light and heat. The samples remained inside the coolers
while at the field site and during transport to Battelle. Samples from each test were transported
to Battelle at the end of the test day or the following morning. While at Battelle's laboratories,
the scrubber water samples were kept refrigerated until analysis.
5.2.2 Scrubber Water Analysis
5.2.2.1 PCB Analysis
Scrubber water samples were analyzed for PCBs according to the draft method,
"Determination of Toxic Polychlorinated Biphenyls in Sewage Incinerator Scrubber Water Using
Isotope Dilution High Resolution Gas Chromatography/High Resolution Mass Spectrometry"
dated July 20, 1999. The extraction procedures are illustrated in Figure 5-7. The complete
method is provided in Appendix N to this report.
5-23
-------
Scrubber Water Sample
Spike ~1L of Sample
with Labeled
Internal Standards
Visually Estimate Percent
Solids Content of Sample
(all samples <5% solids)
Extract Using SPE
Extract Brought to 20 mL Volume
Spike Second 10 mL Extract Aliquot
with Cleanup Standard
Proceed to Sample Cleanup
Archive 10 mL
Figure 5-7. Flow Diagram for Preparation and Extraction
of Scrubber Water Samples for PCB Analysis
5-24
-------
5.2.2.2 D/F Analysis
Scrubber water samples were analyzed for D/F according to EPA Method 8290
"Polychlorinated Dibenzodioxins (PCDDs) and Polychlorinated Dibenzofurans (PCDFs) by
High Resolution Gas Chromatography/High Resolution Mass Spectrometry (HRGC/HRMS)"
with revisions described in Bartelle SOP Nos. SOP0802-01-01 and SOP0802-02-01. The
extraction procedures are illustrated in Figure 5-8. SOP Nos. SOP0802-01-01 and SOP0802-02-
01 are provided in Appendix N of this report. Cleanup and D/F analysis of scrubber water
samples followed EPA Method 8290 with the following modifications:
Sample Cleanup
• 15 labeled compounds were used in the internal standard solution instead of the 9
specified in Method 8290 to provide improved accuracy.
• Cleanup standard 37C14- 2,3,7,8-TCDD was utilized per Method 1613 to monitor
analyte recovery through the cleanup process.
• Reduced volumes of acid, base, and salt solutions were used with no adverse impact
upon internal standard recoveries.
• Modified silica/alumina column to utilize a stacked column approach and enhance
extract transfer from the carbon column to the GC autosampler vials were made.
Sample Analysis
• GC/HRMS was calibrated at levels specified in Method 1613, Table 4 with an
additional standard at concentrations equivalent to one-half the level of Method
1613's lowest calibration point. This provided an expanded calibration concentration
range compared with that of Method 8290.
• Only 1 jLiL of solution/extract was injected on-column per run as opposed to 2 juL
(split-splitless mode) specified in Method 8290.
• A combination solution was utilized on DB-5 columns at the beginning and end of
each 12-hour run period. This allowed the determination of calibration and column
performance in a single run.
• The GC temperature program was modified to permit the solvent peak to elute more
slowly so as to not trip the source ion gauge. In addition, the final temperature was
reduced to 320 °C to accommodate the upper temperature limit of the GC column.
5-25
-------
Scrubber Water Sample
Transfer Sample to
Methylene Chloride Rinsed
Sep Funnel
Add 60 niL
Methylene Chloride
Spike Sample with
1 mL Internal Standard
Shake Sep Funnel 2 Minutes
Allow Phase Separation
20 Minutes
Drain Methylene Chloride
Through Sodium Sulfate
Rinse Sodium Sulfate
with Methylene Chloride
Repeat Extraction
Two More Times
Concentrate Extract
Figure 5-8. Flow Diagram for Preparation and Extraction of Scrubber Water
Samples for D/F Analysis
5-26
-------
All five congener groups were monitored separately.
The mass of the cleanup standard 37Cl4-2,3,7,8-TCDD was monitored per Method
1613, Table 8.
Any other revisions are detailed in the QAPP Change Forms/Corrective Action Records which
are provided in Appendix P.
5.2.2.3 Chlorine Analysis
Analyses of chlorine in scrubber water samples were conducted using a Hach Model
DR2010 photometric analyzer. This unit measures free C12 and total C12 in the 0 to 2 mg/L
range. The measurement technique is equivalent to Method 4500 G of Standard Methods for
Examination of Water and Wastewater. This method employees a color-metric procedure using a
filter photometer. A copy of this method can be found in Appendix N to this report.
5.2.2.4 pH/Temperature Determination
The pH of the scrubber water samples was measured according to Standard Methods for
Examination of Water and Wastewater, Method 4500 H, "pH Value." The temperature of the
scrubber water was measured immediately after collection in the field using a glass thermometer.
5.3 PROCESS SLUDGE FEED
5.3.1 Sludge Feed Sampling
A sludge feed sample was collected every 60 minutes (Figure 5-9) during the test. The
sludge sample was scooped with a precleaned metal scoop and placed in a 750-mL glass
container. The full container was then emptied into a precleaned large stainless steel holding
container. After all six grab samples were collected, the composite was then mixed using the pan
mixing/quartering technique described in ASTM Standard Guide for Composite Sampling and
Field Subsampling for Environmental Waste Management Activities (Designation D6051-96)
5-27
-------
First Hour
Second Hour
Note: Sludge
samples were
collected every
hour throughout
the test
Composite sample in
10-L holding container
Mix composite
using pan
mixing/quartering
technique
Remove five
samples as shown
below using alternate
scoop technique
Figure 5-9. Flow Chart for Sewage Sludge Feed Sampling
5-28
-------
found within the appendices. Six aliquot samples were removed using an alternate scope
technique (also included in ASTM Method D6051-96) and placed into separate containers for
PCB analysis, D/F analysis, chlorine analysis, percent solids analysis, ultimate/proximate
analysis, and archiving as shown below.
PCB analysis: 1000-mL vented amber glass jar (500 cc sample)
D/F analysis: 1000-mL vented amber glass jar (500 cc sample)
Chlorine analysis: 1000-mL amber glass j ar
Percent solids analysis: 1000-mL amber glass j ar
Ultimate/proximate analysis: 1000-mL amber glass j ar
Archiving 1000-mL amber glass j ar.
The sample scoop and all other containers or items that come in contact with the sludge
sample were rinsed with distilled water and then acetone before being reused.
Acid was added for sterilization to the jars for PCB analysis, D/F analysis, and archiving
(40 mL of 1:1 HNO3 for every 500 mL of sample). The sewage sludge feed samples were stored
at <4°C in on-site coolers until transported to Battelle. Containers for chlorine and percent
solids analysis were hand carried to the on-site T&E laboratory.
The samples remained inside the coolers while at the field site and during transport to the
analytical laboratory. Samples from each test were transported to Battelle at the end of the test
day or the following morning. While at Battelle's laboratories, the sewage sludge feed samples
were kept refrigerated until analysis.
5.3.2 Sewage Sludge Feed Analysis
5.3.2.1 PCB Analysis
Sewage sludge feed samples were analyzed for PCBs according to the draft method
"Determination of Toxic Polychlorinated Biphenyls in Sewage Sludge Using Isotope Dilution
High Resolution Gas Chromatography/High Resolution Mass Spectrometry" dated July 20,
1999. The extraction procedures are illustrated in Figure 5-10. This method is provided in
5-29
-------
Sewage Sludge
Sample
^
Take 2
i
r
g Aliquot
r
Spike with Labeled
Surrogate Recovery
Standards
>
r
Mix with Drying Agent
to Produce 1 : 1 Ratio
Soxhlet Extract with
Methylene Choride
Bring to 50 mL
Solvent Exchange
to Hexane
Proceed to Extract
Cleanup
25 mL Archived
Figure 5-10. Flow Diagram for Sample Preparation and Extraction
of Sewage Sludge Feed Samples for PCB Analysis
5-30
-------
Appendix N of this report. Any revisions to this draft method are detailed in the QAPP
Amendments/Corrective Action Records which are included in Appendix P.
5.3.2.2 D/F Analysis
Sewage sludge feed samples were analyzed for D/Fs according to EPA Method 8290,
"Polychlorinated Dibenzodioxins (PCDDs) and Polychlorinated Dibenzofurans (PCDFs) by
High Resolution Gas Chromatography/High Resolution Mass Spectrometry (HRGC/HRMS)"
with revisions described in Battelle SOP Nos. SOP0802-01-01 and SOP0802-02-01. The
extraction procedures are illustrated in Figure 5-11. A copy of SOP Nos. SOP0802-01-01 and
SOP0802-02-01 are provided in Appendix N of this report.
Cleanup and D/F analysis of sewage sludge samples followed EPA Method 8290 with the
following modifications:
Sample Cleanup
• 15 labeled compounds were used in the internal standard solution instead of the 9
specified in Method 8290 to provide improved accuracy.
• Cleanup standard 37C14- 2,3,7,8-TCDD was utilized per Method 1613 to monitor
analyte recovery through the cleanup process.
• Reduced volumes of acid, base, and salt solutions were used with no adverse impact
upon internal standard recoveries.
• Modified silica/alumina column to utilize a stacked column approach and enhance
extract transfer from the carbon column to the GC autosampler vials were made.
Sample Analysis
• GC/HRMS was calibrated at levels specified in Method 1613, Table 4 with an
additional standard at concentrations equivalent to one-half the level of Method
1613's lowest calibration point. This provided an expanded calibration concentration
range compared with that of Method 8290.
• Only 1 juL of solution/extract was injected on-column per run as opposed to 2 //L
(split-splitless mode) specified in Method 8290.
5-31
-------
Homogenize Sample
Weigh Aliquot
Add Drying Medium Na2SO4 or
Equivalent
Mix to Dryness - Free Flowing
Pre-extract Soxhlet and
Concentrate Solvent to
5 mL - Archive
Add Sample to Pre-extracted Setup
and Spike with Internal Standards
Extract for 16/18 Hours
Snyder Column to ~10 mL
Acid Wash NaCl, Base
Wash, NaCl
Concentrate
Acid/Base SiO2 and
A12O3 Columns
Concentrate
Carbon Column
Concentrate, Add
Recovery Standard
Figure 5-11. Flow Diagram for Preparation and Extraction of
Sludge Feed Samples for D/F Analysis
5-32
-------
A combination solution was utilized on DB-5 columns at the beginning and end of
each 12-hour run period. This allowed the determination of calibration and column
performance in a single run.
The GC temperature program was modified to permit the solvent peak to elute more
slowly so as to not trip the source ion gauge. In addition, the final temperature was
reduced to 320 °C to accommodate the upper temperature limit of the GC column.
All five congener groups were monitored separately.
The mass of the cleanup standard 37Cl4-2,3,7,8-TCDD was monitored per Method
1613, Table 8.
Any other revisions are detailed in the QAPP Amendment/Corrective Action Records which are
included in Appendix P.
5.3.2.3 Chlorine Analysis
Analysis of chlorine in sewage sludge feed samples was conducted using a Hach Model
DR 2010 analyzer. This unit measures free C12 and total C12 in the 0 to 2 mg/L range. The
measurement technique is equivalent to Method 4500G of Standard Methods for Examination of
Water and Wastewater. The free and total chlorine analyses of sewage sludge were performed on
an extract obtained by modified ASTM Method D5233. A copy of the Method 4500G, "DPD
Colorimetric Method" and modified Method ASTM D5233 can be found in Appendix N to this
report.
5.3.2.4 Percent Solids Analysis
Percent solids in sludge feed samples were determined following Standard Methods for
Examination of Water and Wastewater, Method 2540 B, "Total Solids Dried at 103-105 °C."
Each sample was analyzed in triplicate for percent solids. A copy of this method can be found in
Appendix N to this report.
5-33
-------
5.3.2.5 Ultimate/Proximate Analysis
Ultimate/proximate analysis of sludge feed samples was performed following ASTM
Methods D3176 and D3173, respectively. Copies of these ASTM methods are included in
Appendix N to this report.
5-34
-------
6.0 INTERNAL QA/QC ACTIVITIES
6.1 QA/QC CHECKS AND ISSUES
6.1.1 Field Sampling
6.1.1.1 MM5 Emission Sampling
Cyclonic Flow. Prior to sampling on the first test day a cyclonic flow check was
conducted on the stack for Incinerator No. 6. The cyclonic flow was checked at each of the test
points shown in Figure 3-3 following procedures described in 40 CFR 60, Appendix A,
Method 1 Section 2. All test points were well below the allowable 20° with a maximum of 8°
and an average rotational angle of 4.58°. The cyclonic flow check sheet is provided in Appendix
B-l to this report.
Gas Stratification Check. At the completion of the cyclonic flow check a gas
stratification check was conducted using a single CEM system. The CEM system determination
indicated that gas stratification was possible in the exhaust stack. The WAM made a decision to
traverse the same MM5 traverse point locations, using the CEM sampling probe simultaneous
with each MM5 sampling run. The results of the stratification check are shown in Table 6-1.
The field data can be found in Appendix B-l of this report.
Leak Check. The MM5 sampling train was leak checked at the beginning and end of
each test run and after moving from one sampling port to another during a run. The leak checks
were considered acceptable if a leak rate of less than 0.02 fWmin was observed at the highest
vacuum recorded during the sampling run.
At the port change of the first sampling run, a leak rate of 0.06 ftVmin was observed.
This leak check was determined not to be acceptable and the sampling run invalidated.
Sampling was discontinued, the sampling train was recovered using the stated procedures in the
SSTP, and the samples were archived.
6-1
-------
Table 6-1. Gas Stratification Check Results
Sampling
' Point
A1
A2
A3
A4
A5
A6
B1
B2
B3
B4
B5
B6
Average
Time
1545
1549
1553
1557
1601
1605
1610
1614
1618
1622
1626
1630
--
4^°a -^
M%dv) >
15.26
14.85
14.73
14.94
15.09
14.86
15.15
14.73
14.38
13.88
13.87
14.03
14.65
% Diff.
from
"Mean
4.2
1.4
0.5
2.0
3.0
1.4
3.4
0.5
-1.8
-5.3
-5.3
-4.2
-
- -\ -g*4V^
< , _ _.N -^Xifj?
1*11 - xH&i * >!&
wl/2'U%j'g
(% dv)W
4.31
4.27
4.35
4.16
4.29
4.44
4.15
4.45
4.76
5.21
5.28
5.15
4.57
|:$>:Diff,J
-j|ffrbm ^
^Mean'^
-5.7
-6.6
-4.8
-9.0
-6.8
-2.8
-9.2
-2.6
4.2
14.0
15.5
12.7
-
i%%:4^$.
iiiiiii'^O^f"^
956
858
947
995
1060
1156
1216
1203
1209
1294
1218
1152
1105
;fii M. nifr , '
^f \ /v,,,WlTT ,( ^ •
p;,'-from>;.'f
•T" Mean
-13.5
-22.4
-14.3
-10.0
-4.1
4.6
9.1
8.9
9.4
17.1
10.2
4.3
-
Note: Results obtained with single CEM analyzer on July 19, 1999, 1543-1630.
During the next three sampling runs all pre-test, post-test, and port change leak checks
were successfully completed. Leak check results can be found on the isokinetic data sheets in
Appendix B-l-2 to this report.
Isokinetic Sampling Check. Isokinetic calculations performed at the end of each test
verified that sampling was conducted within the ±10 percent criteria for all tests. These results
were:
Run 2 91.7% Isokinetic
Run 3 95.9% Isokinetic
Run 4 97.1% Isokinetic
Although acceptable, the isokinetic sampling rate during MSD-MM5-R2 was lower than
expected (91.7 percent), because of an incorrect assumption of flue gas moisture. The K factor
was initially calculated for MSD-MM5-R1, based on an assumed moisture of 10 percent, a value
measured during previous emissions tests. This value was significantly higher than the actual
flue gas moisture content of 4-5 percent measured during the sampling program. Although
6-2
-------
preliminary moisture measurements taken on July 19,1999, supported the lower moisture
values, these readings were thought to be anomalous at the time.
The data from the voided MSD-MM5-R1 also indicated 4.7 percent moisture. However,
this value was also assumed invalid, because of suspected dilution caused by inleakage indicated
by a failed leak check at the midpoint of the sampling run. It is now suspected that the leak
originated during removal of the train from the sampling port and had no bearing on sample or
moisture collection.
Following recovery of MSD-MM5-R2, the flue gas moisture of 4-5 percent was
confirmed and the K factor was recalculated for MSD-MM5-R3 based on this measurement.
Sampling Train Temperatures. Sample probe, filter holder, XAD-2 trap inlet, impinger
train exit, and dry gas meter inlet and outlet temperatures were recorded on the isokinetic data
sheet every five minutes during each of the three MM5 sampling runs. The XAD-2 trap
temperature during all three runs never exceeded the allowable 68 °F. Probe and filter holder
temperatures were maintained within the acceptable range of 248 ± 25 °F. All temperature data
can be found on the isokinetic data sheets in Appendix B-l-2 to this report.
6.1.1.2 Continuous Emission Monitoring
Prior to sampling, the CEM sampling system was checked for leaks by turning on the
sampling system pump, sealing off the end of the sampling probe, and determining that there
was no appreciable flow through the sampling system's flow indicators located in the mobile
sampling laboratory.
CEM Calibration and Linearity Check. On each test day and prior to sampling the O2,
CO2, and CO, the continuous analyzers were calibrated at a low, mid, and high span point to
check the instrument calibration and to verify instrument linearity. Results of the daily
instrument calibration and linearity checks are shown in Table 6-2. The field data can be found
in Appendix L-l to this report. EPA traceability protocol gas certificates of analysis can be
found in Appendix L-5.
6-3
-------
Table 6-2. CEM Calibration and Linearity Check Data
•V" ''••;" Gas" '""•'• '""'-
02
C02
CO
** Certif ied.^jjfiif
' V Concentration? 5
,,v -^ ;:Run24«c;t|-
'• l^uly'ad^'4-®
RuntS^.f ^:J|
lffi|jtjufy 21 '-It /'If
§«>lPRiini*A yf^fjyff
O^I^IIUII Ttf^'S, x
-------
A comparison between the pre-test and post-test bias check was then used to determine
the CEM drift over the test period. Results of the bias check and instrument drift check are
given in Table 6-4. All bias checks and CEM drift checks were within the allowable limits.
6.1.2 Sample Handling
Immediately upon recovery of each MM5 sampling train, all samples including liquid
rinses, filters, and sorbent traps were placed into insulated coolers and packed with frozen blue
ice to protect them from light and heat. While in the custody of the sampling team, the
temperatures inside the coolers were checked every 12 hours to ensure that the samples were
maintained at <4°C. Scrubber water samples and sewage sludge samples were packed in a
cooler separate form the emission samples. Battelle transported all samples requiring off-site
analyses to their Columbus Laboratories at the end of each test day or within 24 hours of
collection. A schedule of sample recovery and transfer is provided in Table 6-5. Sample
temperatures were measured at each point of transfer. All temperatures were maintained at or
below 4°C except in the following cases. The temperature of two coolers containing Run 2
emission samples was 13°C and 8°C, and the temperature of one cooler containing some Run 4
scrubber water samples was 5.4°C upon receipt at Battelle as noted in the laboratory sample
log-in book. These minor exceedances in storage temperature had no apparent impact on sample
results as data for these affected samples were comparable to nonaffected samples. Sample
chain-of-custody forms are provided in Appendix D.
Table 6-5. Sample Transfer Schedule
>.;r . "• ', ;- - ,;•?, .".- ,-', ",
Sample Recovered
Transfer to Battelle Courier
Received at Battelle
Run 2 •!•"
2300 (7/20)
1030 (7/21)
1330 (7/21)
v-?; Run 3' -,'1
1840 (7/21)
1900 (7/21)
2230 (7/21)
Test Run 4
1800 (7/22)
0800 (7/23)
1335 (7/23)
6-5
-------
Table 6-4. Bias and Instrument Drift Check Data
Span
Zero Drift
Initial System Response
Final System Response
Zero Drift (%)
Calibration Drift
Initial System Response
Final System Response
Calibration Drift (%)
System Bias (Zero)
Analyzer Cal. Response
Initial System Response
Initial System Bias (%)
Midpoint System Response
Midpoint System Bias (%)
Final System Response
Final System Bias (%)
Span
System Bias (Upscale)
Analyzer Cal. Response
02
<%„„>
25
0.17
0.07
-0.40
11.80
11.62
-0.72
0.00
0.17
0.68
0.11
0.44
0.07
0.28
25
11.80
Run 2
C02
(%*,)
20
0.12
0.14
0.10
10.99
11.05
0.30
0.10
0.12
0.10
0.15
0.25
0.14
0.20
20
10.96
CO
(pprru)
6000
4.13
0.77
-0.06
1847.30
1830.90
-0.27
6.07
4.13
-0.03
0.00
-0.10
0.77
-0.09
6000
1878.00
02
<%*,)
25
0.02
0.12
0.40
11.55
11.44
-0.44
0.00
0.02
0.08
0.11
0.44
0.12
0.48
25
11.75
Run 3
C02
(%nJ
20
0.10
0.14
0.20
10.84
10.89
0.25
0.11
0.10
-0.05
0.15
0.20
0.14
0.15
20
11.12
CO
(ppmdv)
6000
3.61
0.26
-0.06
1876.80
1831.10
-0.76
-0.45
3.61
0.07
2.06
0.04
0.26
0.01
6000
1878.00
02
(%„„)
25
0.06
0.12
0.24
11.43
11.80
1.48
0.00
0.06
0.24
0.11
0.44
0.12
0.48
25
11.53
Run 4
CO2
{%„„)
20
0.11
0.13
0.10
10.85
10.85
0.00
0.11
0.11
0.00
0.13
0.10
0.13
0.10
20
10.91
CO
(ppmdv)
6000
5.42
5.71
0.00
1831.90
1853.80
0.36
3.63
5.42
0.03
5.42
0.03
5.71
0.03
6000
1852.00
O)
en
-------
Table 6-4. (Continued)
Initial System Response
Initial System Bias (%)
Midpoint System Response
Midpoint System Bias (%)
Final System Response
Final System Bias (%)
02
(%dv>
11.80
0.00
11.59
-0.84
11.62
-0.72
Run 2
C02
(%*,)
10.99
0.15
10.93
-0.15
11.05
0.45
CO
(ppmdv)
1847.30
-0.51
1831.30
-0.78
1830.90
-0.78
02
(%„,,)
11.55
-0.80
11.70
-0.20
11.44
-1.24
Run 3
CO2
(%nJ
10.84
-1.40
10.88
-1.20
10.89
-1.15
CO
(pprrO
1876.80
-0.02
1851.50
-0.44
1831.10
-0.78
02
(%H.)
11.43
-0.40
11.73
0.80
11.80
1.08
Run 4
C02
(%„„)
10.85
-0.30
10.91
0.00
10.85
-0.30
CO
(ppm*,)
1831.90
-0.33
1831.30
-0.35
1853.80
0.03
CD
-------
6.1.3 Laboratory Analysis
Section 6.3 of this report provides a complete review of laboratory QA/QC performance
including listings of method target performance criteria and results achieved. In this section,
only potential issues with laboratory analyses that could impact the quality of the data are
discussed. In discussing PCB, D/F, and PAH analytical issues, the following items were
addressed in order as necessary:
• Calibration (initial and continuing)
• Internal standard recoveries
• Spike recoveries and precision of LCS/LCSD
• Method blank
• Detection limit
• Turnaround time.
6.1.3.1 Emission Samples
PCB Analysis. The initial calibration for both the SPB-Octyl and DB-1 analyses met
the requirement for response factors having less than 35% relative standard deviation (RSD) for
all analytes (actual range = <17% for SPB-Octyl and DB-1 calibrations). The continuing
calibrations met the requirement for response factors being within 35% of the response factors
generated in the initial calibration for at least 70% of the analytes.
Field Samples. Summary tables of PCB results and standard recoveries for the front
half and back half air samples are shown in Tables 6-6 and 6-7a, respectively. 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% and ranged from 35-77%. Internal standard
recoveries in the back half air samples were also within the 30-150% limits and ranged from 49-
84%. These internal standard recoveries indicate analytes were well recovered during laboratory
extraction and were retained during the extract cleanup process. 13C12-PCB-81 and 13C12-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% for
6-8
-------
Table 6-6. Summary of PCB Results and Standard Recoveries for Front Half Air Samples
• ."-"• '-'' 'id'-'V-'ij;- :,,. •
ijllfr' • -'.I """*' ''""""'„
ANALYTESv
PCB-77
PCB-123
PCB-118
PCB-114
PCB-105
PCB-126
PCB-167
PCB- 156
PCB-157
PCB- 169
PCB-180
PCB-170
PCB- 189
tf'^:,::''1' '"'j^,J.,':.^TARGET«a
, -RECOVERY!!
-• -~%6UsS4t
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
10-150
20-130
>''.i"-».
liiitk; ;:'t^
Vl3|ii .-r
,„;_ SPIKE;,;. '
fecONcJgl
(pg/sample)
4000
4000
4000
4000
4000
4000
4000
4000
4000
4000
8000
2000
10000
• '-;';i;if', "
RUN ,2 >''»^,
48190;11-02":
FH-R2-i»CB Jj*."1
; (pg/sample)
750
38.4 B
1300B
91. 6B
624 B
35.5 B
65. 8 B
131 #,B
37.7 #,B
61.8 B
307 B
148 B
17.4B
\\ ' -/ \^!e^ ' " '-
MI,-' - / '' -H$i'' }*4A -'
#':V. RUN
*^8i90-11-b2p/
:;^m-Riz-pCBifi
V (pg/saniple):X
2660
1830
1910
2280
1820
3100 #
2760 #
2170
2360
2350
2860
1290
5690
#&'.-• '*'
DL ••"••y_
(pg/sample)
,, ,u',^^(
ARECOVERY%
'-%'-'(%» -'-ff
67
46
48
57
46
77
69
54
59
59
36
65
57
:.;,,t _RUN^|*._
" '^48190-1^03"^,-
" '' FH-R3-PCB'f*|;
(pg/sample) '*/';
650
38. 7 B
1260 B
72.9 B
585 B
24.7 B
58. 6 B
112 #,B
28.5 #,B
30.5 B
236 B
106 B
12.4B
,-<;,._ ,,/-•%&; * '
,'t '-Ru1i'r3AC-. '
{148196-11^03
;, ' • FHPR3-PCBf|5i
€ (pg/sample) •*%*
2200
1390
1470
1770
1450
2400 #
2210*
1750
1920
2030
3140
1050
4090
~"4' '; ' ' V ';
,/"rf ,-,,.•., '-',:'-.,•',,
•-"DLV _:'i
(pg/sample)
*fv - t;f'' " '
'"J:,"" ' %" -' i
RECOVERY|
.- -'(*)•/.-*
55
35
37
44
36
60
55
44
48
51
39
53
41
_ '-:^RUIY4.~ ,.:,;'r;
:-V 48190-11 -04' ''^
j||i^FH-R4-PCB , '
;'5i; (pg/sample)
551
28.5 B
1120 B
62.4 B
524 B
23.2 B
51.9 B
107 #,B
28.5 »,B
38. 3 B
257 B
112 B
20 B
lA-ittiH^:;;.,;-
.^483j»-11-d|j^-
,^.' 'FHWipCB '^
Sl'li. (pg/sample) 41
2210
1450
1440
1820
1460
2020*
1790 #
1900
1860
1960
3180
1150
4850
]i;' DL;^ :,
(pg/sample)
i& 'y^
•* RECOVERfl
fc, -'j%h;--4?
55
36
36
45
37
51
45
48
47
49
40
58
48
CD
CD
DL = detection limit.
tt = Value from second column confirmation.
B = Congener found in lab blank at >20% of the concentration found in the sample.
-------
Table 6-7a. Summary of PCB Results and Standard Recoveries for Back Half Air Samples
• •- • •"'."•< 1V «y?.V .- -' - ';*"'
RUN 2 V, RUNS RUN 4 ,
48190-09-02^7 ? f 48190-09-03 48190-09-04
'', BH-R2-PCB;'^^r/"rf;,DL;/',r;;!-f'j«^|BH-R3-PCB DL BH-R4-PCB ,DL
ANALYTES ' ' (pg/sample) (pg/sample) (pg/sample) (pg/sample) (pg/sampte) > (pg/sample)
PCB-77
PCB-123
PCB-118
PCB-ii4
PCB- 1 05
PCB- 126
PCB- 167
PCB- 156
PCB- 157
PCB- 169
PCB- 180
PCB- 170
PCB- 189
1 46000 E
90600 *
665
32100
2180
15000
4060
2210
3640*
1250 #
3210
15400
6170
538
•M '-.'• i-giO^' • •'."V'-l^,^,
INTERNAL STANDARDS
13C-PCB-77
13C-PCB-118
13C-PCB-105
13C-PCB-126
13C-PCB-167
13C-PCB-156
13C-PCB-157
13C-PCB-169
13C-PCB-180
13C-PCB-189
1 3C-PCB-209
PRE-SAMPLING SURROGA1
13C-PCB-81
13C-PCB-111
5P RECOVERm|»*CONCj«
•':-*Sl-(%J^»*Apg/*ample)f
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
E STANDARDS
10-150
20-130
4000
4000
4000
4000
4000
4000
4000
4000
4000
4000
8000
2000
i 66'bb
,>ii- "'!•'"•. <"• y";ifcil
,tg;'|',RUN,2'|jiil|i
M48i90r09-02i'|-
S|fBH-ft2^CB.:f-'
sC(pg/sample) -'* '
2510
2360
2480
1960
2540
3290 ff
3360 #
2120
2170
2400
4810
1070
5240
1 26000 E
65800 *
617
29600
1920
13800
3390
1920
3400 tt
10800
2700
13700
5550
430
47400 E
28100 *
229
13700
855
5810
1390
858
1320 tt
499 tt
902
5480
2820
272
•ii*4",: ',,'•• - .:, '• .-:•:• \' ' ' ' -V * ,\'; ' "•'
iytK'"--^'-W ;RUN3. '-,''•, • RUN4; i/r;sf>'-\4,
^^Wl;1£4;''rl-f-"?481 90-09-03 ' " 5 481 90-09-04 -1^ .l<''1?l/2sf'*
-' j!^"8iF|Fi,/tV^r!i'J( !'+-*,g?ii> V^i-'* •"" " * ^&# '*^ ' *v ^
--T- RECOVERX»»f BH^3-PCB , RECOVERY « * BH-R4-PCB^|j:^RECOVERYi-
•'""JT (%)i:|SlWff»f(pgAiample) «%) (pg/sample) '*"• '*','"(%} *"*
63
59
62
49
63
82
84
53
54
60
60
54
52
2780
2450
2650
2270
2550
3270 tt
3330 #
2040
2360
2580
5140
1210
5090
70
61
66
57
64
82
83
51
59
64
64
61
51
2080
2610
2?10
2200
2620
3350
3300
2660
2350
2500
5380
414
2760
52
65
73
55
66
84
82
66
59
63
67
?!
28
O)
—k
O
tt = Value from second column confirmation.
* = Extract was diluted with additional internal standard and re-analyzed to bring PCB-77 concentration within calibration range. Concentration has been
corrected for original extract PCB-77 recovery (shown). Original dilution factor 1:2, PCB-77 result dilution factor 1:25.
E = Original result above calibration range.
DL = Detection limit.
-------
I3C12-PCB-81 and 20-130% for 13C12-PCB-1II.1 Recovery of the cleanup standards in the front half
air samples were within the limits and ranged from 53-65% for 13C12-PCB-81 and from 41-57% for
13C12-PCB-111 indicating that analytes were well retained through the extract cleanup procedures.
Recoveries of the pre-sampling surrogates in the back half air samples were also within the limits
and ranged from 21-61% for I3C12-PCB-81 and from 28-52% for 13C12-PCB-111. The pre-sampling
surrogate recoveries indicate how well analytes are retained from field sampling through laboratory
analysis. While all the pre-sampling surrogate recoveries were within the target recovery range, the
pre-sampling surrogate recoveries in Run 4 (21%, 28%) were approximately half of the recoveries
for the surrogates in Runs 2 and 3 (51-61%). 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 in Run 4
suggests loss of this standard during sampling, handling, and/or transport to the laboratory prior to
the sample extraction process or as the result of sample matrix interferences which resulted in poor
recovery of internal standards. We have witnessed poor standard recoveries for internal standards
for PCB, PAH, and D/F (0 to 30% range) in municipal waste combustion and medical waste
combustion air matrix samples. The cause is unknown as yet. A discussion of what might have
resulted in the lower Run 4 results is provided in Section 2.3. Since PCB concentrations are not
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 are
adjusted for the pre-sampling surrogate concentrations as shown in Table 6-7b, then the results
Method specified limits for the PCB labeled compound recoveries were selected as follows. A very limited method
evaluation was undertaken prior to initiation of this test program. No additional body of recovery data for toxic PCBs in
incinerator emissions using HRGC/HRMS techniques existed to augment the limited method evaluation results. The closest
available data regarding the range of anticipated labeled compound recoveries was EPA Method 1668 for toxics PCBs in other
matrices. Since much of the method sample cleanup was based on Method 1668, the estimate of reasonably achieved recovery
ranges included in the method were the result of merging recoveries achieved in the method evaluation with the recovery range
listed in Method 1668. The recovery ranges for internal standards in the method used (30-150%) are not out of line with
recovery ranges for labeled internal standards in other EPA methods utilizing HRGC/HRMS techniques (e.g., Method 1668 =
21-178% and dioxin methods SW846 Method 8290 = 40-135%; EPA Method 1613 = 25-150%; EPA Method 23 = 40-130% for
tetra through hexa chlorinated compounds and 25-130% for hepta-octachlorinated compounds). The cleanup and pre-sampling
surrogate standard recovery ranges of 10-150% for 13C12-PCB-81 and 20-130% for 13C12-PCB-111 may appear on the surface to
be significantly worse than pre-sampling surrogates in EPA Method 23 for dioxin (70-130%), however, there is a fundamental
difference in that the Method 23 surrogates are quantified against the labeled internal standards added prior to extraction of the
sample, and are therefore inherently corrected for any losses in extraction and/or cleanup, whereas the PCB surrogates are
quantified against the recovery standard added at the end of cleanup, just before HRGC/HRMS analysis. Because this
quantification relationship does not correct for any losses that may be experienced in extraction and cleanup, the recovery range
for the PCB surrogate standard can be expected to be more in line with the recovery of other labeled internal standards as listed
above.
6-11
-------
Table 6-7b. Back Half Air Data Corrected for Pre-sampling Surrogate Recovery
ANALYTES
PCJ3-77 JE
PCJ3-77
PCB-123
PCB-118
PCB-114.
PCJ3-105
PCB-126
PCJ3-167
PCB-156
PCB-157
PCB-169
PCJ3-180
PCB-17Q
PCB-189
- RUN 2 ;
(pa/sample)
276000
171000
125.6.
60800
.4.120.
2820.0
. ..7.6.6.0.
4160 . ...
6860
2360
6040 ...
29QQO
11660
1016
3>:RIJN*3-; *;
(pa/sample)
24.Q.QO.Q
117600
1.1.7.2
56400
3.6.4.0.
2.6.20.0.
6.420.
3.64.0.
6080
19.3.2
5.1.4.0.
26000
1 0.5.4.0
818
RUN 4
(pa/sample)
19.34.0.0
11420.0
9.3.0
.55.8.0.0
3.4.8.0.
23.6.0.0
5.6.6.0.
3.50.0.
53.80
2.Q.4Q.
3.6.8.0.
224QO
1..1.5.2.Q
1110
^ AVERAGE
(Da/sample)
23.64.6.7
13.426.7
1.1.19.
.57.6.6.7.
3.747.
26.0.Q.Q
6.5.8.0.
3.7.6.7.
6.1.0.7.
2.1.11
4.9.5.3.
. .25.8.0.0
1.12.4.0
981
-~; 5-,. ,'<* < ,=
STANDARD
DEVIATION
414.1.3
.318.5.7
16.9
2.7.3.0.
3.3.3
2.3.0.7.
l.Q.1.0.
3.4.8
7.4.0
223
1.19.1
3.30.5.
6.1.0
149
^;Rsbl|y
-? (%i •
.1.8.
24.
.1.5.
5
9
9
.1.5.
9
.1.2
.1.1
24.
.1.3.
5
15
E = Estimated value since calibration range exceeded.
between the three runs agree well within the <50% RSD precision QA/QC requirement for the
analytes with actual RSDs ranging from 5-24%.
Because PCB-77 was detected significantly above the highest calibration level for Runs 2,
3 and 4 back half emission extracts (data flagged with "E" in Tables 6-7a and 6-7b), these
extracts were diluted with additional internal standard in an effort to bring PCB-77 within the
calibration range. These three back-half emission extracts were spiked with an additional 48,000
pg of 13C12-PCB-77 to bring the total amount of 13C12-PCB-77 added to the extracts to 50,000 pg.
The extracts were then diluted to a final volume of 500 /uL in order to bring the concentration of
13CI2-PCB-77 in the diluted extract to 100 pg//uL, which is the same concentration used in the
calibration solutions. Diluting the extracts from 20 /^L to 500 /-iL and adjusting the internal
standard expands the calibration range for PCB-77 from the original 20 - 8,000 pg/sample to
500 - 200,000 pg/sample. Because the additional 13C12-PCB-77 was added after-the-fact, the
concentration of PCB-77 calculated against this is no longer inherently corrected for recovery of
analyte through extraction and cleanup. As a result, the concentrations of PCB-77 detected in the
diluted extracts were corrected for the original recovery of 13C12-PCB-77 in the undiluted extract.
6-12
-------
The PCB-77 concentrations determined in the diluted, recovery corrected extracts were within
the calibration range and are flagged in Table 6-7a with an "*".
Lab Control Samples. Tables 6-8a and 6-8b present PCB results and standard recoveries
for the laboratory control spike and laboratory control spike duplicate (LCS/LCSD) samples for
front half and back half air samples. Recovery of all native PCBs spiked into the LCS/LCSD for
both front and back half air samples were within the 70-130% target recovery range except for
PCB-77 in the LCSD sample for back half airs (134%) and PCB-114 in all LCS/LCSD samples
(146-167%). The relative percent difference (RPD) between duplicates were all under the target
<30% and ranged from 0.1 to 6.3% for front half air samples and from 0.4 to 8.1% for back half
air samples indicating acceptable analytical precision was achieved. Several analytes (PCB-123,
PCB-114, and PCB-105) in both the front half and back half LCS/LCSD samples were detected
above the calibration range and are flagged with an "E" in Tables 6-8a and 6-8b. These samples
were not diluted and reanalyzed since the samples had been spiked intentionally with a level of
these standards close to the upper range of the calibration curve, and with the exception of PCB-
114, concentrations detected were within 20% of the upper calibration level. Internal standard
recoveries for LCS/LCSD samples were all within the target 30-150% and ranged from 33-62%
for front half LCD/LCSD samples and from 34-114% for back half air LCS/LCSD samples.
Cleanup standard recoveries for front half air LCS/LCSD samples were 61-63% for 13C12-PCB-
81 (target recovery = 10-150%) and 42-45% for 13C12-PCB-111 (target recovery = 20-130%).
There were no pre-sampling surrogates added to the LCS/LCSD for the back half air samples as
only XAD which was shipped to the field received the pre-sampling surrogate standard.
Blanks. Table 6-9 lists PCB results and standard recoveries for the method blanks and
the XAD background check sample used to verify cleanliness of XAD before shipping the
sampling trains to the field. Table 6-10 lists PCB results and standard recoveries for field and
proof blanks associated with the front half air samples. Table 6-11 lists PCB results and standard
recoveries for field and proof blanks associated with the back half air samples. PCBs are quite
prevalent in the environment and are commonly found in laboratory solvents and reagents
making excessive background concentrations of PCBs common. The levels of PCBs detected in
the various blanks are typical of background levels detected using the sensitive high resolution
mass spectrometry techniques. Because PCBs are detected in the lab blank and because some
samples did not contain high levels of PCBs above the background levels (such as the front half
6-13
-------
Table 6-8a. Summary of PCB Results and Standard Recoveries for Front Half Lab Control Spike and
Spike Duplicate Samples
en
ANALYTEsiM'i
PCB-77
PCB- 123
PCB-118
PCB-114
PCB- 105
PCB- 126
PCB-167
PCB-156
PCB-157
PCB- 169
PCB- 180
PCB-170
PCB-189
- ',;•"'' '^,"\ ' ••,: ,-iLCS^,-
TARGET , 'SPIKEMji
,"?RECOVERY>'i' ^CONC.lff
"(%¥?;{%)" ~~-'.'i~ (pg/sample)*
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
400
20000
20000
20000
20000
2000
20000
20000
20000
4000
20000
4000
4000
LAB BLANK • •-•.• • .; ,'f->LCS,B*KMfc,s
/I 48190-11-10 '; 48190-li$8|f«
jfji FH-LB-PCB :-; < '. FH-LCS-PCB'jg?
f|f(pg/sample| (pg/sample J '
71.6
570
2010
767
1400
32.0
466
593 #
489 #
36.8
37.3
122
53.1
. ,, ^/'yjj^m^j^^, LCS ^ LAB BLANK ,
•'-,'"• •' :v^Jiftip!rARGET';". -: t SPIKE 'V'' ^48190-11-10 ?
INTERN AL%|||ilRECOVERY CONC, ''•',, FH-LB-PCB'*
STANDARDS 'WlS(%J ? I ! {pg/sample) (pg/sample)
13C-PCB-77
13C-PCB-118
13C-PCB-105
13C-PCB-126
13C-PCB-167
13C-PCB-156
13C-PCB-157
13C-PCB-169
13C-PCB-180
13C-PCB-189
13C-PCB-209
CLEANUP STAr
13C-PCB-81
13C-PCB-111
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
30-150
DARDS
10-150
20-130
4000
4000
4000
4000
4000
4000
4000
4000
4000
4000
8000
2000
10000
1160
352
398
910
436
676 »
682 #
1010
938
742
1700
572
1590
1070
45400 E
35100
59100 E
46200 E
4700
45700
51200 ff
49000 #
7990
45400
10000
8620
"^VJ-'XLCS^iT?
,%,4' 8 190-1 1-b83fl
^FH-LCS-PCB*!!
v'/ (pg/sample) ?'IW
2360
1310
1420
1740
1340
2120*
2000*
1710
1690
1850
2870
1260
4160
•5, ,'{,,»•:-<«-; • ' , LCS DUP ; *>••• ..v, -£jU **:'•,-' - , * r-'W/,,'*
ffj'-'.-i--' "'." . 48190-11-09* ••''^'J'^'^V'''^ , RECOVERY
: RECOVERY) -5FH-LCSDUP-PCB : RECOVERY R^Dlll;
{%) -. ^ .-'.,- (pg/sample| .- " ' v {%) ~- ':' "'" : ' {%|'ffe
125
112
83
146&
112
117
113
127
121
99
113
123
107
^RECOVERY
JK; {%)
59
33
36
43
33
53
50
43
42
46
36
63
42
1040
45000 E
35300
59000 E
45700 E
4590
45700
51300 #
49100 #
7960
44900
9390
8670
121
111
83
146 &
111
1.14 j
113
I??
122
99
111
116
108
3.9
1.0
0.6
0.1
1.2
2.5
0.1
0.2
0.1
0.4
1...3.
6.3
0.5
LCS DUP, -: ; /:^h'.^->r*<^^;^>"l':•i;^f/'
481 90-1 1-09 ; "• ' •.,*;' |:"f 'if& •"• '&* ": %RECOVERY
FH-LCSDUP-PCB ".'''t-. RECOVERY^,'. ,'^VPO^
(pg/sample) ': 1'^-;=(%)i*Jfifr;;',::'(%)fSA
2210
1340
1410
1830
1460
2480 tt
2380 #
1770
1820
1920
3050
1220
4460
55
33
35
46
37
62
60
44
46
48
38
61
45
% Recovery is calculated as ((concentration found - lab blank sample cone.I/spike cone.) x 100.
& = QC value outside the target recovery goal for Method.
# = Value from second column confirmation.
RPD = Relative percent difference.
E = Result above calibration level.
-------
Table 6-8b. Summary of PCB Results and Standard Recoveries for Back Half Lab Control Spike and
Spike Duplicate Samples
O)
•.'. . :>•! TARGET' .-
; /*>,V-,^ , ' RECOVERY'
ANALYTES "'•' " (%)
PCB-77
PCB-123
PCB-118
PCB-114
PCB-105
PCB-126
PCB- 167
PCB-156
PCB-157
PCB- 169
PCB-180
PCB-170
PCB-189
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
70-130
TARGET
INTERNAL RECOVERY
STANDARDS -""•• (%)
13C-PCB-77
""i'3c"-PCB-i'i8
"i'3c-p'c"B-io5
13C-PCB-126
'"i'3C-PCB'-i'67
"'i'3C"PCB-i'56
"'i"3C-PCB-i"57
""i'sc-PCB-i'e'g
13C-PCB-180
"'i'3C-PC"B-'i'89
13C-PCB-209
PRE-FJELD SURR
13C-PCB-81
13C-PCB-111
30-150
30-150""
30-150""
30-150
30-156'""
30-150""
30-150""
30-150""
30-150
30-150""
30-150
OGATESTANp
10-150
20-130
LCS LCS *,."•-.;.- •' . - ' tCS DUP -. fft\f . , ,.'.' ,'-:^^ LAB BLANK = |. - '.i^^ft-
; SPIKE 481 90-09-09 1; :.''•'-. 48190-09-10 -' - "i^ff, , - . ' RECOVERY.jy"; ,481 90-09-1 1- " ^~':~^SJS
"StfCONC. ' 'fr BH-LCS-PCB " "RECOVERY BH-LCSDUP-PCB RECOVERY ' ; ; :;,;s RPD1!;^^; BH-LB-PCB ,.,. , "Jk DL -Iff!-
(pg/sample) (pg/sample) (%) (pg/sample) ' (%) ; V>(%) .:S$" (pg/sample) (pg/sample)
800
40000
40000
40000
40000
4000
40000
40000
40000
8000
40000
8000
8000
1060
45000 E
35500
61800 E
47100 E
4680
44900
47400
45700
7880
44000
9640
8360
127
112
86
154&
116
117
112
118
114
98
110
120
104
1120
46900 E
36600
67000 E
48300 E
4750
47500
4970 tt
47100 #
8100
46600
9600
8080
Ui'$a.-y' -••'-' ••"• ''''.'• LCS ~"K"'. ::"' •'"' LCS DUP
'tSPlKE 48190-09-09 ^ 48190-09-10
CONC.; BH-LCS-PCB '' * RECOVERY BH-LCSDUP-PCB
(pa/sample) (pg/sample) •' ' (%) • • (pg/sample)
4000
4000
4000
4000
4000
4000
4000
4000
4000
4000
8000
\RDS
2000
10000
1.600
1360
i'5'20
1660
i"640
249b"#
253"6"#
1830"
1520
i'660
3460
NA
NA
40
34
38 ;•;
«
41
62
;"""$ci
46
38
4i"
43
:
4550
i'gg'o
"""!;i"MC!"™!;
2410
i'980
2886"#
2870'#
2110
1870
i'930
3820
NA
NA
134&
117
88
167 &
119
119
119
124
118
101
116
119
108
5.6
4.3
3.1
8.1
2.3
1.4
5.5
4.7
3.1
2.8
5.6
0.4
3.7
50.0
40.3
1 23"6
81 .7 E
573 E
4.25
50.4
95.6 #
32.3 #
4.50
181
77.1
6.01
*<:. •"-, . ;~TV, - LABBLANK-- "fe.fr - •«
. _V,;", "".' RECOVERY f ; 48190-09-1 1 < - f/§\ ' ;lt
RECOVERY ? -/RPD '""'"$'/" BH-LB-PCB ', ',1DL'; :***
(%) (%) * ! (pg/sample) (pg/sample)
114
50
54
60
50
72
72
53'
47
48
48
........................
........................
:
2310
1470
i'580
1720
i"680
22"2b"#
2160"#
1680
1560
i"570
3920
NA
NA
58
37
39
43
42
55
54
42
39
39
49
Recovery is calculated as ((concentration found - lab blank sample cone.I/spike cone.) x 100.
& = QC value outside the target recovery goal for Method.
# = Value from second column confirmation.
DL = Detection limit.
NA = Not applicable.
E = Result above calibration range.
-------
Table 6-9. Summary of PCB Results and Standard Recoveries for
Background and Method Blank Samples
ANALYTESi? "'''
PCB-77
PCB-123
PCB-118
PCB-114
PCB- 105
PCB- 126
PCB- 167
PCB-156
PCB-157
PCB-169
PCB- 180
PCB- 170
PCB-189
s i'3*;sy
INTERNAL
STANDARDS
13C-PCB-77
13C-PCB-118
13C-PCB-105
13C-PCB-126
13C-PCB-167
13C-PCB-156
13C-PCB-157
13C-PCB-169
13C-PCB-180
13C-PCB-189
13C-PCB-209
CLEANUP
STANDARDS
13C-PCB-81
13C-PCB-111
„' . - » •' *• - <• "" >
;^-;V ' C- - * V,* -4 '
SPIKE
CONC.
(pg/sample)
4000
4o"6b
4000
4000
4000
4000
4000
4000
4000
4000
8000
2000
10000
:,;•.-- -'Sf-Sft «i»%-
METHOD BLANK
i,4820pt51^03 '
< (pg/sample)
4.92
ND
134
5.09
67.0
ND
4.73
11.4
2.86
(0.59)
21.6
ND
ND
METHOD BLANK
48200-51-03
(pg/sample)
3560
1780
1600
2210
1960
1720
1620
1720
1290
1380
3610
NA
NA
. !i'S-'/M%.S
'Js^^ju ^•-^-^s&fel5
: l4£ipL"-,5;V
(pg/sample)
16.9
2.32
1.28
12.0
11.5
RECOVERY
,'r;-(%),,'V-r'
189&
44
40
55
49
43
40
43
32
35
42
>o, yijfeysiij , "- ,-*|
\'XADJBCKGRD|i"
'--48200!-5J'-02S
*{pg/sample) •
13.0
ND
301
ND
139
ND
12.1
27.6
ND
ND
213
115
ND
XAD BCKGRD
48200-51-01
(pg/sample)
2810
1780
1540
2000
1930
1750
1610
1720
1470
1540
3760
NA
NA
^^ \^DL'$jl -''II
(pg/sample)
19.7
6.02
3.09
2.77
1.67
15.0
RECOVERY
« (%)
70
45
38
50
48
44
40
43
37
38
47
DL = Detection Limits; {EMPC}; (Below Detection Limit).
ND = Not detected, detection limit value provided in adjacent righthand side column.
NA = Not applicable.
6-16
-------
Table 6-10. Summary of PCB Results and Standard Recoveries for Field Blank and Proof Blank Front Half Air Samples
O)
• ;''!'- '• . <''\ .»„", };i'i 7 ,,,"|",:.rt!,;*i
ANALYTES
PCB-77
PCB-123
PCB-118
PCB-114
PCB-105
PCB-126
PCB-167
PCB-156
PCB-157
PCB- 169
PCB-180
PCB-170
PCB-189
i „ , T,,™ a* 4* j"
•',-';' ''iyk^^TARGET/-:''?
INTERNAL & RECOVERY.
STANDARDS ' ' •'>'"' *(%J -AS*
13C-PCB-77 30-150
13C-PCB-118 30-150
13C-PCB-105 30-150
13C-PCB-126 30-150
13C-PCB-167 30-150
13C-PCB-156 30-150
13C-PCB-157 30-150
13C-PCB-169 30-150
13C-PCB-180 30-150
13C-PCB-189 30-150
13C-PCB-209 30-150
CLEANUP STANDARDS
13C-PCB-81 10-150
13C-PCB-111 20-130
•IrV^yy,;;
"Mttf&k'rtfa
•fc.SPIKE'HI
_,.-?_ CONC^
(pg/sample)
4000
4000
4000
4000
4000
4000
4000
4000
4000
4000
8000
2000
10000
FIELD BLANK 1
,-',,,48190-11-07*';
'•'- FH-FB1-PCB
(pg/sample)
67.8
33.5
1460
61.3
655
4.50
37.6
85.7 #
17.8 tt
ND
163
67.2
ND
; FIELD BLANK 1 1?
«'V48190-11-07",--,
•S%FH-FBi-PCBy~-
''•* (pg/sample) * '
2580
1920
2060
2270
1920
2860*
2690 #
2060
2210
2030
1930
1370
5880
-.;,.- DL'y.,
(pg/sample \,
2.13
3.44
RECOVERY,,
(%) • Wi
64
48
51
57
48
71
67
52
55
51
24 &
68
59
PROOF BLANK ,1, T
'/ 48190-1 1-05""4^
• FH-PB1-PCB%->*1
s> (pg/sample)
77.6
30.4
1310
53.6
589
6.19
40.9
85.6
17.5
ND
186
72.8
4.88
PROOF BLANK 1
48190-11-05
FH-PB1-PCB
>* (pg/sammple)
2440
1680
1820
20650
1690
2640*
2580 #
1930
1970
1930
2930
1240
5160
-"* -' • • '*' *~'^~
s '<"»"->'•" • ' ' •'
f ;','!,, DLV^,
(pg/sample)
2.31
RECOVERY^;
(%) f/4:
61
42
46
51
42
66
64
48
49
48
37
62
52
4PROOF BLANK 2
:'i-:H48190-,11-06 • *'"
FH-PB2-PCB
t •" " (pg/sample)
186
206
5450
321
2630
13.1
208
393 #
154#
13.3
555
204
18.3
, PROOF BLANK 2
: 48190-11-06
•y\ FH-PB2-PCB ;/; .
If (pg/sample) -\.
1820
1090
1180
1570
1140
2050 #
18300
1530
1510
1530
2020
930
3470
t *-;\ i \> f ^ ,/~ ^ T
:'':?!|ft4: 'X*
-: ^DL,^.--
(pg/sample)
"",.^ji»^>
«i "t'%jl''«'&'0i,i^
RECOvlfiYx
».;i i%} ^&
46
27 &
29 &
39
298.
51
46
38
38
38
25 &
46
35
DL = Detection Limit, value specified only when analyte is not detected or else flagged {EMPC}; (Below Detection Limit).
ND = Not detected, detection limit value provided in adjacent righthand side column.
# = Value from second column confirmation.
& = QC value outside the target recovery goal for Method.
-------
Table 6-11. Summary of PCB Results and Standard Recoveries for Field and Proof Blank Back Half Air Samples
en
CO
-,, •„ ,«»-» -'-(,», »•/»-,->'-". ••' -• HtLO BLANK ,.1 „ ; • , >- KKUUh BLANK 1 ,,,-,,• 7;, ,, ., •
';"-'"•• ',:---/i ;^ \%-'''*f?v";> • i48190-094>7 ',. ' ' ,',Y/;'48190-09-06;-'-".V-^V "",' •
' ;'';#;. ;,,V/?<:J.-- £~>l£'u!:'-i'i>>: : ' "BH-FB1-PCB«: " . DL '"'""<• ^'BH-PBWCB;/,^. '':" DL .
lANALYTES'.-'-!f£w;A/;W-;'" -"•"-.'"lU^.V • . • ' (pg/samplejil ; (pg/sample . '..' MpgVsample) 34? ; .-'(pg/sample .-•
PCB-77
PCB-i23
PCB-118
PCB-i 14
PCB-ibs
PCB-i "26
PCB-i 67
PCB-I 56
PCB-i 57
PCB-i 69
PCB-i 80
PCB-i 70
PCB-I 89
&$£•.'' •$${ ",; *
flNTERNAfe-v"^
STANDARDS """••
13C-PCB-77
13C-PCB-118
13C-PCB-105
13C-PCB-126
13C-PCB-167
13C-PCB-156
13C-PCB-157
13C-PCB-169
13C-PCB-180
13C-PCB-189
13C-PCB-2b9
PRE-SAMPLING J
13C-PCB-81
13C-PCB-111
fM^l^€<*V:,4%'.^(^',|'?,;s,,*, •/•
iiARGET
flRANQE^glf iCONC/'- 'i'f
*HI:i%) ?<--"'5St'(pl/'8amptej -"' -
30-150
30-150
30-150
30-150
30 - 1 50
30-150
30-150
30 - 1 50
30 - 1 50
30-150
30-150
URROGATE
10-150
20-130
DL = Detection Limits; {EMPC]
& = QC value outside the accur
ft = Value from second column
4000
4000
4000
4000
4000
4000
4000
4000
4000
4000
8000
STANDARDS
2000
10000
178
72.0
1780
130
873
16.2
92.7
155
61.6
7.51
285
116
10.1
FIELD BLANK 1
i, H81 90-09-07 RECOVERY
i'V.BHfBi-PCBV^ • •;,-;•(%) <• '
(pg/sample) ' . (pg/sample)
3140
1980
2120
2370
2280
2900 #
2820 #
2510
2200
2250
5170
1440
4920
79
50
53
59
57
73
70
63
55
56
65
72
49
182
32.1
1740
77.3
835
11.9
55.4
123 ft
28.7
. ..{1...14}
258
121
6.94
PROOF BLANK 1"*
f:><48190-09-05|p
^r*BH-PB1-PCBjff
*.**'- (pflAsampto)^r«v
2740
1860
1940
2430
2060
2760*
2730 #
2500
2020
2200
4790
1310
4610
HHUUIr BLANK Z - -, ., ivr^u*
48190-09-06 ''-' • ", • '^'f^ff';''
, /-.BH-PB2-PCB" ' • DL*"J »'].,-
y,. 'id (pg/sample) "•• >' "-• (pg/sample)
463
167
8010
324
3370
12.4
135
316 it
59.4 #
3.07
536
200
6.13
*'"•'.'"• ' PROOF BLANK 2 t; , , , '
RECOVERY 48190-09-06 :• RECOVERY
; i%) '• • ABH-PBJN&CB • V .. • . (%h3j»''
(pfl/sample) (pg/sample) , (pg/sample)
68
47
49
61
52
69
68
62
51
55
60
65
46
2150
1770
1960
2310
1900
2740 #
2810 #
2300
2090
2390
4950
964
4190
54
44
49
58
48
68
?.Q
57
52
60
62
48
42
(Below Detection Limit).
acy or precision goal for the Method 10% - 1 50% recovery of standard spiked samples).
confirmation.
-------
air samples), there are several instances where the lab blanks exceeded the method performance
criteria of being at less than 20% of the sample concentration. Results for Runs 2, 3 and 4 are
flagged with a "B" in Tables 6-6 and 6-7a and in result tables presented in Section 2 of this
report if the lab blank concentration was greater than 20% of the reported sample concentration.
The target detection limit for these samples was 100 pg/sample. Actual detection limits
achieved were significantly lower than this.
The target turnaround time for the PCB analysis of emission samples was to extract
within 30 days of collection and analyze within 45 days of extraction. These turnaround times
were met with extractions occurring within 11 days of collection and analysis occurring within
30 days of extraction.
D/F Analysis. The initial calibration met the requirement for response factors having less
than 20% relative standard deviation (RSD) for native analytes and less than 35% RSD for
labeled analytes (actual range = <13% for native analytes and <19% for labeled analytes). The
continuing calibrations met the requirement for response factors being within 20% of the initial
calibration response factors for native analytes and being within 30% of the initial calibration
response factors for labeled analytes for all D/F but 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% criteria which is derived from Method 8290. The
emission samples were analyzed using Method 23 calibration and internal standard solutions (see
QAPP amendment 9) and all but the OCDF response factor from the middle continuing
calibration met the Method 23 objective of being within 30% of the initial calibration.
Field Samples. Summary tables of D/F results and standard recoveries for the front half
and back half air samples are shown in Tables 6-12 and 6-13, respectively. 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% and ranged from 54-98%. Internal standard
recoveries in the back half air samples were also within the 40-135% limits and ranged from 47-
95%. These internal standard recoveries indicate analytes were well recovered during laboratory
extraction and were retained during the extract cleanup process. 37Cl4-2,3,7,8- TCDD was added
as a cleanup standard (after extraction, but before any cleanup procedures) in processing the front
6-19
-------
Table 6-12. Summary of Dioxin/Furan Results and Standard Recoveries for Front Half Air Samples
'•'"'"' ~\;' .' ,'4:- ';:"';-Sl|l^,v4:vX
ANALYTES •--. -"•'-.":' >"», -. '•. r-; : - - '• 'Vft'ifr '.
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Total Tetra-Furans
Total Tetra-Dioxins
Total Penta-Furan
Total Penta-Dioxins
Total Hexa-Furans
Total Hexa-Dioxins
Total Hepta-Furans
Total Hepta-Dioxins
Total TEQ
RUN 2
48190-11-02
FH-R2-DIOX
(pg/sample)
6.08 tt
ND
5.44
13.7
24.9
205
689
108 It
23.4
79.1
76.1
29.6
ND
75.4
156
20.6
129
698
324
624
69.9
360
239
244
431
98.4
DL
(pg/sample)
15.0
6.32
RUN 3
48190-11-03
FH-R3-DIOX
(pg/sample)
ND *
ND
ND
9.58
ND
138
429
55.6 #
14.2
34.1
32.3
16.0
ND
37.1
83.9
(7.65) J
102
395
181
263
21.3
136
140
91.5
314
38.6
DL
(pg/sample)
2.98
15.2
5.10
3.11
6.28
9.77
L RUN 4
48190-11-04
FH-R4-DIOX
(pg/sample)
ND.*
ND
ND
10.3
16.0
127
404
85.8 tt
16.7
47.2
41
18.0
ND
40.3
90.4
(10.4) J
82.1
594
142
380
15.9
194
182
98.5
296
52.5
, , sr $'&$.
DL
(pg/sample)
4.49
17.8
5.49
7.17
1.1,0
20.2
O)
NJ
O
-------
Table 6-12. (Continued)
ANALYTES
INTERNAL STANDARDS
13C-2378-TCDD
13C-12378-PeCDD
13C-123678-HxCDD
13C-1234678-HpCDD
13C-OCDD
13C-2378-TCDF
12378-PeCDF
123678-HxCDF
1234678-HpCDF
CLEANUP STANDARDS
37CI-2378-TCDD
KlTARGETII
RANGE *
1 <'•? (%) '-.•- :
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
?i SPIKE , •>>.,
CONC. ;'"'"~'
-, (pg/sample) •
8000
8000
8000
8000
16000
8000
8000
8000
8000
800
RUN 2
, 48190-11-02
? FH-R2-DIOX
(pg/sample)
5580 tt
7640
5980
6660
13000
5170 #
6760
5240
6340
820 #
RECOVERY 4
(%)
70
95
75
83
81
65
84
65
79
103
RUNS
48190-11-03
FH-R3-DIOX*
(pg/sample)
6010 #
7870
6060
6850
14600
5540 H
6920
5400
6484
800 #
RECOVERY
(%)"'-*.-'--
75
98
76
86
91
69
87
67
81
100
? RUN 4
48190-11-04
FH-R4-DIOX
(pg/sample)
4510 #
6780
6060
7160
15500
4300 #
5710
5070
6370
796 #
, * '-%'V.V :
•=b- -" ~'VH>.
RECOVERY
i%) ; ,
56
85
76
90
97
54
71
63
80
100
O)
DL = Detection Limits; {EMPC}; (Below Detection Limit).
# = Value from second column confirmation.
ND = Not detected.
J = Value found below the detection limit
-------
Table 6-13. Summary of Dioxin/Furan Results and Standard Recoveries for Back Half Air Samples
•''"*-'*''', "' '.'' ' '^*4*'f;5iji|;v'!';;';
'*•' • "•*' '\ ' "; '"'"'. X^vvfi/fg,,. .-. '' I' '-'•''•.
ANALYTES ','"•. '. : - -•<•<*% ,-i^Ji--; - '"'••
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Total Tetra-Furans
Total Tetra-Dioxins
Total Penta-Furan
Total Penta-Dioxins
Total Hexa-Furans
Total Hexa-Dioxins
Total Hepta-Furans
Total Hepta-Dioxins
Total TEQ
RUN 2%
48190-09-02 1:
BH-R2-DIOX
(pg/sample)
565 #
97.9
81.5
209
{203}
991
1160
9150*
1110
2190
1240
447
ND
661
1150
109
397
32100
17400
28200
4060
6220
3300
1680
2250
2530
, ' ; ,j"; >*' ,1
DL
(pg/sample) .--
12.2
; I/^'mm&t: '• '
48190-09-03
BH-R3-DIOX,
(pg/sample) ,
418 #
78.4
90.1
235
217
1120
1460
7630 #
920
1720
1070
396
ND
563
1060
99.8
41.2
30000
21800
22500
4070
5330
3490
1530
2500
2080
DL ;;'O
(pg/sample) ~ <
14.1
RUN 4
48190-09-04
BH-R4-DIOX
'} (pg/sample)
225 #
33.2
38.4
76.1
106
496
534
3490 #
433
775
575
213
ND
303
593
46.4
197
16600
4680
9910
1240
2550
1990
815
1290
983
DL
(pg/sample)
15.7
CD
NJ
Ni
-------
Table 6-13. (Continued)
ANALYTES
INTERNAL STANDARDS
13C-2378-TCDD
13C-12378-PeCDD
13C-123678-HxCDD
13C-1234678-HpCDD
13C-OCDD
13C-2378-TCDF
12378-PeCDF
123678-HxCDF
1234678-HpCDF
PRE-SAMPLING
SURROGATE STANDARDS
37CI-2378-TCDD
13C-123478-HxCDD
13C-23478-PeCDF
13C-123478-HxCDF
13C-1234789-HpCDF
> y-~ '••'" -»-
TARGET;
RANGE
.??(%)'.*
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
70-130
70-130
k 70- 130
L 70- 130
70 - 1 30
a,.;,. SPIKE '•':.-
CONC.
(pg/sample)
8000
8000
8000
8000
16000
8000
8000
8000
8000
8000
8000
8000
8000
8000
RUN 2
48190-09-02
. BH-R2-DIOX?
4V»> (pg/sample) '.
4960 ff
6190
5510
5970
14100
3840 #
5600
4880
5730
8440*
8320
7760
7840
6060
RECOVERY
% :• •
62
77
69
75
88
48
70
61
72
106
104
97
98
76
RUNS
48190-09-03
BH-R3-DIOX
(pg/sample)
4420 #
6220
5820
6580
15100
3740 #
5730
5380
6250
8740 #
9730
8490
8530
7610
'' ?">! -*.> A '
RECOVERY
(%)
55
78
73
82
95
47
72
67
78
109
122
106
107
95
RUN 4
48190-09-04
BH-R4-DIOX
(pg/sample)
4460 #
5880
5490
6160
14300
3970 #
5340
4960
5640
3840 #
4280
3620
4110
3460
*; v-^ivn^'.
&.:,'•; ,-•'<; . .' :
RECOVERY
(%) ,«
56
73
69
77
90
50
67
62
70
48 &
53 &
45 &
51 &
43 &
cn
M
CO
DL = Detection Limits; {EMPC}; (Below Detection Limit).
ND = Not detected.
# = Value from second column confirmation.
-------
half air samples. Recovery of this standard in the front half air samples ranged from 100-103%
indicating analytes were well retained in the cleanup process. 37Cl4-2,3,7,8- TCDD, 13C12-
1,2,3,4,7,8-HxCDD, 13C12 -2,3,4,7,8-PeCDF, 13C12 -1,2,3,4,7,8-HxCDF, and 13C12 -1,2,3,4,7,8,9-
HpCDF were added as pre-sampling surrogate standards spiked into XAD resin before shipping
to the field in the back half air samples. The specified recovery ranges for these standards were
from 70-130%. Recoveries of the pre-sampling surrogates in the back half air samples were
within the 70-130% limits for Run 2 and Run 3 (76-122%), but were uniformly low for Run 4
(43-53%). 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. In addition, the same pattern was seen in the back half PCB samples with
Runs 2 and 3 being comparable and Run 4 showing a drop in both analyte concentrations and
pre-sampling surrogate recoveries, while PCB internal standard recoveries were comparable
among all three runs. Since the D/F and PCB pre-sampling surrogate standard additions to XAD
were separate standard spikes, this eliminates the possibility of an error in spiking the XAD
before going to the field. Since the D/F and PCB sample fractions went through separate cleanup
procedures, cleanup activities can also be eliminated as causing the loss of analytes. As with the
PCB pre-sampling surrogate recoveries for Run 4, D/F pre-sampling surrogate recoveries for
Run 4 were approximately half that obtained in Runs 2 and 3. It is anticipated that if back half
D/F analyte concentrations were corrected for the recovery of the pre-sampling surrogates (as in
the example for PCBs in Table 6-7b) that acceptable precision among the replicate runs would be
obtained.
Lab Control Samples. Tables 6-14a and 6-14b present a summary of D/F results and
standard recoveries for LCS/LCSD front half and back half air samples, respectively. The
recovery objective for native analytes in the LCS/LCSD samples was 40-135%. The actual
range for the front and back half control spikes was 79-135% except for 2,3,4,6,7,8-HxCDF
which was recovered high in both the LCS and LCSD for the front half (138% in both), OCDF
which was recovered high in the LCSD for both the front half and back half (136% and 143%,
respectively), and 1,2,3,7,8,9-HxCDF which was recovered high on both the front half and back
half LCSD (141% and 147%, respectively). The RPD between analyte concentrations found in
6-24
-------
Table 6-14a. Summary of Dioxin/Furan Results and Standard Recoveries for Front-Half Lab Control Spike and
Spike Duplicate Samples
i";,"'.''- ' '••,-, Ji:'S' •* • •.'
ND#
ND
ND
ND
ND
ND
31.9
ND tf
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.032
- ^DLj^r
(pg/sample)
3.75
17.6
5.94
5.51
3.63
4.94
6.13
8.70
7.26
7.38
6.44
7.44
7.13
2.63
11.7
20.2
10.7
14.9
14.8
20.1
14.1
8.95
21.5
22.5
.i;HLC8\:,^0
48190-1 1-08, f
FH-LCS-DIOX
(pg/sample) -
930
4140
3860
4100
4270
4060
8290
933
4450
4760
4690
4530
5420
5540
4210
4600
10300
933
930
9210
4140
20200
12200
8810
4060
9080
H**'''^'/^ - i'
;;>';?,• r- ',''.•' "'
'RECOVERY
(%)
116
104
97
103
107
102
103
117
111
119
117
113
135
138&
105
115
128
-...i^tcs-DUP^-H
;-;48i9b^i^9;fe:
FH-LCSDUP-biOX
(pg/sample) ,, ,'
796
3940
3830
4110
3960
3900
7870
851
4300
3170
4710
4480
5650
5520
4160
5120
10800
851
796
7470
3940
20400
11900
9280
3900
8030
y '' ' '•* '' '-•' " ' ' ~
RECOVERY
{%}
99
99
96
103
99
97
98
106
108
79
118
112
141 &
138&
104
128
136&
IftS- '.-4
:'':-';-lt|
RECti^ERY
'"''' -(RPbjl4s
16
5
0.7
0.3
7
4
5
9
3
40
0.4
1
4
0.3
1
11
5.6
O)
ro
01
-------
Table 6-14a. (Continued)
INTERNAL STANDARDS
13C-2378-TCDD
13C-12378-PeCDD
13C-123678-HxCDD
13C-1234678-HpCDD
13C-OCDD
13C-2378-TCDF
13C-12378-PeCDF
13C-123678-HxCDF
13C-1234678-HpCDF
CLEANUP STANDARDS
37CI-2378-TCDD
. "^TARGETrl
RECOVERY;
•?•• (%) ;'*
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
: • >CCS; "( -
; SPIKE ;
4* coNcX- r
(pg/sample)
8000
8000
8000
8000
16000
8000
8000
8000
8000
800
LAB BLANK
„, 48190-11-10
T FH-LB-DIOX
t (pg/sample)
5110 #
6970
5820
6500
13800
4930*
6010
5140
5990
810 ff
.' "• DLV::"'1
(pg/sample)
64
87
73
81
86
62
75
64
75
101
LCS'V'-;'
48190-11-08
',', FH-LCS-DIOX
(pg/sample)
4270
7240
5830
7050
15300
3980
5510
4850
6380
820
!'.^ -:i.''-:,^V
RECOVERY
(%)
53
91
73
88
95
50
69
61
80
102
i'^lCS pUP;?<#'.f
48190-11-09
FH-LCSDUP-DIOX
(pg/sample)
5910
7070
5980
7570
16900
5040
5900
4940
6710
660
^If-gl^iJ
RECOVERY
(%)
74
88
75
95
106
63
74
62
84
83
fW?;f $:-'',;
4't'x.-*Jf , ffi&fA
RECOVERS
RPD
; :J:"(%) -•;'
NJ
Ol
DL = Detectionlimit.
ND = Not detected.
% Recovery is calculated as ((concentration found - blank field sample concen.)/spike cone.) x 100.
& = QC value outside the accuracy or precision goal for Method (40-135% Recovery of native compounds in spike samples).
# = Value from second column confirmation.
-------
Table 6-14b. Summary of Dioxin/Furan Results and Standard Recoveries for Back-Half Lab Control Spike and
Spike Duplicate Samples
''<<&,', •
"*',"., • . :
*~ ,. . ' If >*' * , ,, '!^
ANALYTES
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Total Tetra-Furans
Total Tetra-Dioxins
Total Penta-Furan
Total Penta-Dioxins
Total Hexa-Furans
Total Hexa-Dioxins
Total Hepta-Furans
Total Hepta-Dioxins
Total TEQ
s?7>^4
J>fARGET*''
(| RECOVERY
• V.f'(%)-.jl;i
40-135
40-135
40 - 1 35
40 - 1 35
40-135
40-135
40-135
40 - 1 35
40 - 1 35
40 - 1 35
40-135
40-135
40 - 1 35
40 - 1 35
40-135
40 - 1 35
40-135
'l/i j ;, LCS |%t¥l:
;ii ''*' SPIKE"''" '•
CONG. ji
(pg/sample) •*.-
800
4000
4000
4000
4000
4000
8000
800
4000
4000
4000
4000
4000
4000
4000
4000
8000
; LAB BLANK
48190-09-11
.BH-LB-DIOX
( '*•'. (pg/sample) =
(1.50) #,J
ND
ND
ND
ND
{0.319}
24.5
5.130
ND
ND
ND
ND
ND
ND
3.38
ND
(7.63) J
4.44
12.39
ND
ND
3.00
ND
8.51
{22.2}
0.544
,' "; V J ^' '
DL
(pg/sample .
1.81
10.1
3.19
2.94
1.94
5.00
4.19
4.07
3.50
4.07
3.94
5.76
9.95
8.45
11.4
4.82
-,-;,LCS^,.
48190-09-09 *
BH-LCS-DIOX
(pg/sample)
839
4040
3850
3870
4070
3910
7900
864
4170
4140
4550
4340
5200
1510
3920
4590
9610
884
839
8320
4040
19200
11800
8510
3910
8470
RECOVERY
(%) \ ":•
105
101
96
97
102
98
99
105
104
104
114
109
130
128
98
115
120
HcSDUP
48190-09-09
BH-LCSDUP-DIOX
• (pg/sample)
869
...4180 ,
3920
4190
4100
4100
8260
906
4430
4530
4840
4540
5870
5350
4190
4610
11500
906
869
8960
4180
20600
12200
8800
4090
8960
RECOVERY •„
(%)
109
104
98
105
102
102
103
110
111
113
121
114
147 &
134
105
115
143 &
' tC' , •";!?/
RECOVERY
:(RPD);
4
3
2
8
0
4
4
5
7
9
7
5
17
6
7
0
18
cn
-------
Table 6-14b. (Continued)
^|lf : '$, ;./••"•-;'?.•>.''''>; '" -MrARGETfe
^Xltk'feftW i^m, f|^ ; RECOVER^
INTERNAL STANDARDS 6 ""," (%j?«|tf
13C-2378-TCDD
...1.3.C:.12378.-j?.e.CDD
13C-123678-HxCDD
13C-1234678-HpCDD
13C-OCDD
13C-2378-TCDF
13C-12378-PeCDF
13C-123678-HxCDF
13C-1234678-HpCDF
PRE-SAMPLING SURROGA
37CI-2378-TCDD
40-135
4.0..-..1.3.5....
40-135
40-135
40-135
40-135
40-135
40-135
40 - 1 35
TE STANDARl
40-135
* LCS LAB BLANK
SPIKE 48190-09-1 |i
a >CONC%yt^ BH4.B-DIOX$p' RECOVERY-:
(pg/samplef i i (pg/sample) : iV <%)>
8QQO. ,
.ao.o.0.
8000
8000
16000
8000
8000
8000
8000
)S
800
49.1.0.J ,
.6.280. ,
5120
6040
14100
4660 #
5560
4400
5800
4
61
7.8
64
76
88
58
70
55
73
0.5
',LCS", '".*/' ;U
48190-09-09 *
•' BH-LCS-DIOX^i
(pg/sample) ;
5720
.7.55.0.
5720
7100
17000
5260
6320
4880
6510
NA
^V-'"'*: -: 48190-09309'^'
RECOVERY * '•» BH«LCSDUP-DIOXf?
','•',.!!'.(%) '•'•-"•. (pg/sampte)-«'-
72 ,
9.4
71
89
1.Q6
66
79
61
81
5360
.6.82.0.
5590
7120
16800
4960
5600
4720
6400
NA
RECOVERY RECOVEJi^
67 <
8.5
70
89
105
62
70
59
80
O)
ro
00
DL = Detection limit.
% Recovery is calculated as ((concentration found - blank field sample concen.I/spike cone.) x 100.
J = Estimated value, below detection limit.
& = QC value outside the accuracy or precision goal for Method (40-135% Recovery of native compounds in spike samples).
It = Value from second column confirmation.
ND = Not detected.
-------
the LCS and LCSD in the front half samples met the data quality objective of <20% (actual
values ranged from 0.3 to 16%) except for 2,3,4,7,8-PeCDF with an RPD of 40%. The RPD
between the LCS and LCSD for back half samples met the data quality objective of <20% for all
analytes and ranged from 0 -18%. Recoveries of internal standards and the cleanup standard
associated with the front half LCS/LCSD samples were all within the 40-135% target and ranged
from 50-106%. Recoveries of internal standards added to the back half LCS/LCSD samples
were also within the 40-135% range and ranged from 59-106%. Pre-sampling surrogate
standards were not added to the back half LCS/LCSD samples as only XAD which went to the
field received this standard. The internal and cleanup standard recoveries indicate that analytes
were efficiently extracted from the air sampling media and were retained during the laboratory
cleanup process.
Blanks. Table 6-15 lists D/F results and standard recoveries for all lab blanks and the
XAD background check sample used to verify cleanliness of XAD before shipping the sampling
trains to the field. Table 6-16 lists D/F results and standard recoveries for field and proof blanks
associated with the front half air samples. Table 6-17 lists D/F results and standard recoveries
for field and proof blanks associated with the back half air samples. Very few D/F congeners
were found in the blanks and those which were detected were at levels below the lowest
calibration level (40 pg/sample for tetra compounds, 200 pg/sample for penta-hepta compounds,
and 400 pg/sample for octa compounds). Recoveries of internal standards and the cleanup
standard in the lab blanks were within 40-135% and ranged from 55-101%. Recoveries of
internal standards and the cleanup standard in the front half field and proof blanks were within
40-135% and ranged from 40-101%. Recoveries of internal standards in the back half field and
proof blanks were within 40-135% and ranged from 61-89%. Pre-sampling surrogate recoveries
in the back half field and proof blank samples were all within the 70-130% limit and ranged from
91-127%.
The target detection limit for these samples, based on the lowest calibration level was 40
pg/sample for tetra compounds, 200 pg/sample for penta-hepta compounds and 400 pg/sample
for octa compounds. Actual detection limits achieved were significantly lower than this.
The target turnaround time for the D/F analysis of emission samples was to extract within
30 days of collection and analyze within 45 days of extraction. These turnaround times were met
6-29
-------
Table 6-15. Summary of Dioxin/Furan Results and Standard Recoveries for Lab and Method Blank Samples
ANALYTES '" - •" •"'-:•• ":^:M't
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Total Tetra-Furans
Total Tetra-Dioxins
Total Penta-Furan
Total Penta-Dioxins
Total Hexa-Furans
Total Hexa-Dioxins
Total Hepta-Furans
Total Hepta-Dioxins
Tntal TFO
LAB BLANK
•48190-11-10
FH-LB-DIOX
f- (pa/sample)
ND #
ND
ND
ND
ND
ND
31.9
ND #
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0 032
' i I'- , «
DL •••'••
(pg/sample)
3.75
17.6
5.94
5.51
3.63
4.94
6.13
8.70
7.26
7.38
6.44
7.44
7.13
2.63
11.7
20.21
10.7
14.9
14.8
20.1
14.1
8.75
21.5
22.5
LAB BLANK
S 48190-09-11
BH-LB-DIOX /
(pg/sample)
(1.50)#,J ,
ND
ND
ND
ND
.{0,319}.
24.5
5.13 #
ND
ND
ND
ND
ND
ND
3.38
ND
(7.63) J
4.44
12.39
ND
ND
3.00
ND
8.51
.{22,2}
0 544
DL
(pg/sample)
1.81
10.1
3.19
2.94
1.94
5.00
4.19
4.07
3.50
4.09
3.94
5.76
9.95
8.45
11.4
4.82
METHOD BLANK
48200-51-03
(pg/sampfe)
ND
ND
ND
ND
ND
ND
3,38
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(5.22) J
(0.13) J
ND
ND
(0.60) J
ND
ND
(0.64) J
NA
V--''DL< v',' •'.
(pg/sample)
1.74
4.60
2.35
2,71
3,25
1,68
2.58
1.53
2.62
1.80
1.77
1.55
1.96
1.53
2.74
7.56
11.0
4.38
3.24
47.1
3.98
3.84
4.94
5.68
• f'i",>-K ,-;"
XAD BCKGRD 7
48200-51-02
(pg/sample)
ND
ND
ND
ND
ND
(1.42) J
(3.09) J
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(0.95) J
(0.31) J
(0.24) J
ND
(0.17) J
ND
(0.49) J
(1.52) J
\: :
DL
(pg/sample)
2.46
7.80
2.93
3.30
4.01
1.91
3.66
3.49
2.08
3.61
2.25
2.20
1.79
2.43
1.77
3.05
8.62
14.9
6.20
4.46
79.9
4.87
4.73
5.60
4.98
O)
CO
O
-------
Table 6-15. (Continued)
O)
CO
i0f^^'\. .,11^;" ';: ." ,^;-; ': • '"" ';"''3p;;;i. ' ••• -"•• : -.-' • '. -.
./&;;',.- 4'- 4:*^' *'•' . SPIKE»p^-*481 90-11-10- .- ' 48190-09-11 ? !; METHOD BLANK .'-'':. J;^- , XADBCKGRD •- " '
Lt; '/*--! •'&-. fCONCirV FH-LB-DIOX RECOVERY BH-LB-DIOX RECOVERY * 48200-51-09, <: RECOVERY 48200-51-02 RECOVERY
INTERNAL STANDARDS T (pg/sampfer (Pfl/sample) ?':<(%)' Ipg/sample) {%) (pg/sample); ^ fe *?£(%) ; • '£ (%) VI
13C-2378-TCDD
13C-12378-PeCDD
13C-123478-HxCDD
13C-123678-HxCDD
13C-1234678-HpCDD
13C-OCDD
13C-2378-TCDF
13C-12378-PeCDF
13C-23478-PeCDF
13C-123478-HxCDF
13C-123678-HxCDF
13C-123789-HxCDF
13C-234678-HxCDF
13C-1234678-HpCDF
13C-1234789-HpCDF
CLEANUP STANDARDS/F
37CI-2378-TCDD
13C-123478-HxCDD
13C-23478-PeCDF
13C-123478-HxCDF
13C-1234789-HpCDF
8000
8000
8000
8000
8000
16000
8000
8000
8000
8000
8000
8000
8000
8000
8000
RESAMPLING SI
800
800
800
800
800
5110 #
6940
NA
5820
6500
3800
4930 tt
6010
NA
NA
5140
NA
NA
5990
NA
RROGATE STAN
808 #
NA
NA
NA
NA
64
87
NA
73
81
86
62
75
NA
NA
64
NA
NA
75
NA
DARDS
101
NA
NA
NA
NA
4910 #
6270
NA
5110
6050
14100
4660 #
5570
NA
NA
4410
NA
NA
5810
NA
8
NA
NA
NA
NA
61
78
NA
64
76
oo
oo
58
70
NA
NA
55
NA
NA
73
NA
0
NA
NA
NA
NA
6720
8480
6370
6400
6180
10300
7080
7680
9160
6960
6680
6180
7230
6520
4990
NA
NA
NA
NA
NA
84
106
80
80
77
64
88
96
115
87
84
77
90
81
62
NA
NA
NA
NA
NA
6920
8090
6630
6500
6870
2000
7280
8320
9190
7070
6940
6830
7460
7300
5600
NA
NA
NA
NA
NA
86
101
83
81
86
75
91
104
115
88
87
85
93
91
70
NA
NA
NA
NA
NA
DL = Detection Limits; {EMPC}; (Below Detection Limit).
# = Value from second column confirmation.
J = Value found below detection limit.
ND = Not detected.
NA = Not applicable.
-------
Table 6-16. Summary of Dioxin/Furan Results and Standard Recoveries for Field Blank and Proof Blank Front Half Air Samples
ANALYTES <':'-'> •" "- -: '-^•"•'- '•.<:,'.- .-,
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Total Tetra-Furans
Total Tetra-Dioxins
Total Penta-Furan
Total Penta-Dioxins
Total Hexa-Furans
Total Hexa-Dioxins
Total Hepta-Furans
Total Hepta-Dioxins
Total TEQ
;-t FIELD BLANK 1 W
48190-11-07
FH-FB1-DIOX
(pg/sample) *
ND
ND
ND
ND
ND
ND
23.3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.023
J'H ,„ * ',f ''•''
- ' :DL .v ; '
(pg/sample) -
10.6
19.5
6.07
5.69
3.75
4.57
6.63
10.9
9.20
7.82
6.82
7.88
7.57
2.56
11.2
19.3
13.5
18.4
18.6
22.2
14.9
9.2
3.13
20.8
PROOF BLANK 1
48190-11-05
FH-PB1-DIOX
(pg/sample)
ND
ND
ND
ND
ND
ND
21.5
ND
ND
ND
ND
ND
ND
ND
3.75
ND
ND
14.8
ND
ND
ND
ND
ND
(3.75) J
(5.07) J
0.059
' bCr^'/ /
(pg/sample)
6.38
10.95
3.94
3.69
2.44
3.00
3.94
6.26
5.26
5.00
4.32
5.00
4.82
7.57
13.1
11.1
10.6
12.5
9.51
5.94
13.9
13.8
PROOF BLANK 2
48190-11-06;
f;'- FH4»B2-DIOX
"", (pg/sample)
ND
ND
ND
ND
ND
ND
20.1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.020
.'".':::''DL,'",,
(pg/sample)
12.6
18.9
5.32
4.94
3.25
4.07
7.38
10.2
8.51
7.13
6.19
7.19
6.94
2.31
10.1
17.4
15.0
21.9
17.3
21.5
13.6
8.01
18.5
18.6
cn
CO
ro
-------
Table 6-16. (Continued)
.^/--vSj'.iV/'Vj.' ;•<;/", ":
INTERNAL STANDARDS :
13C-2378-TCDD
13C-12378-PeCDD
13C-123678-HxCDD
13C-1234678-HpCDD
13C-OCDD
13C-2378-TCDF
13C-12378-PeCDF
13C-123678-HxCDF
13C-1234678-HpCDF
CLEANUP STANDARDS
37CI-2378-TCDD
i.. , l.,-£^'^fi'^ -*,T
~''™*^tjjli
' RECOVERY*^
AX;V:{%)'«-:f4C
40-135
40-135
4Q.-.135 J
40-135
40-135
40-135
40-135
40-135
40-135 J
40-135
~lf? ?/'"'• '"^ '"' *, "' " ' :
pfeSPIKE
?•' CONC.
K (pg/sample) '•<
8000
8000
8000
8000
16000
8000
8000
8000
8000
800
, FIELD BLANK 1 :
48190-11-07
,^,V,FH-FB.1-DIOX r.-i,",
^A-'jpg/sa'^jpie) :,>, ;vv(
4380
6440
5480
6690
14200
4280
5190
4560
6030
804
RECOVERY"
{%)
55
81
69
84
89
53
65
57
75
101
PROOF BLANK 1
48190-11-05
FH-PB1-DIOX
(pg/sample)
5380
7620
6150
7360
15800
5120
6330
5290
6690
768
V-'^:4fi
RECOVERY T
{%)
67
95
. . 77.
92
99
64
79
66
84
96
PROOF BLANK 2
-t 48190-1 1-06
*; FH-PB2-DIOX '
(pg/sample)
3190
5450
5150
6350
13600
3170
4450
4270
5700
792
RECOVERY
: (%)
40
68
64
79
85
40
56
53
71
99
O)
CO
CO
ND = Not detected.
DL = Detection Limit.
1 J = Below detection limit.
-------
Table 6-17. Summary of Dioxin/Furan Results and Standard Recoveries for Field Blank and Proof Blank Back Half Air Samples
•",'" '-'I-' :" ". '-^ fsy t- ~ """"'-' ? -'•'•" ' ^Vl-lititfv-*"'*/^' " ••£*"*
ANALYTES ""^'^ - ' -".; • ' .J-%,3,fe,- -VASTC.',-' " '•'*
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Total Tetra-Furans
Total Tetra-Dioxins
Total Penta-Furan
Total Penta-Dioxins
Total Hexa-Furans
Total Hexa-Dioxins
Total Hepta-Furans
Total Hepta-Dioxins
Total TEQ
FIELD BLANK 1"
48190-09-07:'i!:;ff
-", BH-FB1-DIOX??
'*' (pa/sample)
ND
ND
ND
ND
ND
{.1.1,9}.
54.0
4.68
ND
ND
ND
ND
ND
ND
9.76
ND
ND
(4.68) J
ND
ND
ND
(5.44) J
ND
19.7
(11.9) J
0.74
*,;:•::. '-•DL^fK:
(pg/sample)
6.76
16.0
5.52
5.12
3.36
8.08
6.76
6.20
5.40
6.24
6.00
11.0
19.0
9.00
11.8
13.6
18.2
11.8
8.32
21.2
PROOF BLANK 1
48190-09-05
; BH-PB1-DIOX
'"•''' (pg/sample)
ND #
ND
ND
ND
ND
14.3
73.6
(4.08) #
ND
ND
ND
ND
ND
ND
11.1
ND
14.0 J
6.64J
5.96 J
19.6
24.8
1.00
- *-•;"' DL ; ',> '•'•
(pg/sample)
2.96
16.4
5.32
4.96
3.24
4.88
8.12
6.80
6.64
5.76
6.64
6.40
10.5
18.1
9.40
12.1
13.8
18.6
12.6
8.00
PROOF BLANK 2
• 48190-09-06
BH-PB2-DIOX
/:; (pg/sample)
ND ff
.{6,80} ,
.{34,0}
14.3 #
5.76
9.56 J
73.2
41.2
14.7
4.80 J
6.40 J
14.3
14.8
2.2
V r" ,r^'' -
• M|,^,, '^ '/' - ^i(
'Vr^Si>/'v' ''', JW '^."
""I^'DL' '-;
(pg/sample)
2.75
16.2
5.20
4.88
3.20
8.12
6.80
6.64
5.80
6.68
6.44
10.8
18.6
18.4
12.7
7.88
cn
CO
-------
Table 6-17. (Continued)
•"^V-"-' " - . ,,;•;'* :>>*f'T'v' • / rV FIELD BLANK 1 'V*: >£^7!i:ft* ^f'""' PROOF BLANK 1 , ~;i*ifi,r;^ . ""PROOF BLANK-^4r^ %•:%%.--
, 4>i' ,-.-,. /*•.'''<;•'•"/< "'• TARGET ' SPIKE 48190-09-07 ' "'•'/ :' •"-:•'. 48190-09-05
' RECOVERY;P$?; CONC. - BH-FBI-DIOX RECOVERY BH-PBI-DIOX, RECOVERY , BH-PB2-oiox RECOVERY
INTERNAL STANDARDS « «%) " (pg/sample) ? (pglsample) '.!*'>•.• ^v (%) «&«.*..;- '(pg/sample) t? (%) ; (pfl/sample) (%)
13C-2378-TCDD
13C-12378-PeCDD
13C-123678-HxCDD
13C-1234678-HpCDD
13C-OCDD
13C-2378-TCDF
13C-12378-PeCDF
13C-123678-HxCDF
13C-1234678-HpCDF
PRE-SAMPLING SURROGA7
37CI-2378-TCDD
13C-123478-HxCDD
13C-23478-PeCDF
13C-123478-HxCDF
13C-1234789-HpCDF
40-135
40-135 _
40-135 J
40-135
40-135
40-135
40-135 J
40-135
40-135 J
E STANDARDS
70-130 J
70-130
70 - 1 30
70-130
70-130
8000
8000
8000
8000
16000
8000
8000
8000
8000
8000
8000
8000
8000
8000
6000
7080
6080
6200
13600
5560
6200
5680
5800
8240
8960
9360
8080
7280
75
89
76
78
85
70
78
71
73
103
112
117
101
91
5160 #
6320
5400
6040
13400
4840 #
5640
4880
5440
9040*
10200
10200
9440
10000
65
79
67
75
84
61
71
61
68
113
127
127
118
126
5280*
6680
6000
6240
13900
4880 #
5760
5120
5600
8920 tt
9040
10000
9240
9640
66
83
75
78
87
61
72
64
70
112
113
125
115
121
O)
CO
en
DL = Detection Limits; {EMPC}.
ND = No data.
# = Value from second column confirmation.
J = Below detection limit.
-------
with extractions occurring within 13 days of collection and analysis occurring within 15 days of
extraction.
PAH Analysis.
Field Samples. The measured native PAH data and recovery data of internal standards,
surrogate standards, and recovery standards in the front half (FH) and back half (BH) air samples
are summarized in Tables 6-18 and 6-19. The recovery standards (acenaphthene-di0 and pyrene-
d)0) were added to the sample extracts after completing the sample preparation of cleanup steps.
Acceptable recoveries (64-124%) 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
possible sample matrix effect on other relatively more reactive target PAH compounds cannot be
discounted.
Quantitative recoveries (>70%) of all the internal standards except benzo[a]pyrene-d12
and perylene-d]2 were obtained in the FH samples. Recoveries of benzo[a]pyrene-d,2 and
perylene-d12 ranged from 17 to 22% and from 18-32%, respectively. The low recoveries of these
two internal standards could be explained by either loss through the sample preparation process
and/or through sample matrix effects. The internal standards benzo[a]pyrene-d]2 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. It should be noted that the loss of benzo[a]pyrene-d12 does not
directly apply to the relatively more stable benzo[e]pyrene. Originally, the internal standard for
the benzo[e]pyrene was benzo[a]pyrene-d12. The measured values of benzo[e]pyrene could be
overestimated because of the low recovery of the Method 429 specified internal standard.
Ideally, benzo[e]pyrene-d12 could have been used as the internal standard for benzo[e]pyrene;
however, this standard was not included in the specified method. The benzo[e]pyrene was re-
quantified using benzo[k]fluoranthene-d12, an internal standard because the benzo[e]pyrene and
benzo[k]fluoranthene have similar reactivity. Surrogate standards were not used in the FH
samples, thus no recovery data were reported.
6-36
-------
Table 6-18. Summary of PAH Results and Standard Recoveries for Front Half Air Samples
CD
CO
• - <• "•'•>',' •'•'/: f'W. ' *,' , .-,-,;•
'' :,,•<'"'*"•'•*•• . - - ,-.,:/*> V"f ; >, •" /
.,.,-'', .*(•"}' "' U%" ''' ' Jt ""!!'/ >f>
/ • - " ,,- '<**'" ^f ^'Uf&wM'£x * •• >,,?- *
'' • ''. * , I- '",,:, ' - '. ' .' , **i, 'f''"\^M !i> *> ~«- ,r , "' *
' /' ' '',, ^ *• ^''''^'V,** ' ; - - " , -
ANALYTES ' ' ' ' »'~. i- '• /'. ii.,/? ''&'&*>'
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzo(e)pyrene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
lndeno(1 ,2,3-c,d)pyrene
2-Methylnaphthalene
Naphthalene
Perylene
Pyrene
Phenanthrene
V &'• 'RUN 2&f ",
48190-11-02 ,C
FH-R2-PAH
'""'i (ng/sample)
ND
ND
ND
53
350
270
210
110
2000 E
200
85
53
ND
260
40
1700 E,B
ND
43
130
'•'^K.;..-*
(ng/sample) •'•
20
20
20
20
20
64
;^:-,- ',;••" , .
RUNS
48190-11-03
;"Vi^'FH-R3-PAH :."*,"-•- 1
^^
';4->l-RUN4':-^' >
*f-;*48190r11-04' "'
FH-R4-PAH
*'<&* (ng/sample)
ND
ND
ND
ND
96
37
ND
ND
270
43
21
23
ND
29
27
440 B
ND
ND
ND
'x"'1-1':*!]"*
-.?• , :. '^4
';„,' • •::-"/
•^•DL^,-/"
(ng/sample)
20
20
20
20
20
20
20
20
20
64
-------
Table 6-18. (Continued)
,,^- A ffftf '-¥•! '^.'''l.yiy
INTERNAL STANDARDS ^
Acenaphthylene-d8
Benzo(a)anthracene-d1 2
Benzo(a)pyrene-d1 2
Benzo(b)fluoranthene-d1 2
Benzo(g,h,i)perylene-d1 2
Benzo(k)fluoranthene-d1 2
Chrysene-d12
Dibenzo(a,h)anthracene-d1 4
Fluoranthene-d10
Fluorene-d10
Indenod ,2,3-c,d)pyrene-d1 2
Naphthalene-d8
Perylene-d12
Phenanthrene-d10
SURROGATE STANDARDS
13C-Fluorene-d10
RECOVERY STANDARDS
Acenaphthene-d10
Pyrene-d10
,. '/;•' t'^-JSPIKE" '
lH4i _ ', ' 'coNCjfts!«A'iy-,:y
' y?Sl:sf:-/ (ng/sample) •
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
RUN 2
48190-11-02
FH-R2-PAH
(ng/sample)
112
142
34
204
148
172
194
170
188
174
168
174
64
164
148
180
RECOVERY
(%) ,
56
71
17 &
102
74
86
97
85
94
87
84
87
32 &
82
NA
74
90
RUN 3
48190-11-03
FH-R3-PAH
(ng/sample)
100
148
44
214
166
194
204
192
204
194
186
172
36
194
158
192
'RECOVERY,;
- • '-;j%)^>/;*
50
74
22 &
107
83
97
102
96
102
97
93
86
18&
92
NA
79
96
RUN 4
48190-11-04
FH-R4-PAH '",';','
^(ng/sample) -
128
124
42
178
162
206
218
156
266
158
174
176
58
138
150
248
'iRECbVERY
^.iH)'- -
64
62
21 &
89
81
103
109
78
133
79
87
88
29 &
69
NA
75
124
o>
I
CO
00
DL = Detection limit.
& = QC value outside the accuracy goal for Method (10-150% Recovery of Standard Spiked samples).
ND = Not detected, value noted is reporting limit.
E = Estimated result, reported concentration exceeds the calibration range.
NA = Not applicable.
B = Lab method blank contamination of target analytes at level above DL.
-------
Table 6-19. Summary of PAH Results and Standard Recoveries for Back Half Air Samples
en
CO
CO
. •'' ' ' • ,,,-,'^'''\fy,&k'^v', { ••'
:ANALYTES"v*'/'i."^ -SS" ,•••''' ^-^-t^^r,^.
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzo(e)pyrene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
lndeno(1 ,2,3-c,d)pyrene
2-Methylnaphthalene
Naphthalene
Perylene
Pyrene
Phenanthrene
'.''"•"RUN 2'""' ''
48190-O9-02
BH-R2-PAH
(ng/sample) -" ''•';:•'
160
1700DJA
210
83
860
840
130
ND
530 JA
3300 E
20
3900 E
1500E
97
32000 D,E,B
450000 D,E,B
370 JA
2600 E
33000 D,E,B
. , '' oLV'.^v
(ng/sample)
20
20
, RUN*4 '•'"' '•
48190-09-04
BH-R4-PAH
(ng/sample) ;,
26
260 JA
93
82
170
120
85
NQ
120 JA
440
ND
910
130
45
1300 D,B
210000D,E,B
57 JA
490
8000 E,B
DL
(ng/sample)
20
20
20
6-39
-------
Table 6-19. (Continued)
en
•• '• r ; '••$?""'$&
INTERNAL STANDARDS
Acenaphthylene-d8
Benzo(a)anthracene-d1 2
Benzo(a)pyrene-d12
Benzo(b)fluoranthene-d1 2
Benzo(g,h,i)perylene-d1 2
Benzo(k)fluoranthene-d1 2
Chrysene-d12
Dibenzo(a,h)anthracene-d14
Fluoranthene-d10
Fluorene-d10
lndeno(1 ,2,3-c,d)pyrene
Naphthalene-d8
Perylene-d12
Phenanthrene-d10
SURROGATE STANDARDS
13C6-Fluorene
RECOVERY STANDARDS
Acenaphthene-d10
Pyrene-d1 0
•*,;. - ' ''I
SPIKE
CONC.
(ng/sample)
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
RUN 2
48190-09-02
BH-R2-PAH
(ngsample) .,
3.0
84
12.2
204
94
136
132
116
146
186
120
182
3.8
248
48
152
128
RECOVERY
(%)
1.5 &
42 &
6.1 &
102
47 &
68
66
58
73
93
60
91
1.9&
124
24 &
76
64
"RUN 3
48190-09-03
BH-R3-PAH
(ng/sample)
1.4
72
9.8
176
94
172
176
126
164
180
136
178
256
62
174
140
"J,i,:-:
' ' '" '
RECOVERY
(%)
0.7 &
36 &
4.9 &
88
47 &
86
88
63
82
90
68
89
NA
128
31 &
87
70
RUN 4
48190-09-04
BH-R4-PAH
(ng/sample)
2.4
76
172
134
148
146
126
164
216
136
154
3.6
250
26
146
148
1 "1V!
RECOVERY
(%)
1.2 &
38 &
NA
86
67
74
73
63
82
108
68
77
1.8 &
125
13 &
73
74
DL = Detection limit.
& = QC value outside the accuracy goal for Method (50-150% Recovery of Standard Spiked samples).
ND = Not detected, value noted is reporting limit.
NA = Not applicable.
D = Result reported is the analysis of a dilution.
E = Estimated result, reported concentration exceeds the calibration range.
B = Lab method blank contamination of target analyte at the level above DL.
JA = The analyte was positively identified , but the quantification was an estimate.
NQ = Not quantifiable due to low standard recovery of target analyte.
-------
Acceptable recoveries (>50%) 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-d8, benz[a]anthracene-d12, benzo[a]pyrene-d,2, and perylene-d,2. These four
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 effects between the FH and BH
samples could have resulted in more internal standards being located in the BH samples with
lower than 50% recovery. For the same reason discussed before, the internal standard,
benzo[k]fluoranthene-d12, was used for the quantification of benzo[e]pyrene level. Low
recoveries (13-24%) were obtained for the surrogate standard (field spike) in the BH samples.
The loss of the surrogate standards are believed to be from field handling and sample matrix
effects. Acceptable recovery standard results were obtained in the BH samples; ranging from 64-
87%.
Lab Control Samples. This assumption that sample matrix effects influenced the low
recovery of benzo[a]pyrene-d12 and perylene-d12 is further supported with the recovery data
obtained from lab control spike (LCS) and lab control spike duplicate (LCSD) samples. Tables
6-20 (a and b) summarize the recovery data of the FH and BH lab control spikes (LCS) and lab
control spike duplicates (LCSD), respectively. As shown in Table 6-20 (a and b), acceptable
(50-150%) recoveries of all native target PAHs except naphthalene were obtained in the LCS and
LCSD samples. Quantitative recoveries (120-125%) of naphthalene were obtained in the LCS
and LCSD FH samples but were not recovered in the BH samples because of the high reporting
level limit (470 ng/sample) of naphthalene resulting from the background levels present in the
field blank. Note that acceptable recoveries (>50%) of all internal standards were obtained in
these LCS and LCSD samples. Unlike in the field real samples discussed before, quantitative
recoveries of the internal standard, benzo[a]pyrene-d,2, were obtained and ranged from 86-93%.
This finding confirmed that sample matrix effects notably contributed to the loss of the internal
standards of benzo[a]pyrene-d12, perylene-d12 in the field FH and BH samples and
acenaphthylene-dg and benz[a]anthracene-d12 in the field BH samples. As expected, satisfactory
recoveries (>90%) of the recovery standards were established in these LCS and LCSD samples.
Blanks - Lab and Method. Table 6-21 summarizes the results and recovery data for the
FH and BH lab and method blank samples. As shown in Table 6-21, all the target native PAH
6-41
-------
Table 6-20a. Summary of PAH Results and Standard Recoveries for Front Half Lab Control Spike and Spike Duplicate Samples
ANALYTES ''''- - -:' ""'" • '•' "X
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzo(e)pyrene
Chrysene
Dibenzo(a.h) anthracene
Fluoranthene
Fluorene
lndeno(1,2,3-c,d)dipyrene
2-Methylnaphthalene
Naphthalene
Perylene
Pyrene
Phenanthrene
r-.3"->r ,-, ' LCS
; TARGET SPIKE
., RANGE "i CONC.
%!itii(%r • (ng/sample) •'
50-150 I 200
50-150 I 200
50-150 I 200
50-150 I 200
50-150 I 200
50-1 50 I 200
50-150 ! 200
50-150 ! 200
50-150 ! 200
50-150 ! 200
50-150 I 200
50-150 ! 200
50-150 ! 200
50-150 ! 200
50-150 ! 200
50-150 ! 200
50-150 I 200
50-150 ! 200
50-150 ! 200
i
LCS -
48190-11-08
FH-LCS-PAH
(ng/sample)
150
180
260
200
200
190
200
190
220
200
200
220
210
170
180
250 B
200
210
210
RECOV.
(%)
75
90
130
100
100
95
100
95
110
100
100
92
105
85
90
125
100
94
105
i LCS DUP
: 48 190-1 1-09
FH-LCSDUP-PAH
(ng/sample)
170
180
250
190
210
200
210
200
220
210
200
210
250
200
190
240 B
200
210
210
RECOV. :
(%}
85
90
125
95
105
100
105
100
110
105
100
87
125
100
95
120
100
94
105
I RECOV.
ty RPD,
'S?{%)*
48190-1 1-07 :C
FH-FB1-PAH^
(ng/sample)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
36
ND
ND
ND
ND
ND
21
68 B
V' '''^~^'f^' •'"•'' '-\,
I ' \4U .-""%' $i'' ?° , ! » * '
&|Dtp;
(ng/sample)
20
20
20
20
20
20
20
20
20
20
20
20
20
20
100
20
64
O)
^
ro
-------
Table 6-20a. (Continued)
,'; ,-wkV-"- " "' ,'fji^ ' V""1
"•''• Vj.V-V*7*'T "' , ", I? fjli'"-',*" r ,'%' ; ;-:l
INTERNAL'*'5"'"1' "?'"';:,'s >?;,;>' '/"": ."
STANDARDS' - ,¥->v ' ; -',#
Acenaphthylene-d8
Benzo(a)anthracene-d1 2
Benzo(a)pyrene-d1 2
Benzo(b)fluoranthene-d1 2
Benzo(g,h,i)perylene-d1 2
Benzo(k)fluoranthene-d1 2
Chrysene-d12
Dibenzo(a,h)anthracene-d1 4
Fluoranthene-d10
Fluorene-d10
Indeno(1,2,3-c,d)pyrene-d12
Naphthalene-d8
Perylene-d12
Phenanthrene-d 1 0
SURROGATE STANDARDS
1 3C6-Fluorene
RECOVERY STANDARDS
Acenaphthene-d 1 0
Pyrene-d10
^TARGET
Y RANGE
!Jfff ?>(%)*'
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
'y.f-'^.iics , '•'
": •' SPIKE ./.;v
-, v CONC: — ,
: (ng/sample)
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
LCS AVM
,'48190-11-08
* FH-LCS-PAH
(ng/sample) . '
198
162
178
194
220
214
226
204
200
132
224
198
178
130
216
204
RECOV,
(%)
99
81
89
97
110
107
113
102
100
66
112
99
89
65
NA
108
102
V LCSDUP ?"
48190-11-09
FH-LCSDUP-PAH
? •"' (ng/sample)
190
178
172
194
168
196
204
158
196
140
170
172
174
134
194
190
,'.*<••;,<'! •('f-'-'U-tA,
•'<_,;, >.">;' ~'."4f '*
-' •'" " ' *f^"
RECOV.
(%) •"..-
95
89
86
97
84
98
102
79
98
70
85
86
87
67
NA
97
95
RECOV,
RPD
: (%)
4
8
3
0
26
9
11
23
2
4
27
13
2
2
11
7
FIELD BLANK
48190-11-07 ;
FH-FB1-PAH :f
(ng/sample)
162
156
142
220
184
206
206
174
188
150
190
174
100
152
192
184
U'lf-"- -
* RECOV.
(%)
81
78
71
110
92
103
103
87
94
75
95
87
50
76
NA
96
92
o>
^
CO
DL = Detection limit.
& = QC value outside the accuracy of precision goal for Method (50-150% Recovery of Standard Spiked samples).
ND= Not detected.
NA = Not applicable.
B = Lab blank contamination of target analyte at concentration above the reporting level.
-------
Table 6-20b. Summary of PAH Results and Standard Recoveries for Back Half Lab Control Spike and Spike Duplicate Samples
.,.;•••",-:„ • ••'•• •*-„- •"?&"- "s'""!4,fr ' "• LCS <-. - , LCS -* ', . - LCS DUP
'"%•-•' •*&•'•' -:'"•,•',- "•'••',- • ^"V^TARGETfct..1 SPIKE; ? 48190-09-09 - 48190-09-10
'>,. ". " ',. , *<••'.:• -i\<;'., '. "^RANGE %ft;#. CONC. %BH-LCS-PAH RECOV. BH-LCSDUP-PAH
ANALYTES'i, ;V ,•'-•' "Sfe' ¥?*t%) ^Ing/sample) • ^(ng/sample) i (%) s*5' (ng/sample)
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzo(e)pyrene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
lndeno(1,2,3-c,d)dipyrene
2-Methylnaphthalene
Naphthalene
Perylene
Pyrene
Phenanthrene
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
170
180
250
200
200
200
190
200
210
190
210
220
230
190
210
NQ*
200
210
210
85
90
125
100
100
100
62
100
93
95
105
85
115
95
105
NQ»
100
78
105
150
170
200
190
170
200
190
190
230
180
190
200
230
170
200
NO"
190
190
210
•f, •'," ; • • -•"' '•'*. --"'"c'c ; ; FIELD " BLANK .-
<
RECOV. RPD BH-FB1-PAN,
(%) ; 4 f (%) (ng/sample) £
75
85
100
95
85
100
62
95
103
90
95
75
115
85
100
NQ*
95
68
105
10
5
25
5
15
0
0
5
10
5
10
10
0
10
5
NA
5
10
0
ND
ND
ND
ND
ND
ND
67
ND
25
ND
ND
50
ND
ND
ND
ND
ND
55
ND
v'Af'L y ,' '*
WalSv
20
20
20
20
20
20
20
20
20
20
20
120
470
20
20
120
O)
-------
Table 6-20b. (Continued)
INTERNAL ' *^/; '. ;-' p yl»y^^ '4
STANDARDS . ;^:-'-'"""' ' 'J
Acenaphthylene-d8
Benzo(a)anthracene-d1 2
Benzo(a)pyrene-d1 2
Benzo(b)fluoranthene-d1 2
Benzo(g,h,i)perylene-d1 2
Benzo(k)fluoranthene-d1 2
Chrysene-d12
Dibenzo(a,h)anthracene-d14
Fluoranthene-d10
Fluorene-d10
Indenod ,2,3-c,d)pyrene-d1 2
Naphthalene-d8
Perylene-d12
Phenanthrene-d 1 0
SURROGATE STANDARDS
13C6-Fluorene
RECOVERY STANDARDS
Acenaphthene-d 1 0
Pyrene-d10
fffjrARGET
"h; RANGE
?,(%) r,
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50-150
SPIKE
'- ; 'CONC.y:Y'i>i:
' (ng/sample)
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
100
100
48190-09-09
xBH-LCS-PAH
(ng/sample)
196
182
186
198
196
212
228
198
212
176
198
184
182
152
218
204
,*?"!f! '"•*"
'. '" .•',.'
"' RECOV/$f
/ (%)
98
91
93
99
98
106
114
99
106
88
99
92
91
76
NA
109
102
WLCSDUP "
;?48190-09-10
BH-LCSDUP-PAH
(ng/sample) ;; '
178
172
162
200
174
196
222
172
204
186
178
178
152
166
200
196
RECOV.
" (%)
89
86
81
100
87
98
111
86
102
93
89
89
76
83
NA
100
98
RECOV.
'.-' RPD
(%)
48190-09-07
BH-FB1-PCB
(ng/sample)
172
166
176
208
220
208
222
238
198
154
228
156
182
142
122
190
190
• f-i'S'i "
RECOV.
86
83
88
104
110
104
111
119
99
77
114
78
91
71
62
95
95
o>
i.
01
DL = Detection limit.
& = QC value outside the accuracy goal for Method.
ND= Not detected.
NQ* = Not determined because of high detection limit of analyte resulting from BH lab blank contamination.
NA = Not applicable.
-------
Table 6-21. Summary of PAH Results and Standard Recoveries for Lab and Method Blank Samples
^t|^&;%i^ -•>. - :• *tf ;!|»|>::^ ;>>!%; ?.K>';' LAB BLANK''**;
''i^-r;.'- 9^,>-';''W%-/- ." -'•"'••^iW^-:-''.%%^fe;,48i90-11-10'"J:
•..-'•' $&>> !*K<; '-, tfrf j,V/- ' -.' :; '^^fe-^lfcFH-LB-PAH •
•.ANALYTES.--isfc%«^>^;»( ,;„• v4**!MiN* *>4fet?i (ng/sample) >•.
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzo(e)pyrene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indenod ,2,3-c,d)pyrene
2-Methylnaphthalene
Naphthalene
Perylene
Pyrene
Phenanthrene
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
21
ND
ND
ND
>-v f^lll LAB BLA^^ir^^llf^METHOD .-> ' '
3&tri'---^'::SAQ\ 90-09-1 1V~V r.->\ " •.--;^-BLANK . • ^^\^^,-;BACKQTOUND>j^J»K»lt,
::*:;-DL\ : BH-LB-PAH .^'DL:" "-48200-51-03; .^DCff^ 48200-51-02 * ":-'^Dl|*/f
(ng/sample) (ng/sample) (ng/sample) (ng/sample) .; (ng/sample) (ng/sample) (ng/sample)
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
25
94
ND
ND
25
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
D
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
59 J,B
ND
ND
ND
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
150
ND
ND
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
cn
-------
Table 6-21. (Continued)
' 1 .. "f '.'','" f > ", f ,
' '~ "' t< '' '• s" „ . ,'<<
INTERNAL STANDARDS *
Acenaphthylene-d8
Benzo(a)anthracene-d1 2
Benzo(a)pyrene-d1 2
Benzo(b)f luoranthene-d 1 2
Benzo(g,h,i)perylene-d1 2
Benzo(k)f luoranthene-d 1 2
Chrysene-d12
Dibenzo(a,h)anthracene-d1 4
Fluoranthene-d10
Fluorene-dIO
Indenod ,2,3-c,d)pyrene
Naphthalene-d8
Perylene-d12
Phenanthrene-d 1 0
SURROGATE STANDARDS
1 3C6-Fluorene
RECOVERY STANDARDS
Acenaphthene-d 1 0
Pyrene-d10
TARGET
RANGE
-:ir {%),;;,;"
50-150
50-150
50-150
50-150
50 - 1 50
50-150
50-150
50-150
50-150
50-150
50-150
50-150
50 - 1 50
50 - 1 50
50-150
50-150
ISSPIKE :v-
"I^CONC*''-
(ng/sample)
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
LAB BLANK
48190-11-10
FH4.B-PAH
(ng/sample) >'
182
158
152
182
166
186
218
148
188
152
160
184
156
124
192
188
RECOV.
<%)
91
79
76
91
83
93
109
74
94
76
80
92
78
62
NA
96
94
LAB BLANK
48190-09-11
BH-LB-PAH
(ng/sample)
194
130
158
162
172
218
270
134
260
156
158
200
172
132
246
194
- &i i f<
> ' J,
RECOV.
(%)
97
65
79
81
86
109
135
67
130
78
79
100
86
66
NA
123
97
METHOD
-:'¥ BLANK
« 48200-51 -03
'•- (tig/sample)
186
144
172
182
172
204
238
146
208
154
156
208
146
132
214
232
RECOV.
(%} i
93
72
86
91
86
102
119
73
104
77
78
104
73
66
NA
107
116
XAD r
BACKGROUND
48200-51-02
(ng/sampta)
192
170
202
200
196
222
234
174
222
176
190
218
172
164
214
228
RECOv!
•••': , ,'(%) -,,
96
85
101
100
98
111
117
87
111
88
95
109
86
82
NA
107
1 14
O)
•^
vj
DL = Detection limit.
ND = Not detected.
NA = Not applicable.
B = Lab method blank contamination of target analyte at concentration above the reporting level.
J = Estimated value, below detection limit.
-------
compounds except naphthalene were not detected in the method blank. Naphthalene and
phenanthrene were detected in the clean XAD-2 trap and the BH lab blank. This result is typical
of background levels for these compounds (per M-429 PQL for HRMS analyses) in XAD which
has not been stringently cleaned to remove these manufacturing by-product contaminants. In the
BH lab blank, 2-methyl naphthalene was also detected. Per the WAM's instructions and the
method, five times the detected concentration in the blank was noted as the reporting limit for the
compounds detected. As expected, acceptable recoveries (50-150%) were obtained for all
internal standards and recovery standards in the lab blank, method blank, and XAD-2 blank
samples.
Blanks - Field and Proof. The measured native PAH data and recovery data of internal
standards, surrogate standards, and recovery standards in the FH and BH field and proof blank
samples are summarized in Tables 6-22 and 6-23, respectively. As shown in Table 6-22, only
trace amounts of phenanthrene, fluoranthene, and pyrene were detected in the field and proof
blank FH samples. These compounds are likely oxygenated artifacts which are sometimes
generated when air is induced to XAD during field blank collection. Acceptable recoveries (50-
150%) were obtained for all the internal standards and recovery standards in these samples.
As shown in Table 6-23, trace amounts of pyrene, fluoranthene, benzo[e]pyrene, and
benzo[g,h,i]perylene were detected in the field and proof blank BH samples. Acceptable
recoveries (50-150%) were established for all the internal standards and recovery standards in
these blank samples. Acceptable recoveries of the surrogate standards were also established and
ranged from 61 to 69%.
6.1.3.2 Scrubber Water Samples
PCB Analysis. The initial calibration for both the SPB-Octyl and DB-1 analyses met the
requirement for response factors having less than 35% relative standard deviation (RSD) for all
analytes (actual range = <17% for SPB-Octyl and DB-1 calibrations). The continuing
calibrations met the requirement for response factors being within 35% of the response factors
generated in the initial calibration for at least 70% of the analytes. In fact, all analytes in all
continuing calibrations were within 35% of the initial calibration.
6-48
-------
Table 6-22. Summary of PAH Results and Standard Recoveries for Field and Proof Blank Front Half Air Samples
ANALYTES'' '. ,:'''^;'-'-: • -.l^ffM'^''.' , -
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzolalpyrene
Benzo(e)pyrene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indenod ,2,3-c,d)pyrene
2-Methylnaphthalene
Naphthalene
Perylene
Pyrene
Phenanthrene
FIELD BLANK;?*
48190-;! 1-07 '
FH-FB1-PAH
. (ng/sample) < •
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
36
ND
ND
ND
ND
ND
21
68 B
: DL.'-'K-'
(ng/sample)
20
20
20
20
20
20
20
20
20
20
20
20
20
20
100
20
64
PROOF BLANK 1
48190-1 1-05,» H
FH-PBI-PAHf
(ng/sample)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
53
440 B
ND
ND
ND
>"- ' • DL-4;^ ;"",'s
(ng/sample) /
20
20
20
20
20
20
20
20
20
20
20
20
20
20
100
20
20
64
.jljlfSfiiJ ff':?: ,";••!' . :
PROOF BLANK 2
48190?11-06
?f FH-PB2-PAH , ;
•"* {ng/sample}
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
58
350 B
ND
ND
ND
.'"'-,' -' , '. '"'":
'•'' :- i^lli^f ':-
^''.'•.';pL;;0
(ng/sample)
20
20
20
20
20
20
20
20
20
20
20
20
20
20
100
20
20
64
O)
-^
CO
-------
Table 6-22. (Continued)
O)
CJI
O
' j, ' '' ?'•!»' * ' A"-
"^"
-------
Table 6-23. Summary of PAH Standard Recoveries for Field and Proof Blank Back Half Air Samples
:•••;• ; • •' /:" *' ' '"'• ^'"t?^-* '-:'-•' ~ ' -,,•*•%
•*'•.''' ' ' '~- >JitP1&^"')v ; ••,'/'-"
ANALYTES .-,v,^, ^W.^^-V-iV-.s^^**^
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzol k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzo(e)pyrene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
lndeno(1,2,3-c,d)pyrene
2-Methylnaphthalene
Naphthalene
Perylene
Pyrene
Phenanthrene
FIELD BLANK;
48190-09-07 ;
if'^BH-FBI-PAH . ""
*" : (ng/sample) 'wl'""
ND
ND
ND
ND
ND
ND
67
ND
25
ND
ND
50
ND
ND
ND
ND
ND
55
ND
; ''.'•> '•' '>'jl\>f..?r«>
'-. DL/"^S|
(ng/sample)
20
20
20
20
20
20
20
20
20
20
20
120
470
20
120
«%h
PROOF BLANK!
.48190-09-05
f BH-PB1-PAH
(ng/sample)
ND
ND
ND
ND
ND
ND
29
ND
ND
ND
ND
21
ND
ND
ND
ND
ND
28
ND
, .• •v:,l«".-,;;' •".
. W$W
, (ng/sample)
20
20
20
20
20
20
20
20
20
20
20
20
120
470
20
120
PROOF BLANK 2
^ 48190-09-06
BH-PB2-PAH
(ng/sample)
ND
ND
ND
ND
ND
ND
69
ND
ND
ND
ND
37
ND
ND
ND
ND
ND
58
ND
•-", '.'A.fftt!,, >-rl *
, I ••
?*V>sti'!.i-;^li'':iv"
~, DL1' ' ••'•'"
"": (ng/sample)
20
20
20
20
20
20
20
20
20
20
20
20
120
470
20
120
O)
01
-------
Table 6-23. (Continued)
en
01
NJ
•''i*ife«v ,/.'%'•*:' J^i^fcii- i >' ^
INTERNAL STANDARDS -^ ' V *-'
Acenaphthylene-d8
Benzo(a)anthracene-d 1 2
Benzo(a)pyrene-d1 2
Benzo(b)fluoranthene-d1 2
Benzo(g,h,i)perylene-d1 2
Benzo(k)fluoranthene-d1 2
Chrysene-d12
Dibenzo(a,h)anthracene-d1 4
Fluoranthene-d10
Fluorene-d10
Indenod ,2,3-c,d)pyrene-d1 2
Naphthalene-d8
Perylene-d 1 2
Phenanthrene-d 1 0
SURROGATE STANDARDS
13C6-Fluorene
RECOVERY STANDARDS
Acenaphthene-d 1 0
Pyrene-d10
0" SPIKE "'
?*fiCONC;;..-
(ng/sample)
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
FIELD BLANK ||
48190-09-07
BH-FB1JPAH
(ng/sample)
172
166
176
208
220
208
222
238
198
154
228
156
182
142
124
190
190
?' A '
; RECOVERY
(%)
86
83
88
104
110
104
111
119
99
77
114
78
91
71
62
95
95
PROOF BLANK 1
48190-09-05
BH-PB1-PAH v
(ng/sample) "K
192
194
194
204
184
218
242
180
206
168
188
182
200
156
122
222
206
RECOVERY
•i, (%)
96
97
97
102
92
109
121
90
103
84
94
91
100
78
61
111
103
, PROOF BLANK 2
48190^09-065
;v/BH-PB2-PAHS;
1 (ng/sample) ;•
178
190
196
210
170
204
232
170
172
166
178
154
190
140
138
188
172
*i*"'
RECOVERY*.
- - (%);"&
89
95
98
105
85
102
116
85
86
83
89
77
95
70
69
94
86
DL = Detection limit.
ND = Not detected.
-------
Field Samples. Summary tables of PCB results and standard recoveries for the water
inlet samples are shown in Table 6-24. Water outlet sample results are in Table 6-25. Internal
standard recoveries were within the method specified limits of 20-160% and ranged from
42-83% for inlet samples and from 38-76% for outlet samples. These internal standard
recoveries indicate analytes were well recovered during laboratory extraction and were retained
during the extract cleanup process. 13C12-PCB-81 and 13C12-PCB-111 were added to the water
samples as cleanup standards after extraction but before any cleanup procedures. Method
specified recovery ranges for these standards were from 20-160% for 13Ci2-PCB-81 and 40-140%
for 13C12-PCB-111. Recovery of the cleanup standards in the inlet and outlet samples were
within the limits and ranged from 58-107% for 13C,2-PCB-81 and from 53-85% for 13C12-PCB-
111 indicating that analytes were well retained through the extract cleanup procedures. Results
for water inlet Run 4 and water outlet Run 3 are from the archive portion of these sample
extracts. Internal standard recoveries from analysis of the initial portion of these two samples
were indicative of a laboratory error resulting in the combining of WO-R3-312B and WI-R4-
41 IB during the final carbon column cleanup step. In order to verify this assumption and
provide results for these two samples, the archive portions of these two samples along with the
archive portion of the lab blank were then analyzed.
Lab Control Samples. Table 6-26 presents PCB results and standard recoveries for the
laboratory control spike and laboratory control spike duplicate (LCS/LCSD) scrubber water
samples. Recovery of all native PCBs spiked into the LCS/LCSD were within the 40-160%
target recovery range except for PCB-77 in the LCS sample (166%). The relative percent
difference (RPD) between duplicates were all under the target <50% and ranged from 1-48%
indicating acceptable analytical precision was achieved. Several analytes (PCB-118 in the LCS
and PCB-114 in both the LCS and LCSD) were detected slightly above the upper calibration
range of 40,000 pg/L and are flagged with an "E". Internal standard recoveries for the LCS were
below the acceptable range of 20-160%. Recoveries of cleanup standards for the LCS indicate
that the internal standard losses did not occur in the cleanup process and were most likely a result
of inefficient extraction. The low recoveries for the LCS internal standards did not affect
accuracy as evidenced by good recovery of analytes in the LCS sample (only PCB-77 was
6-53
-------
Table 6-24. Summary of PCB Results and Standard Recoveries for Scrubber Water Inlet Samples
ANALYTESi T " *••
PCB-77
PCB- 123
PCB-118
PCB-114
PCB-105
PCB-126
PCB-167
PCB-156
PCB-157
PCB-169
PCB- 180
PCB-170
PCB- 189
-".%, :l"-^-y;-k- :V:
' - •'•$'! 4f;v-w^%i -'¥
INTERNAL STANDARDS
13C-PCB-77
13C-PCB-118
13C-PCB-105
13C-PCB-126
13C-PCB-167
13C-PCB-156
13C-PCB-157
13C-PCB-169
13C-PCB-180
13C-PCB-189
13C-PCB-209
CLEANUP STANDARDS
13C-PCB-81
13C-PCB-111
i < ' , ;
,''.-.• "-^ljff:i:
• TARGET^ n
RECOVERY^
'- ^'(%) '9?*''
20 - 1 60
20-160
20 - 1 60
20-160
20 - 1 60
20-160
20- 160
20-160
20 - 1 60
20 - 1 60
20 - 1 60
20-160
40- 140
"';'' . vi% '•'•';•.
'¥:>''"•'*& -A
iffer' :,'*1J", V, ,
y/m. • >«? :'- • •
%ft •••:'•$'<:. ';":,' •
': : J ',!„,•-.*,
ill}*; 'SPIKE ".-'--.>
^-.CONC.vKf
vJflfjpg/sarnptej "'»
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
4000
1000
5000
,"..', RUN 2if : ' '.
48200-56-03
WI-R2-211BV
(pg/U
158 B
177B
1200 B
233 B
690 B
24.0 B
186B
243 #,B
166 #,B
26.8 B
338 B
105 B
29.0 B
' 'J;'.RUN'2|P: ", '
48200-56-03 -,
WI-R2-211B
*: (pg/sample)
952
910
996
1150
1060
1310*
1320 #
1210
1180
1270
2530
585
2720
: DL;p^
(pg/L)
RECOVERY 1
J%)
48
45
50
57
53
65
66
60
59
63
63
58
54
••RUNV-'j$£'
48200-56-05 >
WI-R3-311B ;
(pg/LJ
166B
31.6B
1060 B
68.0 B
491 B
6.91
44.4 B
85.2 #,B
28.5 #,B
5.81 B
190 B
79.9 B
9.14 B
RUNS
48200-56-05
WI-R3-311B
(pg/sample)
1230
1170
1180
1430
1250
1570 tt
1460 #
1400
1510
1510
3010
735
3380
T',,
'•••• DL'J-y.
(pg/L) V
RECOVERY!
' K (%) ,' V,
62
59
59
71
63
79
73
70
76
76
75
74
68
''•' . , '•':'4*'.'...
RUN 4-ARCHIVE
48200-56-07
*WI-R4-411B
(pg/LJ '!,-
138
17.8 B
1060B
45.1 B
504 B
3.66 B
36.1 B
80.5 #,B
19.6#,B
1.97 B
177 B
78. 2 B
{5.12} B
RUN 4-ARCHIVE
48200-56-07
WI-R4-411B
i (pg/sample)
1660
1190
1171
1350
1150
1330 #
1300 #
1180
1100
1370
1670
1070
4240
^,IV*r' ' v "1,
*: >j;jf, -'^!( ' ^
?^DL:!'V-
ipg/L}tt
RECOVERY
(%)
83
59
59
67
57
67
65
59
55
54
42
107
85
O)
cii
# = Value from second column confirmation.
DL = Detection Limit.
B = Congener found in lab blank at >20% of the concentration found in the sample.
-------
Table 6-25. Summary of PCB Results and Standard Recoveries for Scrubber Water Outlet Samples
''.-.. •: , i,,f', "'*•
v%^;> £ f'v; -•&•
ANALYTES , '*-' ; ~4"f ;
PCB-77
PCB-123
PCB-118
PCB-114
PCB-105
PCB- 126
PCB-167
PCB-156
PCB-157
PCB-169
PCB-180
PCB- 170
PCB- 189
"'"' '"• ,' ' if * ,"' %"*>*
' T'* V ' K " ' ^1" * "
INTERNAL STANDARDS
13C-PCB-77
13C-PCB-118
13C-PCB-105
13C-PCB-126
13C-PCB-167
13C-PCB-156
13C-PCB-157
13C-PCB-169
13C-PCB-180
13C-PCB-189
1 3C-PCB-209
CLEANUP STANDARDS
13C-PCB-81
13C-PCB-111
tK|^v|;,:/;
,i|^';ij;'r||
4% /"i " 'f *"*
" ' •• ' / ' ', /,'*'?
"^ -*m
.-vTARGETsp,
Pi RECOVERY?'
&: .-,-(%! **:'H-
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
20-160
20 - 1 60
29-160
20-160
20 - 1 60
20 - 1 60
20 - 1 60
40- 140
*f i'|#: .-•';•;
^f:J$K'
•^'".••-^•V ";' -
-»*"'" 'few *
«;'^%K- /.:,V
r ^SPIKE :4|!
'>;fJCONC4l|»l
53?(pfl/sample)'S
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
4000
1000
5000
RUN 2 ,
48200-56-04 ;i
WO-R2-212B
.'.-,
RECOVERY, ;
-,;/, " (%):v/,4V
67
57
61
71
64
76
7.6 .
71
68
75
73
66
53
>),< . . " I'''
RUN 3-ARcHlVE
48200-56-06
WO-R3-312B ?
(pg/L) - ti:
3630
65.1 B
3520 B
155 B
1870 B
iis
164 B
413 #
110 #,B
80.7
1000
414
23.8 B
RUN 3-ARCHIVE
48200-56-06
f; :,WO-R3-312B
(pg/sample) ,
1440
1130
1170
1250
1080
1360 #
1300 #
iio'6
1020
ioob
1520
840
3670
-•*" , f'!'''"/-,-
, . V( * t j /
•' -DL:-^.''
(pg/L)
•,/-:. ., \fj:&
;tRECOVERY
(%) '';•"'
72
57
59
63
54
68
65
55
61
50
38
85
73
RUN 4
48200-56-08
WO-R4-412B
(pg/L)
2520
50.2 B
1620B
124B
854 B
98.3
125 B
236 #,B
83.0 ff.B
97.6
653 B
298 B
44.4 B
RUN 4
48200-56-08
WO-R4-412B
(pfl/S3mpio)
1110
1010
1110
1300
1100
1390 tt
1370#
1260
1250
1300
2280
684
3080
DL;':^
(nn/L)
.•r^"<
>A i, '';~-
RECOVERY
- ' '••''''' (%)• -f '•'
55
51
55
65
55
69
68
63
63
65
57
68
62
O)
01
01
DL = Detection limit.
ff - Value from second column confirmation.
B = Congener found in lab blank at >20% of the concentration found in the sample.
-------
Table 6-26. Summary of PCB Results and Standard Recoveries for Lab Control Spike and Spike Duplicate
Scrubber Water Samples
AN'ALYTES'-V** '"•:. ".
PCB-77
PCB-123
PCB-118
PCB-114
PCB-105
PCB- 126
PCB-167
PCB-156
PCB-157
PCB- 169
PCB-180
PCB- 170
PCB- 189
INTERNAL V*X/tr ' ,,V,
STANDARDS, i !,
13C-PCB-77
13C-PCB-118
13C-PCB-105
13C-PCB-126
13C-PCB-167
13C-PCB-156
13C-PCB-157
13C-PCB-169
13C-PCB-180
13C-PCB-189
1 3C-PCB-209
CLEANUP STANDARDS
13C-PCB-81
13C-PCB-111
RECOVERY!
40 - 1 60
40 - 1 60
40 - 1 60
40 - 1 60
40 - 1 60
40- 160
40 - 1 60
40 - 1 60
40 - 1 60
40 - 1 60
40 - 1 60
40 - 1 60
40 - 1 60
„ TARGET
RECOVERY
' (%)•';'<
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
20-160
20 - 1 60
20 - 1 60
40 - 1 40
8pP
40000
40000
40000
40000
4000
40000
40000
40000
8000
40000
8000
8000
. ,rm '""
-ASPIRE; t
(pg/sample)
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
4000
100
5000
'V"'.tcs""^,?*-, __,-
'y&ff LCS-PCB 7
»pg/U
1360
31800
40740 E
56630 E
36460
2770
27630
30300 #
27740 #
4420
27900
6380
4680
tcsll|l:;Jf
48200-56-09 'Sll
' , LCS-PCB|f||,Sl
53
32
35
50
29
41 #
37 #
46
39
31
58
475
1930
"<*•• RECOVERY; -"^
166&
79
99
141
90
69
69
75
69
55
69
79
58
fcA^cdVERY,ll|Sf-
3 &
2 &
2&
3 &
1 &
2&
2 &
2&
2 &
2&
1 &
48
39
,- • -,;', • ,*i , /
•A," :=--> •,''• -^-'ifii- '• y- „•;, yft
||!, .. 48200-56>lb;;, ^
l||: LCSDUP-PCBj;: ••'?
853
31440
25970
48740 E
33080
3270
28320
30500 #
28600 #
4690
2466"6
4780
4300
^fe ,;48266-56-10§>- -'
'- i'SMLCSDllP-PCBflf^" t
j iilfi|;; (pg/sampie)',^^,-.
1060
657
650
809
572
835
752
677
727
726
1240
743
2820
Sj. RECOVERY
102
78
62
121
82
81
71
76
71
59
61
59
54
5C
3C
3:
4C
2J
4:
3£
3"
3(
3£
31
7J
5e
* ^RECOVERY:
48
1
46
15
10
16
2
1
3
6
12
29
8
•-*^i|£^:ISIi--
/ERYjfel^ltf;,.
i
J
i
)
)
»
5
t
5
)
i
OJ
01
o>
Lab Control Spike % Recovery is calculated as ((concentration found - lab blank conc.)/spike cone.) x 100.
& = QC value outside the target recovery goal for Method.
# = Value from second column confirmation.
E = Estimated value reported is outside of calibration range.
-------
recovered slightly above the data quality objective of 40-160%). Precision also was not
affected.
Blanks. Table 6-27 lists PCB results and standard recoveries for the lab blanks. All
water sample lab blanks were made using 1 L of HPLC grade reagent water in the laboratory.
The levels of PCBs detected in the various blanks are typical of background levels detected using
the sensitive high resolution mass spectrometry techniques. Because PCBs are detected in the
lab blank and because some samples did not contain high levels of PCBs above the background
levels there are several instances where the lab blanks exceeded the method performance criteria
of being at less than 20% of the sample concentration. Results for Runs 2, 3 and 4 are flagged
with a "B" in Tables 6-24 and 6-25 if the lab blank concentration was greater than 20% of the
reported sample concentration. Internal standard recoveries for the blanks were within the 20-
160% limits and ranged from 29-65%. Cleanup standard recoveries ranged from 54-84% for
13C12-PCB-81 (target recovery = 20-160%) and from 45-67% for 13C12-PCB-111 (target recovery
= 40-140%).
The target detection limit for these samples was 25 pg/L. Actual detection limits
achieved were significantly lower than this.
The target turnaround time for the PCB analysis of scrubber water samples was to extract
within 30 days of collection and analyze within 45 days of extraction. These turnaround times
were met with extractions occurring within 7 days of collection and analysis occurring within 29
days of extraction. The only exception is for the two archive samples (inlet Run 4 and outlet
Run 3) which were analyzed within 56 days of extraction.
D/F Analysis. The initial calibration met the requirement for response factors having less
than 20% relative standard deviation (RSD) for native analytes and less than 35% RSD for
labeled analytes (actual range = <10% for native analytes and < 8% for labeled analytes). All
analytes in all continuing calibrations met the requirement for response factors being within 20%
of the initial calibration response factors for native analytes and being within 30% of the initial
calibration response factors for labeled analytes.
Field Samples. Summary tables of D/F results and standard recoveries for the water inlet
samples are shown in Table 6-28. Water outlet sample results and standard recoveries are shown
in Table 6-29. Several internal standard recoveries were below the acceptability range for
Method 8290 of 40-135%, but most were within the range allowed by Method 1613 of 25-150%.
6-57
-------
Table 6-27. Summary of PCB Results and Standard Recoveries for Lab Blank Scrubber Water Samples
'• "'%" : '4l'1*''-:'''«v-- • '>' ' • 'ft' "
.:;%-, -%', *%*••>;? . ,-:
-&/-/:f,:,_r?'%;-v>?. - /•-. - -~, •
'ANALYTES *><*'•' ' ' ""'
PCB-77
PCB-123
PCB-118
PCB-114
PCB- 105
PCB- 126
PCB- 167
PCB-156
PCB-157
PCB- 169
PCB- 180
PCB- 170
PCB-189
ft * ,
INTERNAL STANDARDS
13C-PCB-77
13C-PCB-118
13C-PCB-105
13C-PCB-126
13C-PCB-167
13C-PCB-156
13C-PCB-157
13C-PCB-169
13C-PCB-180
13C-PCB-189
13C-PCB-209
CLEANUP STANDARDS
13C-PCB-81
13C-PCB-111
-T;- " "':•-% €*k
'"• '''*:<• "iipS!
TARGET <;V
RECOVERY , -
(%} •"',
20 - 1 60
20-160
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
20-160
20-160
20 - 1 60
20 - 1 60
20 - 1 60
40- 140
^m^ ^ <*..
$&:$>*. ."*;,
^>Af,^,;
SPIKE
- CONC.
(pg/sample)
2000
2000
2000
2000
2000
2000
2000
2000
2000
2000
4000
1000
5000
- /V:-S¥«-'*' •""'*;.- '•*;•
,; "^"LAfe'BLANK;/''^
48200-56-il'r *
l^:.- LB-PCB 'C/-.
'• ''*"'f (pg/U ':'>>..
38.7
83.0
985
152
480
8.25
93.0
124 #
70.6 #
8.97
173
60.5
13.7
LAB BLANK H!
48200-56-11 3; |
' LB-PCB Jll/"."
. (pg/sampteF'tfv-
821
628
617
878
712
919#
800 #
972
940
973
2220
540
2240
- ' '"• * " 'I/" ''?i'
• fj r S'fe
^s";,! ;; l -,/" '/*-*iS^u' "t •''''"&&:
'•'^'••- DL:\; *"'
(pg/U~i
is. ^ - ••,-,'.:•
S / ,'yj •" ' , '." : . •-
", *, ^"^--~ 4^' ,""'"
JS* RECOVERY
•^&. := (%j . >&::
41
31
31
44
36
46
40
49
47
49
56
54
45
'-%k- /te- . .-'J%
fc--'^,r-'-".-k-v-' -:t
| LAB BLANK-ARCHJVE
5>; 48200-56-11
-"%;. . "•"qpg/L) ",'f;:- V-
26.8
41.0
858
91.3
396
(4.19) J
45.4
73.7 #
33.8 #
5.14
131
46.1
10.4
;S LAB BLANK-ARCHIVE "
'"V- -48200-56-11? '''-'
-v**|^ ": BH-LB-PCBgv,; _ . , 1
'"s*: (pg/sample) "-tlii r'
1290
729
659
1080
749
890 #
720 tt
912
859
684
1140
843
3360
#:}*.•*$$».
1', '• 'I"' : "'"• >-">''''"'
'•9Z[. DL "'1,
%3;:(pg/L) .*
4.82
|f «^"\ ••";?
/?i><> % " • '. ^ V - , -
?*i RECOVERY
^fc;->- j%>*s- -
65
36
33
54
37
44
36
46
43
34
29
84
67
O)
en
oo
DL = Detection limits.
# = Value from second column confirmation.
J = Estimated value, below detection limit.
-------
Table 6-28. Summary of Dioxin/Furan Results and Standard Recoveries for Scrubber Water Inlet Samples
^ C,,'"-^'-'™" '" "r /i""'"' ??~ ""4 1i '" M"a.
. -: '•' ./, '•" .';';^^- '•*.$•*{''.."-$&•'•• : -1;i*f
' ANALYTES :. *•?? \ ' '"'<£$*•' ' 'fr? <' . >?'AK=; -/<
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Total Tetra-Furans
...T.Q.taL.T.etra:Dipx.in.5 _
Total Penta-Furan
Total Penta-Dioxins
Total Hexa-Furans
Total Hexa-Dioxins
Total Hepta-Furans
Total Hepta-Dioxins
Total TEQ
, RUN 2
48200-57-02
ri,';,wi-R2-2iiAi'<;
•i'/-- - .'-,.
~(pg/L|^ft4:
12.6
27.4
12.7
13.5
12.9
32.8
9.50
17.7
11.1
14.4
12.7
17.5
14.1
9.31
35.0
46.7
28.7
35.5
45.9
53.4
29.2
19.1
98.7
-'-I-'/ RUN3,;;<:>»
48200T57-04>
, WI-R3-311A
1 y'-. -.
'"•..""•"''bt
''."" (pg/U '' v •
2.59
7.06
2.06
2.22
2.11
4.32
2.07
3.80
1.58
2.29
2.25
2.50
2.26
4.72
5.87
4.88
5.89
6.27
11.8
2.26
4.77
10.5
13.0
RUN 4
48200-57-06 ,
WI-R4-411A
(pg/LJ
ND
ND
ND
ND
ND
ND
15.7
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(2.93) J
ND
0.02
•'•", '•*--"' A
J»;14f?*J!6!l>~ '."'.:
'•iflfi Vt/J ";"
f ' ,"."-b'c *'
(pg/L)
7.66
23.2
6.10
6.49
6.19
12.2
6.33
11.4
5.02
6.42
6.17
7.70
6.77
3.35
13.5
15.8
14.9
17.4
19,4
38.8
24.8
14.0
29.4
36.7
O)
01
CO
-------
Table 6-28. (Continued)
•f 7^/;- ;""f^" " ''^%' '
Hr?' ;*i^^fi
INTERNAL STANDARDS
13C-2378-TCDD
13C-12378-PeCDD
13C-123478-HxCDD
13C-123678-HxCDD
...1.?C:.1.234678.:HpCDD
...13C:.1.234678.:HpCDD
13C-OCDD
13C-2378-TCDF
13C-12378-PeCDF
13C-23478-PeCDF
13C-123478-HxCDF
13C-123678-HxCDF
13C-123789-HXCDF
..l.3C:.1.2.34_678-HpCDF.
13C-1234789-HpCDF
CLEANUP STANDARDS
'jf'A',,-:,, ,~ -i&iZ
-'TARGET J 4s
RECOVERY
»t, (%)'$!iy
40-135
40-135
40-135
40-135
40..-..1.35
40..-..1.35
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40 -..1.35
40 - 1 35
40 - 1 3 5
V ^|4j/"^l'*
|'.V SPIKE V
%>it*mtrW?'
,yVwwl»\**/>^'
(pg/sample)
2000
2000
2000
2000
2000
2000
2000
4000
2000
2000
2000
2000
2000
2000
2000
200
%^RUN'2llfei,
48190-57-02$
<<--WI-R2-211 A ;*>;';
(pg/sample)
1180
1480
1070
1160
860
1.540
1220
1200
959
1010
1095
920
1030
820
760
121
"."• ?fSgv.^
;•'; RECOVERY,!!^
,V- '-• (%} "&iX'
59
7.4
53
58
43
38&
61
60
48
50
55
46
51
41
38 &
60
. .Zfttyff.'tf., £:'•, .,-. - *
-' '^"R(JN"3;<; '
48190-57^04
/Sjr-wi-Rs-anA;!,,
l:ff> (pg/sample) ''•', ' "
670
7.92
698
797
726
1310
633
720
756
690
717
703
713
680
623
132
""''r!1''' ' •''""*?>
"RECOVERY-:^
";•(%) >-' . •'
33 &
.40
35.&
40
36 &
33 &
32 &
36 &
38 &
35 &
36 &
35 &
36 &
34&
31 &
66
- "S'^-'i'^^'-WJ^ ~ *• *+fl'"""; ? ,
7.1.4
802
7.7.3
?.Q2
830
1580
666
761
753
788
862
765
793
798.
725
140
fl *** ' ~~" %"" " ™-
, iRECOVERY
Sf^(%r^
36 &
40
39 &
45
41
40
33 &
38 &
38 &
39 &
43
38&
40
40
36 &
70
O)
O)
o
DL = Detection Limits; {EMPC}.
& = QC value outside the target recovery for Method.
ND = Not detected.
J = Estimated value, below detection limit.
-------
Table 6-29. Summary of Dioxin/Furan Results and Standard Recoveries for Scrubber Water Outlet Samples
',-'', ' - / , , f« rr 3"~/
ANALYTES > „ '..' • ,'- '( :.- •'&*•' " '.'.' . ,' /* ,
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Total Tetra-Furans
...T.9.taLTetr.a.-Dip.xi.n§
Total Penta-Furan
Total Penta-Dioxins
Total Hexa-Furans
Total Hexa-Dioxins
Total Hepta-Furans
Total Hepta-Dioxins
Total TEQ
/•;''-. RUN 2.--«; "•.'
48200-57-03
WO-R2-212A
(pg/L)
9.06 tt
ND
1.48
2.82
2.78
11.0
29.5
181 tt
14.3
29.4
11.6
4.56
ND
6.23
12.4
ND
6.19
824
.475
318
46.4
48.1
29.5
17.3
27.4
39.6
•'•'"" DL-V^
(pg/L)
4.94
1.77
3.24
/>•>"', -• , . " •/;
!K~' RUN3^» :"'
48200-57^05
WO-R3-312A
(pg/L)
(13.3) #,J
ND
ND
ND
ND
24.6
58.7
222 tt
24.5
45.4
16.4
6.66
ND
12.8
19.6
ND
10.4
1120
821
493
57.3
80.2
53.5
28.9
52.9
55.3
' :DLoi i^
(pg/U
4.38
13.1
3.90
4.02
3.89
4.83
8.33
RUN 4
48200-57-07
; WO-R4-412A
: (pg/L)
13.5 tt
ND
2.61
6.07
5.73
31.9
47.0
256 tt
25.4
53.1
25.0
10.7
ND
16.5
25.0
ND
8.16
866
277
495
65.6
113
102
35.3
73.6
61.7
>,;, ^','i,,. _ . -•
. < i '- " •
>~ ,ff - * , - ,
DL
(pg/L)
4.12
1.68
3.34
O)
I
O)
-------
Table 6-29. (Continued)
liSSt," ..SV-:- '*,,'-,-" •*5t#is. ' ';'?"
t^ffk^'-vf^/v-^*;*?.?^-.., ' '•'
INTERNAL STANDARDS ,,
13C-2378-TCDD
13C-12378-PeCDD
13C-123478-HxCDD
13C-123678-HxCDD
...1.3C;.1234678:HpCpp
13C-OCDD
13C-2378-TCDF
13C-12378-PeCDF
13C-23478-PeCDF
13C-123478-HxCDF
13C-123678-HxCDF
13C-123789-HXCDF
13C-234678-HpCDF
13C-1234678-HpCDF
13C-1234789-HpCDF
CLEANUP STANDARDS
'«*»'- It,*,;/-.,.
«-;'.TARG|T^;;
*CRECOVERY||r
' '%;<%) •'-" ••
40-135
40-135
40-135
40-135
40.-.135
40-135
40-135
40-135
40-135
40 - 1 35
40-135
40-135
40-135
40-135
40-135
40 - 135
I'|':.-""'":>CI^
"*: SPIKE '-'>
CONC.
; ~
>{pg/L) V
1010#
1220
1100
1110
1060
2040
1020*
1100
1120
1020
1060
1070
1050
1010
976
127
/*'•„•' • . -
';"";,',; (i {, , ,<";;«;
RECOVERY!^
' ',/ff",'i
(%)
50
61
55
55
53
51
51
55
56
51
53
54
53
51
49
63
\ - „ ^A ' /$$,('*' fA?^' ,
'^:-v-RU*l;%-- •
; V481 90-57-05
p,VyO-R3-312AU
ll*;1,'' (pan.}
384 #
457
404
466
449
813
406 #
408
423
408
425
412
418
403
382
131
- ^-'H £i,'%,t' "^'jt%
- " life ?*
: REGOVERYi*
(%!*'.
1?.&
23 &
20 &
23.8.
22&
20 &
20 &
20 &
21 &
20 &
21 &
218.
21 &
20 &
19 &
65
Jfi: rf RUN 4 v" '•;
1*8)1 90-57-07 ','''
|wp-R4-412A*;^
(pg/Lj
1320 tt
1420
1220
1340
1130
1960
1310 tt
1300
1300
1200
1210
1160
1250
1080
989
139
^'^REiM^ERyS
.'''(%iifM
66
71
61
67
56
49
65
65
63
60
61
58
62
54
49
69
cn
en
ro
& = QC value outside the target recovery goal for Method.
ND = Not detected, detection limit value provided in adjacent righthand side column.
it = Value from second column configuration.
J = Estimated value, below detection limit.
-------
All of the internal standard recoveries for Run 3 outlet water sample (WO-R3-312A) were below
Method 1613 limits. Because the cleanup standard recovery for this sample (65%) is within
acceptable limits and similar to recovery of cleanup standard in other outlet samples, the low
internal standard recoveries are attributed to inefficient extraction rather than losses during
cleanup procedures. The particulate matter found in the scrubber water samples may have
contributed to the lower recoveries as the samples required processing through several solid
phase extraction (SPE) columns (see Corrective Action Report in Appendix P-3). Low internal
standard recoveries can increase the degree of uncertainty about the accuracy of concentrations
measured in a sample. However, because the internal standard recoveries for WO-R3-312A (19-
23%) did not diverge greatly from the acceptable limit for Method 1613 (25%) and because there
was good precision in the concentrations of analytes found between Runs 2, 3 and 4, it is not
expected that the low internal standard recoveries for this sample had any significant impact on
reported results.
Lab Control Samples and Blanks. Table 6-30 presents D/F results and standard
recoveries for the laboratory control spike, laboratory control spike duplicate (LCS/LCSD), and
lab blank scrubber water samples. Recovery of all native D/F spiked into the LCS/LCSD were
within the 40-135% target range (actual range = 54-111%). The relative percent difference
(RPD) between analytes in the duplicates were all under the target <20% except for OCDF (RPD
= 57%). Internal standard and cleanup standard recoveries for the LCS/LCSD were all within the
40-135% target and ranged from 47-74%. Only a trace of OCDD was detected in the lab blank.
All water sample lab blanks were made using 1 L of HPLC grade reagent water in the laboratory.
Low levels of OCDD in blanks are not uncommon due to the prevalence of this analyte in the
environment. Internal and cleanup standard recoveries in the lab blank ranged from 53-70% and
were all within the target range of 40-135%.
The target detection limit for these samples, based on the lowest calibration level using
the Method 1613 calibration curve was 10 pg/L for tetra compounds, 50 pg/L for penta-hepta
compounds and 100 pg/L for octa compounds. These detection limits were achieved.
The target turnaround time for the D/F analysis of scrubber water samples was to extract
within 30 days of collection and analyze within 45 days of extraction. These turnaround times
were met with extractions occurring within 8 days of collection and analysis occurring within 21
days of extraction.
6-63
-------
Table 6-30. Summary of Dioxin/Furan Results and Standard Recoveries for Lab Control Spike, Spike Duplicate, and
Lab Blank Scrubber Water Samples
'**. %;;• -;fi
• ',.",: ' ,V Vi -' ' • "',
'- <<
ANALYTES > .'"".
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Total Tetra-Furans
Total Tetra-Dioxins
Total Penta-Furan
Total Penta-Dioxins
Total Hexa-Furans
Total Hexa-Dioxins
Total Hepta-Furans
Total Hepta-Dioxins
Total TEQ
' "'v*!',<^' .- . ; ~
r-,' TARGET;',.;
ItRECOVERYjf
llrj%) • ••''••.
40-135
40 - 1 35
40 - 1 35
40 - 1 35
40-135
40-135
40-135
40-135
40-135
40-135
40 - 1 35
40-135
40 - 1 35
40-135
40-135
40-135
40-135
''^'LCS " "
r SPIKE
£r~coNcl*::*r-
lw.?{pa/u -•-••'
200
1000
1.000
1000
1000
1000
2000
200
1000
1000
1000
1000
1000
1000
1000
1000
2000
%"',;.•'<• ;'. . '/'•:•,
.-''•sties: '•
48200-57-08
(pfl/U
223
1.Q50
964
1010
985
1020
2030
207
1090
1090
1040
1050
1020
1110
1080
1060
1940
210
223
2190
1050
4220
2960
2140
1020
2120
RECOVERY
{%)
111
105
96
102
98
102
101
101
109
109
104
105
102
111
108
106
97
':'">''lf',iW-''
'•LCs"i>U>;
48200-57-09
;<:i-
6
1
8
2
1
4
5
5
3
8
3
2
6
5
3
5
57 &
'LAB BLANK
48200-57-28
ND
ND
ND
ND
ND
ND
5.30
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.005
' ,-';; DL^Y
"•.-'•:•• (pg/DH
1.52
3.96
1.11
1.21
1...15
2.08
1.09
2.06
0.830
1.23
1.21
1.25
1.15
0.62
2.12
2.66
2.58
3.46
3.34
6.63
4.50
2.60
5.05
6.26
CD
O>
-------
Table 6-30. (Continued)
'^^-:'-':,;.';,;,,.^..>'V':"' ;
INTERNAL STANDARDS
13-2378-TCDD
13C-12378-PeCDD
13C-123478-HxCDD
13C-123678-HxCDD
13C-1234678-HpCDD
13C-OCDD
13C-2378-TCDF
13C-12378-PeCDF
13C-23478-PeCDF
13C-123478-HxCDF
13C-123678-HxCDF
13C-123789-HxCDF
13C-234678-HpCDF
13C-1234678-HpCDF
13C-1234789-HpCDF
CLEANUP STANDARDS
37CI-2378-TCDD
' ' . '.--^^1
TARGET
RECOVERY;
- {%)%|g#i'i>
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
40-135
f >•; LCS
SPIKE
-i cone.
(pg/sample)
2000
2000
2000
2000
2000
4000
2000
2000
2000
2000
2000
2000
2000
2000
2000
200
' ,:i£s1£Kf t
48200-57-08
(pg/sample)
1190
1480
1360
1440
1360
2560
1270
1340
930
1310
1280
1370
1420
1260
1260
127
RECOVERY
(%) ;
59
74
68
72
68
64
63
67
47
65
64
69
71
63
63
64
Jyf:.:>'v " -
f '/? *"' -' <
LCSDUP/.
*.;, 48200-57-09;;%'
Kr*- {pg/sample) "'•• .'.
1090
1360
1330
1380
1310
2170
1170
1260
1430
1270
1280
1260
1370
1240
1050
125
RECOVERY^
(%>
54
68
67
69
66
54
59
63
71
63
64
63
69
62
53
62
j£ LAB BLANK
• 48200-57-28
(pg/sample) .,
1060
1360
1280
1380
1390
2770
1140
1260
1390
1220
1230
1340
1320
1260
1290
117
" ''{fi^'l?
• , ,DL;-£/J;
(pg/sample)
53
68
64
69
70
69
57
63
70
61
61
67
66
63
65
59
cn
O)
01
Lab Control Spike % Recovery is calculated as ((concentration found - lab blank cone.I/spike cone.) x 100.
ND = Not detected.
DL = Detection limit.
& = QC value outside the target recovery for Method.
-------
Chlorine Analysis. Samples for chlorine analysis were collected from both inlet and
outlet scrubber water systems. Chlorine is metered into the final effluent at a known and
constant rate; however, there is no control on the Cl concentration in the effluent utilized by the
scrubber water system. MSD expected the chlorine concentration in the effluent water to range
from 3 to 4 mg/L. Samples from the first day of sampling were analyzed by the USEPA T&E
laboratory and found to contain negligible Cl. MSD analyzed duplicate samples using the
amperometric method (APHI Method 4500-Cl-d). Table 6-31 shows that the MSD results
verified the results obtained by the T&E Laboratory.
Table 6-31. Intercomparison of Total Chlorine Analyses
-•\-.--'% Date
July 21
July 22
Scrubber Water
In
Out
In
Out
T&E, mg/L V f'
0.09
0.00
0.08
0.03
/' •*'" MSD, mgflf
0.04
0.00
0.00
0.00
6.1.3.3 Sewage Sludge Feed Samples
PCB Analysis. The initial calibration for both the SPB-Octyl and DB-1 analyses met the
requirement for response factors having less than 35% relative standard deviation (RSD) for all
analytes (actual range = <17% for SPB-Octyl and DB-1 calibrations). The continuing
calibrations met the requirement for response factors being within 35% of the response factors
generated in the initial calibration for at least 70% of the analytes. In fact, all analytes in all
continuing calibrations were within 35% of the initial calibration.
Field Samples. PCB results and standard recoveries for the sewage sludge feed samples
are shown in Table 6-32. Internal standard recoveries were within the method specified limits of
20-160% and ranged from 34-62%. These internal standard recoveries indicate analytes were
well recovered during laboratory extraction and were retained during the extract cleanup process.
13C12-PCB-81 and 13C12-PCB-111 were added to the sewage sludge samples as cleanup standards
after extraction but before any cleanup procedures. Method specified recovery ranges for these
standards were from 20-160% for 13C12-PCB-81 and 40-140% for 13C]2-PCB-111. Recovery of
6-66
-------
Table 6-32. Summary of PCB Results and Standard Recoveries for Sewage Sludge Samples
"' *f '"'f'f '','
y^"",V?
ANALYTES
PCB-77
PCB-123
PCB-118
PCB-114
PCB-105
PCB-126
PCB-167
PCB-156
PCB-157
PCB-169
PCB-180
PCB-170
PCB-189
INTERNAL
STANDARDS
13C-PCB-77
13C-PCB-118
13C-PCB-105
13C-PCB-126
13C-PCB-167
13C-PCB-156
13C-PCB-157
13C-PCB-169
13C-PCB-180
13C-PCB-189
13C-PCB-209
CLEANUP
STANDARDS
13C-PCB-81
13C-PCB-111
• ••$£•••-:*
•: ''•.. '-'&
i ?V,^pf|?
;-5g;ifci".'
:- TARGET!:-'
RECOVERY
" (%)
20 - 1 60
20-160
20-160
20-160
20-160
20-160
20-160
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
40 - 1 40
*M,!'.;?' , • v
"Xt4 • •!• '•
?:-,*£ '-^
f^ ', i' ,
""'*''• SPIKE :
• • CONC/;/;i'fi
(pg/sample)
15000
15000
15000
15000
15000
15000
15000
15000
15000
15000
30000
6000
30000
V'"'':RUN~2*.jf>|li
• 48290-15-08 $
S-R2-213B r
(pg/gdry)
40900
231 B
12250 B
691 B
7010 B
1120
878 B
1770 it
472 0
453
6000
2530
181 B
....' ' -••*> is ..,„.
"•••,- RUN '3 *";i'
* 48190-15^08
§f|*!S-R2-213B\ ;
"j (pg/sample)
7330
6920
7080
5990
6620
9330 0
91900
5260
7420
7180
12650
2370
13940
;• " ._' DL' :"':}\"
?'!? (pg/g dry)
RECOVERY'S
(%> r''r.r
49
46
47
40
44
62
61
35
49
48
42
40
46
' $ -',
RUNS
48190-15-09
? S-R3-313B I
i:'r* (pg/g dry) •'•"-'
41090
276 B
13500 B
674 B
7390 B
1210
968 B
18800
565 #
601
6780
2570
198 B
RUN 3
48190-15-09
*?f;S-R3-313B "••'
(pg/sample)
6910
7230
7370
6120
6610
8860 #
8540 #
5050
7460
7230
13400
2180
13300
'"'ii\ DL - ;""-:
:; '" (pg/fl dry)
RECOVERY
(%)
46
48
49
41
44
59
57
34
50
48
45
36
44
RUN 4
48190-15-10
S-R4-413B
(pg/g dry)
45380
241 B
12860B
738 B
7290 B
1480
959 B
18800
536 #
656
6710
2780
218B
RUN 4
48190-15-10
S-R4-413B
(pg/sample)
7300
7380
7540
6250
7220
90000
88000
5490
7960
7680
14600
2410
13900
'• Viyt 'ifj'flsJ&t-i'
, __..-_ /^.iUIL ;,,,.; >,-
' '••• ipg/g"dry)- -
RECOVERY
(%)
49
49
50
42
48
60
59
37
53
51
49
40
46
O)
I
O)
DL = Detection limit.
0 = Value from second column confirmation.
B = Lab method blank contamination of target analytes at the level above DL.
-------
the cleanup standards were within the limits and ranged from 36-40% for I3C]2-PCB-81 and from
44-46% for 13C12-PCB-111.
Lab Control and Blank Samples. Table 6-33 presents PCB results and standard
recoveries for the matrix spike and matrix spike duplicate (MS/MSD) sewage sludge samples
and the lab blank. Recovery of all native PCBs spiked into the MS/MSD were within the 40-
160% target and ranged from 83-160%. The relative percent difference (RPD) between
duplicates were all under the target <50% and ranged from 1-20 % indicating acceptable
analytical precision was achieved. Internal standard recoveries for the MS and MSD were within
the acceptable range of 20-160% and ranged from 37-65%. Cleanup standard recoveries for the
MS/MSD samples were 40-42% for 13C12-PCB-81 (target recovery = 20-160%) and 50-53% for
13C12-PCB-111 (target recovery = 40-140%). As with the emission and water samples, the lab
blank for the sewage sludge samples contained background levels of PCBs that are not
unexpected due to the ubiquitous nature of PCBs. The levels of PCBs detected in the lab blank
are typical of background levels detected using the sensitive high resolution mass spectrometry
techniques. Because PCBs are detected in the lab blank and because some samples did not
contain high levels of PCBs above the background levels there are several instances where the
lab blanks did not meet the method performance criteria of being less than 20% of the sample
concentration. Results for Runs 2, 3 and 4 are flagged with a "B" in Table 6-32 if the lab blank
concentration was greater than 20% of the reported sample concentration. Several internal
standard recoveries for the lab blank (13C12-PCB-77,13C12-PCB-118 and 13CI2-PCB-105) were
lower than the acceptable limit of 20-160%. Cleanup standard recoveries were also slightly lower
than the acceptable limit with 13C12-PCB-81 recovered at 15% (target recovery = 20-160%) and
13CI2-PCB-111 recovered at 13% (target recovery = 40-140%). The low cleanup standard
recoveries indicate that analyte losses may have occurred during the cleanup process and are not
representative of inefficient extraction of analytes in the lab blank. Low internal standard
recoveries increase the uncertainty about the accuracy of reported native analyte concentrations;
however, the concentrations of PCB-77, PCB-118, and PCB-105 found in the sewage sludge lab
blanks when compared to the concentrations of these analytes in the lab blanks for emission and
water samples (comparing all on a pg per 20/uL extract basis) are very similar. This increases the
6-68
-------
Table 6-33. Summary of PCB Standard Recoveries for Matrix Spike, Spike Duplicate, and Lab Blank Sewage Sludge Samples
^\,*-: $&#•.{&&&•
•' •%''•% ''$>**:>;" • -• TARGET,;*!
'"'' **" "•"- 'tf'ti&.&'l, "' "RECOVllfP
ANALYTES'tW'f **J*' «*''•(%}"';"«?
PCB-77
PCB-123
PCB-118
PCB-114
PCB-105
PCB-126
PCB-167
PCB-156
PCB-157
PCB-169
PCB- 180
PCB-170
PCB-189
40 - 1 60
40 - 1 60
40 - 1 60
40 - 1 60
40- 160
40 - 1 60
40 - 1 60
40 - 1 60
40 - 1 60
40 - 1 60
40 - 1 60
40- 160
40 - 1 60
Y"~<'- *'•"''" TARGET*!
INTERN AL-^8|? . ;,r : RECOV,?
•-STANDARDS^!". ?'•?'' •;'.{%}&&.
13C-PCB-77
13C-PCB-118
13C-PCB-105
13C-PCB-126
...13C;PCB:167
13C-PCB-156
13C-PCB-157
..13C;PCB:169
13C-PCB-180
13C-PCB-189
13C-PCB-209
..CJUEAMUP.S.IANDAR
...13.C:PCB;8.1
13C-PCB-11 1
20 - 1 60
20 - 1 60
20 - 1 60
20 - 1 60
...20..-..1.60...
20-160
20-160
...20..-..1.60...
20- 160
20- 160
20 - 1 60
tQS
20 - 1 60
40 - 1 40
: JMATRIX MATRIX SPIKE? JV
^flef SPIKE> '',Tt; " - - 48190-15-11 ', "'''
^€cbNC:^S|il5';;':{s-R474JI3B MS.-?- •
'" (pg/g dry) ''' •"'">'' <'lpg/a*"dry)fc<' >>;'>s-
84200
84200
84200
84200
84200
8420
84200
M200.
84200
16800
84200
. . 1 6800
16800
|ia/iATRix,j /;
ti" (pg/sample)
15000
15000
15000
15000
1.5000
15000
15000
1.5000
15000
15000
30000
6000
30000
130300
100090
{02570
135300
..116600
11040
98450
109500*
1 00000 ft
16750
112500
23600
18800
.%•;;;/ u-;i ' , , MSDUP>'V-;*J&
* '' '•"'••" •'::;48190-,15-iil2;'S
, RECOV^r^:||S-R4-413B ' "'""»
„, -,(%jj "'. W*'(pg/odry) '
101
119
107
1.60
1.30
114
116
128
118
96
126
124
110
1 1 5000
99400
88000
132800
107700
10420 . ...
99000
1 06200 tt
102100*
17100
107600
21.560
19100
|>i .-. . • ' • " -""'; " >H-sfe,LAB,BLANK ^'>;lfiM;»;'SSfe
Illf ?':;. .": ' .RECOV^t '^48190-15-1 5 ';J
'REcbvTf/^RPD -•" *;/ LB-PCB; y-:S#^^f>fc^"':f
- •(%) ^».M??(%> • •'. *(pg/g dry) .'v-'ttl^fipgifa^ryjSj;;
83
118
89
1.57 „
1.1.9
106
..117
124
1.21
..97
120
112
112
. 20 . . J
1
18
2
8
7
1.
3
2
ry
5
10
2
238
122
4690
253
21.30
ND
309
296 tt
89...5..C
ND
724
319
91.9
1.7.6
67.9
:'*' MATRI|C£HKE»W..,C- ;-. ' v.'-'';' MS DUP -,-'.'- -.- -,,.-:. ' • '?l., V"*'^?^.
/, 48190?15-1 1 S$8 •'•-&%$. 4^1-ife?1 48190-1 5-12 ' -' ' '"//V '•> j^j, : •..;•;-, -, 48190-1 5-16 ;,i;f ^^JK^-'C^- '. '•
|t?:2S-R4-413BMS':"" -' RECW;/rM|S'rli4-413B MSD RECOVi»^||;i, ^ A LB-PCB ' >* -'''l^^mKCOV^i-
^•^'(pg/nmple) '->••' (%) -' *' :-^(pg/sample)fe^r''- M%> '"""'''^'^C'Jpg/isample) • "A^Si(%l5fe- '"'
7470
7870
7900
6150
7.770
9630 ff
9600 #
5550
7960
7540
14500
2500
15000
50
52
53
41
52
64
64
37
53
50
48
42
50
7830
. 7970
8240
6640 . . .
.7.490
9730 #
9380*
5640
8150
7570
14900
2400
15800
52
53
55
44
50
65
63
38
54
.50....
50
40
53
2390
2040
23QO
3290
31.60
435.QJ
4030 tt
4380.
41.60
4900
10560
872
3980
1.6.&
14&
15 &
22
21.
29
.27
29
28
33
35
1.5.&
13 &
cn
O)
CO
DL = Detection limit.
Matrix Spike % Recovery is calculated as ((concentration found - Run 4, 48190-1570, S-R4-4138 cone.I/spike conc.i
& = QC value outside the accuracy of precision goal for Method (40-160% spike recovery of lab spike samples.
tt = Value from second column confirmation.
x 100.
-------
confidence in the accuracy of the concentrations reported for PCB-77, PCB-118, and PCB-105
for the sewage sludge lab blank.
The target detection limit for sewage sludge samples was 55 pg/g dry weight. Actual
detection limits achieved ranged from 45-209 pg/g dry weight. Since actual levels of PCBs in
the three sewage sludge feed samples are at least two times the detection limits, and since the
detection limits achieved were all lower than the lower calibration range for the PCBs, these
higher than expected detection limits are not expected to affect the quality of the PCB sludge
concentrations reported.
The target turnaround time for the PCB analysis of sewage sludge samples was to extract
within 30 days of collection and analyze within 45 days of extraction. These turnaround times
were met with extractions occurring within 18 days of collection and analysis occurring within
18 days of extraction.
D/F Analysis. The initial calibration met the requirement for response factors having less
than 20% relative standard deviation (RSD) for native analytes and less than 35% RSD for
labeled analytes (actual range = <10% for native analytes and < 8% for labeled analytes). All
analytes in all continuing calibrations met the requirement for response factors being within 20%
of the initial calibration response factors for native analytes and being within 30% of the initial
calibration response factors for labeled analytes.
Field Samples. D/F results and standard recoveries for the sewage sludge samples are
shown in Table 6-34. All internal standard and cleanup standard recoveries were within the
target range of 40-135% (actual range = 60-87%).
Lab Control and Blank Samples. Table 6-35 presents D/F results and standard
recoveries for the matrix spike, matrix spike duplicate (MS/MSD), and lab blank sewage sludge
samples. Recovery of all native D/F spiked into the MS/MSD were within the 40-135% target
range (actual range = 49-65%). The relative percent difference (RPD) between analytes in the
duplicates were all under the target <20% and ranged from 0-8%. Internal standard and cleanup
standard recoveries for the MS/MSD were all within the 40-135% target and ranged from 60-
87%. Only a trace of OCDD was detected in the lab blank. Low levels of OCDD in blanks are
not uncommon due to the prevalence of this analyte in the environment. Internal and cleanup
standard recoveries in the lab blank ranged from 47-74% and were all within the target range of
40-135%.
6-70
-------
Table 6-34. Summary of Dioxin/Furan Results and Standard Recoveries for Sewage Sludge Samples
*iil5"' ;-';'",-: ',-'/'!, f'^' ,, . • z'"fl'*!--- ' -^t,
ANALYTES ''''":' " • -. „ :/'> " V
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Total Tetra-Furans
Total Tetra-Dioxins
Total Penta-Furan
Total Penta-Dioxins
Total Hexa-Furans
Total Hexa-Dioxins
Total Hepta-Furans
Total Hepta-Dioxins
Total TEQ
*-;Kl|l*;'K.RUN2' f^\
v ^;8|!48190-15-02 ;',:.?? Vl
^'ik 5 S-R2-213A -;•;•'
,'E;,%tf •..,>, (pg/gdry) '" ,z»r'
(2.75) #,J
ND
ND
15.0
27.3
229
2510
20. 6 #
ND
8.09
{1.3.7}.
ND
ND
6.21
134
ND
313
{76.5}
67.7
90.2
30.3
97.7
128
239
431
19.5
i r"" V, A",/^";1 V" •- "'' "~^'>l~
*t$l?"'"~ DL "
(pg/gdry) -'
14.6
15.0
4.71
7.75
5.04
5.88
11.7
'. -" miti's'^f ' ••
48189-15-03
S-R3-313A ;«f
(Pfl/g dry) l?- ?
(2.87) #,J
ND
ND
17.9
{24.3}
281
2690
24.1 #
ND
9.21
19.3
7.51
ND
{8.43}
159
ND
340
{95.9}
82.6
95.2
23.3
117
135
284
520
22.8
, '*J~vff,-~",;'; ,.'', "'. "
.^.''C1« '- •'
i~rji«k-.--
;;:>„ r- DL
<4 (pg/fl dry) «/
15.6
17.0
5.40
8.48
6.64
12.6
• >:;RUN4if*':7
48190^5-04 C
>,tS-R44l3A" '
;'S?v'A (pg/g dry) "
(5.14) #,J
ND
8.24
30.7
39.9
384
3690
35.1 #
12.7
13.4
29.6
{10.0}
ND
13.3
222
ND
441
£120)
95
163
29.6
171
{204}
377
701
34.6
DL
(pg/g/dry)
14.5
17.4
6.99
13.0
O)
-------
Table 6-34. (Continued)
fSiiSf/ '•4^f'*4f,''^''i- ".'•?'?'•
r^flff' ,'^?j^|j|h -'"** r ' v
,;;,'%- "'-'"j ^ftffin&fjj}, "f^,, ' ' '»
INTERNAl5STAr>ibARDS
13-2378-TCDD
13C-12378-PeCDD
13C-123478-HxCDD
13C-123678-HxCDD
1 3C-1 234678:HpCDD
13C-OCDD
13C-2378-TCDF
13C-12378-PeCDF
13C-23478-PeCDF
13C-123478-HxCDF
13C-123678-HxCDF
13C-123789-HxCDF
1 3C-234678-HpCDF
1.3.C.-1234678:HpCDF
..13C-1.234789:HjpCp.F
CLEANUP STANDARDS
37CI-2378-TCDD
';"*'l5S"fi/*!i
;, TARGET,;- V
f«RECOVf!?
40-135
40-135
40-135
40-135
...40.- 135.
40-135
40-135
40-135
40 - 135..
40-135
40-135
40-135
...40-135 1..
..40-135.
40-1.35
40-135
^,-'-r'^'V, '"'"••','
f$|£. SPIKE »" ","'
feffcoNcfe' -
(pg/sample)
2000
2000
2000
2000
2000
4000
2000
2000
2000
2000
2000
2000
2000
2000
2000
200
• . 'RUN 2f-': v
48190-15^02 ;
f -jl-'i; S-R2-21 3A |M*
• (pg/sample) tj.-1^
1470 #
1600
1470.
1550
1370
2470
1390 #
1520
1440
1410
1.460
1360
1490
1330.
1200
121
=ffS|||«. _" - '• , ' -;"
:/r^jff%:v> .. -y
i>l'r • ' RECO V.;; „ ' v-
i^'t . fCU.1 ''^ -
K'£"*-t' \*"J ( ••„,
73
80
73
77
69
62
70
76
72
71
73
68
74
67
60
61
"¥»i*;,K 'RUN S'lPvl:?" '-Ji'.'
"':;348190-15^03 f-rr- %
S*+6'S-R3-313A5te;: •- •:
' ; • '
1590 ff
1740
1590
1580
1430
2720
1540 #
1670
1630
1510
1540
1440
1530
1410
1260
131
., - ,' \'f./y'~>f!ill
"*•' ' tf--"'- ' -?*
*','" ;RECQV;V' " ' .
'6;i. J%)^-' •
79
87
79
79
72
68
77
84
82
76
77
72
72
71
63
65
fe;<-//.RUN4--,--:-.^
1^48190-15-04.^4
iS;t|S-R4^413A;:i ;;
(pg/sample) ;
1 600 #
1700
1570
1650
1470
2900
1410 #
1670
1530
1560
1.590
1450
1610
1440
1290
134
ftej,..- -.'
*yljllsf#f i-
JjRECbVfe
• r I Qit- ", -'
~ A^ V*" * "^*"/«^
80
85
79
82
74
72
71
83
77
78
.7.9
72
80
72
64
67
O)
DL = Detection Limits; {EMPC}; (Below Detection Limit).
tt = Value from second column confirmation.
ND = Not detected.
J = Estimated value, below detection limit.
-------
Table 6-35. Summary of Dioxin/Furan Results and Standard Recoveries for Matrix Spike, Spike Duplicate, and Background
Sewage Sludge Samples
^'J'/i. 2" ' ~* " t ™ „•* l"^
i>f',l/^f ., ,*^ ,^'' '"' • "*' ,*|f"
:,-.& lf( ;'? ' _,/. ;jjlf;:W"f:"f
ANALYTES • y:,>|if
2378-TCDD
12378-PeCDD
123478-HxCDD
123678-HxCDD
123789-HxCDD
1234678-HpCDD
OCDD
2378-TCDF
12378-PeCDF
23478-PeCDF
123478-HxCDF
123678-HxCDF
123789-HxCDF
234678-HxCDF
1234678-HpCDF
1234789-HpCDF
OCDF
Total Tetra-Furans
Total Tetra-Dioxins
Total Penta-Furan
Total Penta-Dioxins
Total Hexa-Furans
Total Hexa-Dioxins
Total Hepta-Furans
Total Hepta-Dioxins
Total TEQ
~ . '?
TARGET
f;RECOVERYff
" / (%)< ,'-";'
V«f; MATRIX '_V ,r
4J|Ct|p?:SPIKEj||S%, ; "
. :\ 'f. *_, coNcSfF"'-'/ " ?
'.^4f(pg/g dry>"-;'«;"#
1400
7020
7020
7020
7020
7020
14000
1400
7020
7020
7020
7020
7020
7020
7020
7020
14000
MATRIX SPIKE ,*,?
• - 1*; 481 90-1 5-05 fA^'
^;|!S-R4^»13A MSr; '""
••> - ... $
48190-15-06
t S-R4f413A MSD
;^-. (pg/gdry) ;
922
4270
3760
4050
4000
4450
10800
862
4320
4140
4260
4210
4070
4410
4440
4310
7570
884
985
8460
4270
16950
11800
8850
4660
8450
/' i '
RECOvf
(%) -
65
61
53
57
57
58
51
59
61
59
60
60
58
63
60
61
51
RECOV.
RPD
:, (%>;.,
3
1
8
4
5
0
2
4
0
1
1
1
1
0
0
2
1
BACKGROUND
48190-15-04
•~:/jS-R4-4i3A-f v<;'£
,',»*"?'.-, (pg/g dry)vtvi-- ':>
(5.14) #,J
ND
8.24
30.7
39.9
384
3690
35.1 #
12.7
13.4
29.6
{10.0}
ND
13.3
222
ND
441
{120}
95
163
29.6
171
{204}
377
701
34 6
f||-DK^">
f~f~ T-~: UL; >,*/>•! s4
s (pfl/fl dry
14.5
17.4
6.99
13.0
O)
•Ij
CO
-------
Table 6-35. (Continued)
af %»-* - " -".^V : ''***'- - '
'fii' 'H4*'A • ' "'' 'I'''V '"%'"f:>
INTERNAL STANDARDS
13C-2378-TCDD
13C-12378-PeCDD
13C-123478-HxCDD
13C-123678-HxCDD
1 3C:1 234678-HpCDD
13C-OCDD
13C-2378-TCDF
13C-12378-PeCDF
13C-23478-PeCDF
13C-123478-HxCDF
13C-123678-HxCDF
13C-123789-HxCDF
!.3c.:234678-HpCDF
1 3C-1 2346.78.-Hp.CDF
J.3.c.:.i23.4.78j3-HpCp.F
CLEANUP STANDARDS
37CI-2378-TCDD
'': '.'*>«:'
""' ' TARGET?^
•• -RECOVERY 4*6
40 -135
40 - 1 35
40-135
40-135
40.-.135
40 - 1 35
40-135
40 - 1 35
40-135
40-135
40-135
40-135
40-135
40-135
40.- 135
40-135
"'4'' -'MATRIX
-•!$•' SPIKE •>"; -
>".. ''V'CONC;r»^'Vi
|/;Jpg/sampiejXt>
2000 ,
2000
...2000
2000
2000
4000
2000
2000
2000
2000
2000
2000
2000
2000
2000
200
'/ MATRIX SPIKE 1
48190-15-05
S-R4-413BMS •
,;, {pg/sa'mpteHfe;
1570
1680
1490
1460
1420
2760
1390
1590
1540
1390
1430
1370
1410
1310
1210
132
, •• . f,,'
RECOVERY,
'* /(%)&•:• „•
79
84
75
73
71
69
.7.P
80
77
7.Q
71
68
71
65
60
66
MS DUP*
48190-15-06
S-R4-413B MSD
(pg/samplel f J>.|;;
1.61.P.
1740
1530
1620
1450
2850
1500
1630
1630
1440
1460
1360
1510
1370
1230
141
':••'• >,
RECOVERY i
'••• '(%$£,
80
87
7.6
81
72
71
7.5
82
81
72
73
68
76
68
62
. 70
BACKGROUND
t 48190-1 5-04
^ ;S-R4^13A- v
i|S,«pg/8arnple),- ,-;
160.0.# ,
1700
1570.
1.650
1.470
2900
1410 #
1670
1530
1560
1590
1450
1.610
1440.
1.290
134
v^|iljjiy'.',",!'4;
*i fiicOVERY,"
80
85
79
82
74
72
71
83
77
.7.8
79
72
80
72
64
67
o>
DL = Detection Limits; {EMPC}; (Below Detection Limit).
Matrix Spike % Recovery is calculated as ((concentration found - (Run 4, 48190-15-04, S-R4-41 3A cone.I/spike cone.) x 100.
J = Estimated value, below detection limit.
# = Value from second column confirmation.
-------
The target detection limit for these samples, based on the lowest calibration level using
the Method 1613 calibration curve was 44 pg/g dry weight for tetra compounds, 217 pg/g dry
weight for penta-hepta compounds and 435 pg/g dry weight for octa compounds. Actual
detection limits achieved were significantly lower than this.
The target turnaround time for the D/F analysis of sewage sludge samples was to extract
within 30 days of collection and analyze within 45 days of extraction. These turnaround times
were met with extractions occurring within 18 days of collection and analysis occurring within
10 days of extraction.
6.2 QA PERFORMANCE AUDITS
6.2.1 Field Sampling Audits
6.2.1.1 Dry Gas Meter
The dry gas meter used for MM5 sampling was fully calibrated every six months against
a NIST-traceable wet test meter. This calibration audit is documented in Appendix C-2. The full
calibration factor Y was used to correct actual metered sample volume to true sample volume.
This full calibration was verified by performing a post-test dry gas meter calibration. This post-
test calibration is presented in Appendix C-2. The full and post-test calibration coefficients were
within 5 percent which met internal QA/QC criteria. The results of the full calibration and post-
test calibration are summarized in Table 6-36.
6.2.1.2 Pitot Tube
The Type S pitot tube utilized in the MM-5 sampling train was inspected to ensure that its
orientation met the requirements of EPA Method 2. The pitot tube calibration record is
documented in Appendix C-2. The pitot tube orientation during all sampling runs met the
established criteria for alignment in Figures 2-2 through 2-4, 2-7 and 2-8 of EPA Method 2 in 40
CFR 60, Appendix A.
6-75
-------
Table 6-36. QA Results for Dry Gas Meter
Meter Box ID
Meter Box Gamma
Meter Box dH @
Full Calibration Date
Test Meter No.
Barometric Pressure
Previous Gamma
Post-Test Calibration
Date
ETS-12
0.9968
1.6953 in. w.c.
7/14/1999
9548
29.02 in. Hg
0.9792
7/22/1999
Audit - Run 2
Audit - Run 3
Audit - Run 4
Ave. Cal. Check (Yga)
1.047
1.0718
0.9985
1.039
Ave. Cal. Check Error
4.23%
QA
Criteria
Notes: Complete calibration data sheets are presented in Appendix C,
Sections C-2-1 and C-2-2 for Full Calibration and Post-Test Calibration
Audit.
6.2.1.3 Thermocouples
The thermocouples utilized in the MM5 sampling train were checked against an ASTM-
traceable thermometer. Calibration log sheets documenting the results of these checks appear in
Appendix C-2.
6.2.1.4 Analytical Balance
The gravimetric balance used in the moisture determination (EPA Method 4) was
checked against ASTM-traceable weights. Documentation of this performance check is provided
in Appendix C-2.
6-76
-------
6.2.1.5 Total Hydrocarbon Analyzer
The calibration of the total hydrocarbon analyzer operated by the MSD at the site was
verified via a calibration gas audit (CGA), consistent with the procedure of 40 CFR 60,
Appendix F, Section 5.1.2.
The total hydrocarbon analyzer was challenged with two audit gases of known propane
concentrations based on a span value of 300 ppm. The audit gases were introduced into the
sampling system at the sampling probe. A high calibration gas of 124.6 ppniy and a low
calibration gas of 86.6 pprr^ propane were used. Each gas was introduced into the sampling
system three times, and the average value was used to calculate analyzer accuracy. Audit results
are provided in Table 6-37.
Table 6-37. Total Hydrocarbon Analyzer Audit Results
CEMS Information
Analyzer Type
Manufacturer
Model Number
Serial Number
Span Value/Range
Cylinder Gas Information
Certified Audit Value (C2)
Cylinder ID Number
Type of Certification
Certification Date
Audit Results
Test 1
Test 2
Test 3
Average Response (CJ
Accuracy (A)
PRE-TEST AUDIT
Total Hydrocarbon
Horiba
MPA-510
57034007
300 ppmwv
Audit Point 1
86. 6 ppm
CC90980
Protocol 1
04/22/98
July 19, 1999
(ppm) Time
85.9 11:22
85.9 11:28
85.9 11:37
85.9 ppm
Audit Point 2
124.6 ppm
CC94773
Protocol 1
10/05/98
July 19, 1999
(ppm) Time
124.1 11:17
124.1 11:24
124.1 11:33
124.1 ppm
POST-TEST AUDIT
Total Hydrocarbon
Horiba
MPA-510
57034007
300 ppmriv
Audit Point 1
86. 6 ppm
CC90980
Protocol 1
04/22/98
July 22, 1999
(ppm) Time
82.8 14:47
81.0 14:57
78.1 15:11
80.6 ppm
Audit Point 2
124.6 ppm
CC94773
Protocol 1
10/05/98
July 22, 1999
(ppm) Time
120.3 14:43
119.1 14:57
114.6 15:03
118.0 ppm
6-77
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Accuracy was calculated as a percentage of the audit gas value as stated in Equation 1.1
of 40 CFR 60, Appendix F. During the post-test calibration on July 22, 1999, moisture
condensation was observed in the flow panel of the analyzer. The post-test CGA revealed a
slower response time and degraded accuracy. However, the accuracy (5.3%) was still within the
allowed 15 percent of the audit gas value. The data were thus deemed valid since the accuracy
error of the hydrocarbon analyzer did not exceed the QA criteria of ±15 percent.
6.2.1.6 CEM Systems Audit
A performance audit of the CO, CO2 and 02 CEMs was conducted on July 22, 1999.
This was accomplished by challenging each of the measurement system with an independent
reference standard in accordance with procedures described in 40 CFR 60, Appendix F. Results
of this audit are presented in Table 6-38.
Results of this audit found that all three analyzers were operating well within the
allowable ±10% limit.
Table 6-38. Results of the CEM Audit
Reference Standard
Uncorrected Analyzer
Reading
Average
Concentration
Percent Difference
C02
6.13%
5.93%
5.94%
5.90%
5.92%
-3.4
0,
14.2%
14.10%
13.94%
14.25%
14.10%
-0.7
CO
467 ppm
443.8 ppm
444.4 ppm
444.3 ppm
444.2 ppm
-4.9
6.2.2 Laboratory Analysis Audit
EPA provided a blind evaluation sample to Battelle for D/F analysis as a laboratory
performance evaluation audit for the test program. This sample was prepared and analyzed in
6-78
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exactly the same manner as the emission samples, including sample splitting. Results of the
analysis of this audit sample are provided in Table 6-39 and Appendix F-3-2.
EPA's evaluation of these audit results concluded that for the reported data, 9 of 11
dibenzodioxins were within the 90% confidence limit including the 2,3,7,8-TCDD isomer. For
the dibenzofurans, 11 of 14 dibenzofurans were within the 90% confidence limit. According to
EPA the reported data for this audit sample met the acceptable performance limits for the target
analytes.
Table 6-39. Results of the Lab Dioxin/Furan Audit
*:" 1, Compound ? •'
2,3,7,8-TCDD
Other TCDD
1,2,3,7,8-PeCDD
Other PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7, 8, 9-HxCDD
Other HxCDD
1,2,3,4,6, 7, 8-HpCDD
Other HpCDD
OCDD
>. Audit ee Result
*€'• 'a'(ng/sampie)fe>:
0.504
7.09
0.481
1.291
0.466
0.537
0.564
1.067
1.133
0.622
1.301
•f Compound1': v"~-"
2,3,7,8-TCDF
Other TCDF
1,2,3,7,8-PCDF
2,3,4,7,8-PCDF
Other PCDF
1, 2,3,4,7, 8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
Other HxCDF
1,2,3,4,6,7,8-HpCDF
1, 2,3,4,7, 8,9-HpCDF
Other HpCDF
OCDF
"||[ Au(Utee>Result7,5;,|
v o%, (rig/sample) : ' <%<
0.662
1.015
0.586
0.568
1.061
0.589
0.625
0.529
0.604
1.274
1.192
0.953
0
0.615
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6.3
QA/QC PERFORMANCE REVIEW
6.3.1 Program Performance Targets and Results
Program performance targets for precision, accuracy, and completeness were specified
in the QAPP. These program performance targets and the achieved results are provided in Table
6-40. The detailed discussion of these objectives and the achieved results are found in Section
6.1.3.1.
Table 6-40. Overall Program QA/QC Results
QC Type/
Parameter
Precision
Accuracy"11
Completeness
Analyte
D/Fs
PAHs
Toxic PCBs
D/Fs
PAHs
Toxic PCBs
D/Fs
PAHs
Toxic PCBs
Program
Targets'8'
< 50% RSD
< 50% RSD
< 50% RSD
40% - 135%
50% - 150%
70% - 130%
100%
100%
100%
Achieved Result"0
<50% for all 2,3,7,8 isomers 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% except perylene and
benzo(a)pyrene
<50% for all but PCB-169,
PCB-126, and PCB-77.
Met (79-134%) except for 3
analytes10'
All within range except as
specified on Quanterra's report and
surrogate spike in field blanks.
84-1 28% except for PCB-1 14 (FH-
146%, LCS DUP BH-167%) LCS
DUP
100%
100%
100%
{al For emission testing only.
lb) Based on recovery of laboratory spikes for emission samples.
(cl 1,2,3,7,8,9-HxCDF, FH-LCS DUP (141%), BH-LCS DUP (147%); 2,3,4,6,7,8-HxCDF,
FH-LCS DUP (138%), FH-LCS (138%); OCDF, FH-LCS DUP (136%), BH-LCS DUP (143%).
6-80
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Table 6-41 indicates the data quality objectives for CEM and moisture parameters for this
test program. The objectives for the THC measurement were not specifically addressed in the
QAPP since the equipment was operated by the MSD facility. However, the accuracy of the
CGA performed is reported in Table 6-41.
Table 6-41. Data Quality Objectives for Precision, Accuracy, and Completeness for
CEM and Moisture Field Measurements
Measurement
Carbon Dioxide
(EPA Method 3A)
Oxygen
(EPA Method 3A)
Moisture
(EPA Method 4)
CO
(EPA Method 10)
THC
Precision (BSD)
Target Achieved
5% 1.0%
5% 1.2%
Not
determinable
5% 0.8%
5% Not
evaluated
Accuracy
Target Achieved
10% -3.4%
10% -0.7%
Not
determinable
10% -4.9%
Not -5,3%
defined
Completeness
Target Achieved
90% 100%
90% 100%
90% 100%
90% 100%
Not 100%
defined
6.3.2 Method Specific Performance Targets and Results
6.3.2.1 Air Emissions
Detailed discussion of achieved results are contained in Section 6.1.3.1.
PCB Analysis. Performance criteria for the draft PCB emission analytical method and
achieved results are listed in Table 6-42.
D/F Analysis. Performance criteria for D/F analysis of emission samples and achieved
results are listed in Table 6-43.
PAH Analysis. Target performance criteria for PAH analysis of emission samples and
achieved results are listed in Table 6-44.
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Table 6-42. Draft PCB Emission Method Performance Target Criteria and Results
Performance Parameter
Initial Calibration
Continuing Calibration
Accuracy
Precision
Laboratory Method Blank
Estimated Detection
Limit
Sample Turnaround
Target Criteria
<35% BSD
RFs within 35% of initial
calibration results for 70% of
analytes
70-130% spike recovery for
laboratory spike samples
^30% RPD for duplicate
laboratory spike samples
<20% of sample concentration
100 pg/sample(al
Extraction within 30 days of
collection; analyze within 45 days
of extraction
Achieved Result
Met
Met
84-128% except for PCB-
114 (147-167%)
Met
<20% for all BH samples;
>20% for 10 of 13 PCBs
in FH samples""
Met
Met
lal Will vary for each PCB isomer; assumes 50% of MM5 train is used for PCB analysis.
lbl PCB-123 (-1500%), PCB-118 (159%), PCB-114 (1000%), PCB-105 (240%),
PCB-126 (114%), PCB-167 (-800%), PCB-156 (520%), PCB-157 (1100%),
PCB-169 (93%), PCB-70 (98%), PCB-189 (350%).
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Table 6-43. D/F Emission Analysis Performance Target Criteria and Results
Performance Parameter
Initial Calibration
Continuing Calibration
Accuracy
Precision
Laboratory Method
Blank
Sample Turnaround
Target Criteria
5-point; %RSD<20 percent for native
standards; <35% for labeled standards
Beginning of each 12-hour shift; RF
.+.20% of average value from initial
calibration
40 - 135% recovery of labeled internal
standards in all samples
40 - 135% recovery of native
compounds in laboratory spike sample
40 - 135% recovery of native
compounds in emission audit sample
<20% RPD for laboratory duplicates
<3 x target detection limit
Extracted within 30 days; analyzed
within 45 days of extraction; or to meet
test report delivery date
Achieved Result
Met
OCDF RF >20% on two of
three continuing calibrations
Met (40-106%)
Met (79-134%) except for
234678-HxCDF (138%),
123789-HxCDF {141-
147%), and OCDF (136-
143%)
9 of 1 1 CDD native
compounds were within the
90% confidence interval, 1 1
of 14 CDF native
compounds were within the
90% confidence interval.
<18% except 23478-PeCDF
in one FH sample (40%)
Met
Met
6-83
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Table 6-44. PAH Emission Performance Target Criteria and Results
Performance Parameter
Target Criteria
Achieved Result
Initial Calibration
5-point; %RSD
percent for unlabeled and
labeled standards
Met; <20% in all cases
Continuing Calibration
Beginning of each 12-
hour shift; RF±30% of
average value from initial
calibration
Met except on 8-30-99, RF
of 77.3% for fluorene
Accuracy
50-150% recovery of
labeled internal standards
and surrogate standards
Generally within range
except for three internal
standards; and surrogate
level in field blanks >250%
Precision
RPD<50% for ongoing
analysis of test 2
duplicate samples
Maximum RPD 22% for
anthracene in BH controls
Laboratory Method Blank
Target analytes
-------
6.3.2.2 Scrubber Water Samples
PCB Analysis. Target performance criteria for the draft PCB scrubber water method and
achieved results are listed in Table 6-45.
Table 6-45. Draft PCB Scrubber Water Method Performance Criteria
Performance Parameter
Initial Calibration
Continuing Calibration
Accuracy
Precision
Laboratory Method Blank
Detection Limit
Sample Turnaround
Target Criteria
<35% RSD
RFs within 35% of initial calibration
results for 70% of analytes
40-160% spike recovery for
laboratory spike samples
^50% RPD for duplicate laboratory
spike samples
< 20% of sample concentration
25 pg/L(al
Extraction within 30 days of
collection; analysis within 45 days
of extraction
Achieved Result
Met
Met
54-141o/0 except
PCB77 in LCS (166%)
Met U48%)
>20% for 10 of 13
PCBs (outlet) and all
13 PCBS (inlet)lbl
1.35-13 pg/L except
LCS
Met
lal Will vary for each PCB isomer; assumes 50% of scrubber water extract is used.
|B) PCB-77 (25%), PCB-123 (124%), PCB-118 (89%), PCB-114 (132%), PCB-105 (85%),
PCB-126 (70%), PCB-167 (105%), PCB-156 (91%), PCB-157 (99%), PCB-169 (78%),
PCB-180 (74%), PCB-170 (69%), PCB-189 (95%).
D/F Analysis. Target performance criteria for D/F analysis of scrubber water samples and
achieved results are listed in Table 6-46.
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Table 6-46. D/F Scrubber Water Analysis Performance Target Criteria and Results
Performance
Initial Calibration
Continuing Calibration
Accuracy
Precision
Laboratory Method
Blank
Sample Turnaround
Target Criteria
5-point; %RSD<20 percent for native
standards; <35% for labeled standards
Beginning of each 12-hour shift; RF ±20%
of average value from initial calibration
40-135% recovery of labeled internal
standards in all samples
40-135% recovery of native compounds in
laboratory spike sample
<20% RPD for laboratory duplicates
<3 x target detection limit
Extracted within 30 days; analyzed within
45 days of extraction; or to meet test
report delivery date
Achieved Result
Met
Met
31-74% excluding
sample WO-R3-312A
Met (54-111%)
*8% except OCDF (57%
RPD)
Met
Met
6.3.2.3 Sewage Sludge Feed Samples
PCB Analysis. Target performance criteria for the draft PCB sewage sludge method and
achieved results are listed in Table 6-47.
6-86
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Table 6-47. Draft PCB Sewage Sludge Method Performance Criteria
Performance Parameter
Initial Calibration
Continuing Calibration
Accuracy
Precision
Laboratory Method Blank
Detection Limit
Sample Turnaround
Target Criteria | Achieved Result
<35% RSD
RFs within 35% of initial calibration
results for 70% of analytes
40-160% spike recovery for
laboratory spike samples
<50% RPD for duplicate laboratory
spike samples
<20% of sample concentration
55 pg/g (dry weight)'3'
Extraction within 30 days of
collection; analysis within 45 days
of extraction
Met
Met
Met (96-157%)
Met (<;20% RPD)
Met for 5 of 1 1 PCBs (>20%
for six PCBs)lb)
45-169 pg/g
Met
la) Will vary for each PCB isomer; assumes 30% of sewage sludge extract is used for analysis.
lb) PCB-123 (50%), PCB-118 (36%), PCB-114 (36%), PCB-105 (29%), PCB-167 (33%),
PCB-189 (46%).
D/F Analysis. Target performance criteria for D/F analysis of sewage sludge feed
samples are listed in Table 6-48.
6-87
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Table 6-48. D/F Sewage Sludge Feed Analysis Performance Target Criteria and Results
Performance Parameter
Initial Calibration
Continuing Calibration
Accuracy
Precision
Laboratory Method Blank
Sample Turnaround
Target Criteria
5-point; %RSD<20 percent for native
standards; <35% for labeled standards
Beginning of each 12-hour shift; RF
±20% of average value from initial
calibration
40-135% recovery of labeled internal
standards in all samples
40-135% recovery of native compounds
in laboratory spike sample
<20% RPD for laboratory duplicates
<3 x target detection limit
Extracted within 30 days; analyzed
within 45 days of extraction; or to meet
test report delivery date
Achieved Result
Met
Met
Met (54-87%)
Met (51-65%)
Met (<8%)
Met
Met
6-88
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TECHNICAL REPORT DATA
(Please read Instructions on reverse before completing)
1. REPORT NO.
EPA-454/R-00-038b
3. RECIPIENT'S ACCESSION NO.
4 TITLE AND SUBTITLE
Source Characterization For Sewage Sludge Incinerators
Final Emissions Report, Volume I of III
Metropolitan Sewer District (MSD) Mill Creek Wasterwater Treatment Plant
Cincinnati, Ohio
5. REPORT DATE
September 2000
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Clyde E. Riley, USEPA
Jeffery A. Ferg, Battelle
Anthony S. Wisbith, Battelle
Dennis A. Falgout, PES
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle
505 King Avenue
Columbus, Ohio 43201-2693
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO. 68-D-99-009
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 27711
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, 1999. 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 MACT 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
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATI
Field/Group
PCBs
PAHs
Dioxins/furans
Air Pollution control
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (Report)
Unclassified
21. NO OF
PAGES
20 SECURITY CLASS (Page)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77)
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